年代:1992 |
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Volume 89 issue 1
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21. |
Chapter 21. Electronic conductors, including high temperature superconductors |
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Annual Reports Section "A" (Inorganic Chemistry),
Volume 89,
Issue 1,
1992,
Page 393-407
C. Greaves,
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摘要:
21 Electronic Conductors including High Temperature Superconductors By C. GREAVES School of Chemistry University of Birmingham Birmingham B 15 2TT UK 1 Introduction Chemical research into electronic conductors in 1992 has resulted in further major developments in the areas of high temperature oxide superconductors and fullerene- based materials. As in the past this report therefore focuses on these two areas which remain of overwhelming importance (Sections 2 and 3). However a variety of new materials with interesting chemical and electrical features have also been reported and some of the more interesting papers are described in Section 4.As always this report aims to illustrate the major chemical advances in these topical areas as described in the 1992 literature but of necessity it is a personal and subjective analysis.2 High Temperature Superconductors The 1992 literature on the chemistry of high temperature superconducting oxides has continued to provide evidence for the complexity of the chemistry that controls the physical characteristics of these materials. The way in which chemistry can be used positively to tune electrical properties is still in its infancy but provides an important target for synthetic solid-state chemists. A major development in the search for new superconducting phases has been the demonstration of superconductivity in a number of oxy-carbonates containing copper. Although the parent materials have been known for some time the precise chemical manipulation needed to induce superconductivity has only now been achieved.Given that these materials are probably only representative of an as-yet undiscovered broader class of compounds containing oxy-anions they provide an important pointer to the possible synthesis of new superconducting phases. An additional major advance is the growing appreciation of thin-film methods for the synthesis of novel superconducting materials. Several thin films have been reported of materials with very simple known structures but which demonstrate superconduct- ing behaviour at high temperatures. The thin-film methods for these phases must be compared with the very high pressures which have previously been used in order to demonstrate superconducting behaviour in such structures. 393 394 C.Greaves Synthesis.-Although the synthesis of superconducting Sr -,Nd,Cu02 y -0.14 T = 40 K has been previously described,' high hydrostatic pressures of around 25kbar were employed. The attraction of this material relates to it being an electron-rich superconductor and having the simplest possible structure which was initially determined for Ca,,,,Sr,~,4Cu02 and is shown in Figure 1. The use of thin-film methods for the synthesis of similar materials has been investigated but using an RF-magnetron sputtering technique the maximum value of y was found2 to be only 0.05 since at higher concentrations a phase related to Sr,,Cu,,O, was identified. However using similar procedures a phase with composition Sr,~,,Nd,,,,Cu02 and having the required structure was synthesized on a SrTiO substrate and found3 to have a T of up to 16K.Using pulsed laser ablation from stoichiometric targets of Nd,O, SrCO, and CuO (sintered at 900 "C in air) similar films have been reported4 with higher critical temperatures ( -30 K). cu 00 Sr/Ca Figure 1 The 'injinite layer' perovskite structure of Ca ,,Sr ,4Cu02 The synthesis of high quality thin films of Bi2Sr2Ca2Cu30, using in situ MOCVD without any subsequent annealing treatments has been de~cribed.~ c-Axis oriented films on LaAIO substrates were obtained from precursors which did not include lead [Bi(C,H,),] Sr(DPM), Ca(DPM), and Cu(DPM) (DPM = 2,2,6,6-tetramethyl-heptane-3,Sdione). The films were found to have high values for T (97K) and J (4 x 10-5Acm-2 at 77K in zero field).The use of protracted annealing treatments to enhance the T of T1,Ba2Ca2Cu30, has been further studied. A study of other T1-based superconductors suggested that the ' M.G. Smith A. Manthiram J. Zhou J. B. Goodenough and J.T. Markert. Nature (London),1991,351. 549. N. Sugii M. Ichikawa K. Kubo T. Sakurai K. Yamamoto and H. Yamauchi Physica C 1992.196.129. H. Adachi T. Satoh Y. Ichikawa K. Setsune and K. Wasa Physico C 1992 196. 14. N. Sugii K. Kubo M. Ichikawa K. Yarnamoto H. Yamauchi and S. Tanaka Jpn. J. Appl. Phys. 1992. 31 L1024. K. Endo H. Yamasaki. S. Misawa S. Yoshida and K. Kajimura Narure (London),1992 355. 327. Electronic Conductors including High Temperature Superconductors 395 anneal which involves vacuum encapsulation at 750°C for 10 days produced an increase in hole density due to a decrease in the T1 content in the superconductor.6 An electron microscopy examination of samples before and after the anneal provided evidence for the formation of intergrowths of T1,Ba,Ca,Cu40 ,during the anneal which was also attributed to partial T1 loss.The optimization of the superconducting properties of the previously reported (Pbo~,Cao,,)Sr,(Ca,,5Yo,5)Cu207 by the careful control of the synthesis conditions has been described.' For critical tempera- tures higher than 60K a treatment at 90Ck950"C in 100 bar oxygen followed by a quench to room temperature was required to secure the optimum oxygen content. A similar examination of (Pb,Cu)Sr,(Ca,Y)Cu,O was found to yield superconducting materials with T > 77 K only under appropriate annealing conditions.' An excess of oxygen was found to reduce the Tc,and synthesis in air at 1020°C followed by annealing in argon at 750 "C was reported to give the optimum oxygen content for a material of composition (Pbo,,Cuo,,)Sr,(Cao~4Yo~6)Cu20z.Developments in the Main Superconducting Families.-The La -,Sr,Cu04 system which remains of fundamental importance to the development of superconductivity mechanisms has been re-examined in the overdoped (0.15 5 x I 0.30)region. ' It was found that the disappearance of superconductivity was coincident with the low temperature orthorhombic-tetragonal phase transition which occurs near x = 0.2. These results suggest a much narrower composition range for bulk superconductivity than previously assumed.Studies to clarify the microstructural features of YBa,Cu,O and their influence on superconductivity have continued. An electron microscopy examination of microstructural changes in ABa,Cu,O (A = Er Nd Pr Sm Yb) as a function of 6 has been reported.' ' A clear correlation was observed between the 60 K plateau in plots of T,against 6 and the occurrence of oxygen ordering to give the ortho I1 structure with composition ABa,Cu,O,,,. By making assumptions about the electronic effects of oxygen deficiency in YBa,Cu,O this plateau has also been rationalized in terms of hole density changes on the superconducting CuO planes.' In an HREM examination of ABa,Cu,O (A = La Gd Er),' decomposi- tion was observed to occur in air at 20 "C to give regions of composition ABa,Cu,O and ABa,Cu,O o formed from intercalation of additional CuO layers.The latter phase appeared to have a different structural arrangement for the CuO units than seen in the ABa,Cu,O phases which was attributed to the partial replacement of Cu by CO groups. The oxygen-excess phase YBa,Cu,O,,, prepared under very high pressure is potentially of great significance since it apparently has an extremely high hole density (p = 0.8) whilst retaining a critical temperature (92 K) identical to that of YBa,Cu,O,. An ultra-high-resolution high voltage electron microscopy study of this material has ' T. Kaneko K. Hamada S. Adachi and H. Yamauchi Physica C 1992 197 385. ' R.S. Liu M. Hervieu C. Michel B.Raveau and P. P. Edwards J. Solid State Chem. 1992 100 186. ' H. B. Liu. D. E. Morris A. P.B. Sinha X. W. Cao and J.C. Ho Physica C 1992; 197. 101. H. Zhang G.S. Chen S.Q. Feng K. Wu X. Zhu and Q. R. Feng Solid Stare Commun. 1992 83 601. 10 H. Takagi R. J. Cava M. Marezio B. Batlogg J. J. Krajewski W. F. Peck Jr.. P. Bordet and D. E. Cox Phys. Ret.. Lett. 1992 68 3777. T. Krekels H. Zou G. Van Tendeloo D. Wagener. M. Buchgeister S. M. Hosseini. and P. Herzog Physica C 1992 196 363. J.K. Burdett Physica C 1992 191 282. l3 H. W. Zandbergen Physica C 1992 193. 371. 396 C. Greaves enabled direct resolution of the 0 atoms in both sites of the unit cell basal layer (non-superconducting Cu layer). l4 The effects which oxygen stoichiometry and structure have on the critical temperature of T1,Ba2CaCu208 -,15 and Tl,Ba,Ca,Cu,O, -616 have been evaluated in a neutron powder diffraction study of materials synthesized under various conditions.For both compositions it was concluded that the 0 sites in the T10 layers were completely occupied only after annealing treatments in high oxygen pressure (500 bar 500 "C). The as-prepared samples and those annealed in Ar were found to have up to 11% vacancies in these sites. Approximately 7% of the TI sites were also vacant. Interesting variations in and very high values for T have been reported for T12Ba2CU06+,. For 6 -0 a critical temperature of 93 K was recorded and a large positive change of T with pressure ((dTJdP) = 0.2Kkbar-') was found." Single crystals obtained from melts containing an excess of Cu exhibited l8 even higher values of T (110K).Single crystal X-ray diffraction studies suggested the partial substitution of TI by Cu which appeared to be present as Cu+ from ionic radii considerations. On this basis the stoichiometry T1 ,s5C~0.1 ,Ba,Cu06 was assigned which might account for the superconducting behaviour since it corresponds to a hole density of 0.3 per Cu. Although the presence of holes in Bi,Sr,CaCu,O has normally been attributed to the oxygen excess 6 a recent report questions the validity of this assumption." Very careful control of the synthesis conditions (a multistage treatment in argon using gradually increasing temperatures) and precise thermal analysis (520 "C in 10% H in argon) suggested that stoichiometric Bi,Sr,CaCu,O could be made.The fact that the sample was superconducting (T = 86K) suggested that an excess of oxygen is unnecessary for superconductivity and supports the view that the BiO layers act as charge reservoirs for hole injection into the CuO layers. Effectively charge transfer to give Bi3-" and CU,'~ species was suggested. Similar charge transfer involving T1 and Cu has been supported2' by measurements on T1(Srl~,Ba,)LaCuO,. As x was increased the superconducting samples (0 5 x _< 0.3) with T z 40K became semimetallic at x = 0.4 and semiconducting at x = 0.6. The results are consistent with the extent of hole transfer from T1 to Cu being modified by changes in the energy levels of the Cu 3d,2-y2 and T1 6s bands caused by increases in unit cell size with x.The previously reported enhancement of superconductivity by photoexcitation has been studied further. 1-24 Laser illumination of thin films of YBa,Cu,O,- and GdBa,Cu,O,- (6 z0.5) was found to increase T (e.g. by 5 K for a sample with T = 25 K) and decrease the normal state resistivity.21.22 On standing in air at room l4 S. Horiuchi Y. Matsui and B. Okai Jpn. J. Appl. Phys. 1992 31 L59. D. M. Ogborne M.T. Weller and P.C. Lanchester Physica C 1992 200 207. D. M. Ogborne M.T. Weller and P.C. Lanchester Physica C 1992 200 167. J. E. Schirber D. L. Overmyer E. L. Venturini D. S. Ginley and B. Morosin Physica C 1992 193 126. N.N. Kolesnikov V. E. Korotkov M. P. Kulakov R. P. Shibaeva V.N. Molchanov R.A. Tamazyan and V.I. Simonov Physica C 1992 195 219. l9 A.Q. Pharn A. Maignan M. Hervieu C. Michel J. Provost and B. Raveau. Physica C 1992 191 77. 2o M.A. Subramanian and M. H. Whangbo J. Solid State Chem. 1992 % 461. 21 G. Nieva. E. Osquiguil J. Guimpel M. Maenhoudt B. Wuyts Y. Bruynseraede M. B. Maple and I. K. Schuller Phys. Rev. B 1992 46 14249. 22 G. Nieva E. Osquiguil J. Guimpel M. Maenhoudt B. Wuyts Y. Bruynseraede M. B. Maple and I. K. Schuller Appl. Phys. Lett. 1992 60 2159. 23 V. I. Kudinov A. I. Kirilyuk. and N. M. Kreines. JETP Lett.. 1992. 56,102. 24 C. Ayache I. L. Chaplygin A. 1. Kirilyuk. N. M. Kreines and V. I. Kudinov. Solid State Commun. 1992.81 41. Electronic Conductors including High Temperature Superconductors 397 temperature the samples had reverted to their original states after six days.The relaxation of the photoconductivity in YBa,Cu,O has been studied as a function of temperature and time and the data interpreted on a model of photoinduced charge tran~port.,~The spectral dependencies of the persistent photoconductivity in YBa,Cu,O,, thin films have been measured at room temperature and rationalized in terms of electronic transitions involving the conduction band (Cu 3d and 0 2px,y)and the upper Hubbard sub-band (3dx2-y2) of the CuO planes.24 Using second derivative 0 1s spectra angle-resolved XPS measurements have di~tinguished,~ inequivalent oxygen sites in YBa,Cu,O,. In addition to differentiation between 0 atoms in the CuO planes and chains a surface-related signal was attributed to 0atoms terminating CuO planes at the surface.Photoemission methods have also been used26 to monitor changes in surface degradation of BaPb -xBi,O,. Marked changes in surface reactivity were noted to occur at the metal-insulator transition and significant surface instability was noted for all metallic compositions (x < 0.4). XPS measurements27 on sputtered thin films of Bi,Sr2Ca,Cu,0, have revealed two components to the Bi 4f'core level which were assigned to Bi2 + and Bi3 + . The critical temperature was found to decrease as the mean Bi valance decreased. High-resolution angle-resolved photoemission measurements have been made2 8.29 on YBa2Cu30,- as 6 was varied between 0.1 and 0.7. The sharp and intense features observed near E for small values of 6 disappeared or significantly broadened at 6 = 0.7 when the sample became insulating.It was concluded that these particular features must therefore be correlated with the transport properties. Recent studies relating to the Fermi surface and their importance to theories of high temperature superconductors have been reviewed by Pickett et ~1.~' Cation Substitutions in Known Structure Types.-Our incomplete understanding of the absence of superconductivity in PrBa,Cu307 prompted a core and valence level photoemission study3 of Y ,-,PrxBa,Cu30 for 0 Ix I1. The Pr 3d core level spectra were suggestive of a Pr"' oxidation state and the lack of superconductivity for x > 0.5 was attributed to the effects of mixing of the Pr 4fand 0 2p levels at the Fermi energy.The simultaneous substitution of equal amounts of Ca2 + and Th4+ ions at the Y site in YBa2Cu307 -,has been investigated., Although the charge-compensating nature of the substitutions enabled the overall oxygen content to remain constant (6 = 0.04) the critical temperature was found to decrease in a similar way to that previously reported for simple Ca substitution. This observation provides important support for the view that the T is not simply related to hole density in this system. The effects of substituting half the Ba2+ ions by isovalent Sr2+ ions in REBa2Cu30 (RE = rare earth metal) have been examined.33 " R.P. Vasquez B.D. Hunt. M.C. Foote. L.J. Bajuk. and W. L. Olson Physicu C 1992 190. 249. 26 W. R. Flavell A.J. Roberts. B.C. Morris. D. R.C. Hoad I. Tweddell A. Neklesa. R. Lindsay. G. Thornton. P. L. Wincott and T. S. Turner. Supercond. Sci. Techno[. 1992 5 648. 27 K. Ohbayashi K. Yoshida. M. Anma. Y. Takai and H. Hayakawa Jpn. J. Appl. Phys. 1992 31. L953. " R. Liu B. W. Veal A. P. Paulikas J. W. Downey P. J. Kostic. S. Fleshler U. Welp C. G. Olson X. Wu A. J. Arko and J.J. Joyce Phys. Rrr. E 1992 45 5614. 29 R. Liu B. W. Veal A. P. Paulikas J. W. Downey. H. Shi. C.G. Olson. C. Gu A. J. Arko. and J. J. Joyce Phqs. Rec. E 1992 46 I1 056. '"W. E. Pickett H. Krakauer. R. E. Cohen and D. J. Singh. Science. 1992. 255 46. 3' 0.Cohen F. H. Potter C.S.Rastomjee and R. G. Egdell Physicu C 1992. 201 58. '' M. Andersson 0.Rapp. and R. Tellgren. Solid Stute Commun.. 1992 81.425. 33 X.Z. Wang B. Hellebrand and D. BLuerle. Physicu C 1992. 200 12. 398 C. Greazies Except for RE = Pr which was semiconducting all phases were superconducting with T values of 54 to 86K. For the smaller rare earth cations the structures were orthorhombic but tetragonal symmetry was found for the larger ions. The maximum T was observed for RE = Gd or Dy which have sizes close to the orthorhombic- tetragonal phase boundary. Although pressure has a large effect on the critical temperature of YBa,Cu,O ((dT,/dP) = 5.5 K GPa-') the use of Sr doping to provide chemical pressure has been found to have little effect and this inconsistency has been inve~tigated.~~ Since structural data and Bond Valence Sum (BVS) calculations were consistent with a significant increase in hole density in the superconducting layers it was concluded that hole densities based on BVS calculations should be treated with caution.The ability of Ga substitutions at the Cu sites to stabilize Sr analogues of YBa,Cu,O has been further examined.35 Single phase YSr,Cu,-,Ga,O samples were found for 0.4 2 .Y 5 1.0 and these were either tetragonal (0.4 5 x 5 0.7) or orthorhombic (0.8 2 x 2 1.0). The samples were only superconducting after high pressure treatments e.y. for x = 0.4 T = 10K after treatment at 1000°C in 1800 bar of 20% 0 in argon. A comprehensive study of the extent to which cation substitutions can stabilize phases with the general composition YSr,Cu -,M,O has been reported.36 It was found that stabilization occurred for M = Li Al Ti V Cr Fe Co Ga Ge Mo W and Re and superconductivity was observed for all substituents except M = Li Al and Cr.The highest critical temperature measured was 73 K for YS~,CU,,,~R~,, 507.12. Various reports have described the effects of partially substituting Ca2 + for Y3 in a + variety of materials with composition Y(Ba,Sr),Cu,-,M,O, M = Co Al and Fe.37-40 The changes were attributed to an increase in hole density in the CuO layers. For a fixed Co content in YBa,Cu3~,Co,0, T was found to be increased substantially by such substitution e.g. for x = 0.36 the material was transformed from non-superconducting to superconducting with T = 82 K by replacing 36% of the Y ions.37 Similar results were reported for YSrBaCU2,6Mo,407 (M = Al Fe):38939 for M = A1 the material became superconducting after 10% (T = 29 K) and 20% (T = 47K) ~ubstitution~~ of Ca for Y; for M = Fe 20% substitution induced39 superconductivity with T = 24 K.Although YSrBaCu2,,Co,,,0 is itself supercon- ducting (T = 22K) the critical temperature was found to be increased by Ca substitutions (T,= 58 K for Y,,,Ca,,,SrBaCu,,,Coo,307).40 Conversely the effects of reducing the hole density by substituting Y for Ca in T1 -,Ba,CaCu,O,- have been monitored.,l The critical temperature was reduced from 94 K in the parent material to 82 K (10% substitution) and 72 K (20% substitution); semiconducting behaviour was observed at 30% substitution. By making assumptions concerning the number of electrons transferred from the CuO layers to the Tl2-,O2- layers it was concluded that the maximum T occurred at a hole density of 0.17 per Cu.34 T. Ishigaki F.Izumi T. Wada. N. Suzuki Y. Yaegashi. H. Asano H. Yamauchi and S. Tanaka Physica C 1992 191 441. 35 S. Adachi S. Takano and H. Yamauchi Physica C 1992 196 125. 36 T. Den and T. Kobayashi Physica C 1992. 196 141. 3' E. Suard A. Maignan V. Caignaert and B. Raveau Physica C 1992 200 43. 38 R. Suryanarayanan L. Ouhammou M. S. R. Rao 0.Gorochov P. K. Mukopadhyay and H. Pankowska Solid State Commun. 1992 81 593. 39 C. V. Narasimha Rao T. Young M. T. Weller P. A. J. de Groot. P. C. Lanchester R. Suryanarayanan L. Ouhammou. 0.Gorochov and H. Pankowska Supercond. Sci. Techno/. 1992 5. 353. 40 R. Suryanarayanan L. Ouhammou 0.Gorochov and H.Pankowska. Physica C 1992. 199 37. 41 M. Paranthaman A. Manthiram. and J. B. Goodenough J. Solid Srate Chem.. 1992 98 343. Electronic Conductors including High Temperature Superconductors 399 The effects of substituting Ni Zn and Ga on the Cu sites in (La,Sr),CuO have been studied and related to the changes in T with the La Sr ratio., The minimum in T observed at x = 0.125 in La,-,Ba,CuO is less pronounced in the analogous Sr material but was found to become more pronounced in La ~,Sr,Cu,,,,M,,,,O (M = Ni Zn Ga). Although the minimum T in La -,Ba,CuO could be associated with a low temperature orthorhombic-tetragonal transition low temperature X-ray diffraction was unable to detect a similar transition in the Sr-containing phases examined.New Superconducting Oxides.-Superconductivity and other resistive and magnetic anomalies have been reported in Sr -.Ca,CuO thin films prepared using MBE synthesis.43 SrCuO and Sr,,,Ca ,CuO, both with the simple 'infinite layer' structure of Figure 1 showed clear diamagnetic signals at 90 K and 120 K respectively. The latter composition also gave a small diamagnetic signal and a resistivity decrease at 180K. The alkaline earth deficient material (Sr -xCax)l -,CuO with the same structure has also been synthesized with y z 0.1 using4 high pressure techniques 6GPa at 1000°C. This material with T = 110K is of considerable interest since it provides the first example of an apparently p-type superconductor with this structure tY Pe. Superconductivity has been rep~rted,~,,~ in the system RE -,Ca,Sr,Cu,GaO, which is structurally related to YBa,Cu,O but has chains of GaO tetrahedra replacing the chains of square planar CuO units.Superconductivity was found to occur only after treatment in high pressure oxygen (e.g. 200 bar at 910 " gives T up to 70 K).,' EELS has been used to examine the 0-K and Cu-L absorption edges and two types of holes were detected:46 one appeared after Ca doping and was attributed to 0 sites not on the CuO planes whilst the other which was seen only after high pressure treatment was associated with these planes. Similar superconducting phases but with Ga partially substituted by Cu have also been studied., In this system (Y ,-,Ca,)Sr,Cu,(Ga _,Cu,)O, at the maximum Ca content (x = 0.4) T was reported to increase from 40K to 50K on replacing 10% or 20% of the Ga by Cu.These materials were prepared at 1800 bar in 20% 0 in argon. Two closely related superconductors in this structural family have also been rep~rted:~*,~~ YSr,Cu (Bi, 5CuO. ')O and (Yo,7Cao.3 )Sr,Cu,( Pb, ,Cd, ')07.Superconductivity in the Bi-containing phase (T = 68 K) was detected following an oxygen anneal at 500 "C whereas the Cd phase (T = 92 K) required only a simple treatment in air at 850 "C. Several new superconducting phases containing fluorite-type layers separating the superconducting CuO sheets have been reported. (Y,Ce),Sr,Cu,GaO is structurally 42 Y. Koike A. Kobayashi T. Kawaguchi M. Kato T. Noji Y. Ono T. Hikita and Y. Saito Solid State Commun.1992 82 889. 43 X. Li T. Kawai and S. Kawai Jpn. J. Appl. Phys. 1992 31 L934. 44 M. Azuma Z. Hiroi M. Takano Y. Bando and Y. Takeda. Nature (London),1992. 356 775. 45 B. Dabrowski P. Radaelli D.G. Hinks. A.W. Mitchell J.T. Vaughey D.A. Groenke and K.R. Poeppelmeier Physica C 1992 193 63. 46 V. P. Dravid and H. Zhang Physica C 1992 200 349. 47 S. Adachi K. Kubo S. Takano and H. Yamauchi Physica C 1992 191 174. 4R A. Ehmann S. Kemmler-Sack S. Losch M. Schlichenmaier W. Wischert P. Zoller T. Nissel and R. P. Huebener Physicu C 1992 198 1. 49 T. P. Beales C. Dineen W. G.Freeman S.R. Hall M. R. Harrison D. M. Jacobson and S.J. Zammattio. Supercond. Sci. Technol. 1992 5. 47. 400 C. Greaves related to YSr,Cu,GaO but has a (Y,Ce),O block replacing the Y layer.50 Treatment in oxygen (30 bar) induced superconductivity with T z 13K.Similarly (Eu,Ce),(Sr,Eu),Cu,(Ga,Cu)O, with T = 28 K5' and (Ho,Ce),(Sr,Nd),Cu,-(Pb,Cu)O with T = 10K5 can be related to the mixed Cu,Ga phase (Y,-xCax)-Sr,Cu,(Ga -,Cu,)O described above. In (Y,Ce),Sr,Cu,(Fe,Cu)05 + ," similar mixed (Fe,Cu)O layers are formed but the thickness of the fluorite block can be varied n = 1,2,3 et~.~~ Although the simple material with n = 1 was superconducting (T = 10K) the higher members of this series were not. Superconductivity at 28 K has been reported54 in (Nd,Ce),Sr,Cu,NbO,, which has a similar structure but has layers of octahedrally coordinated Nb as shown in Figure 2. Interestingly simple doping of Nb @ cu 00 @ Nd/Ce Sr Figure 2 The structure of (Nd,Ce),Sr,Cu,NbO the parent materials containing such layers e.g.LaBa,Cu,NbO, has not been achieved and it has required the more complex substitution -[(Nd,Ce),0,](3 -x)+ for La3+ -to achieve superconductivity albeit at low temperatures. The microstructure of this phase has been investigated by HREM," and cooperative rotations of the NbO octahedra around an axis perpendicular to the layers have been shown to give rise to a superstructure Figure 3. The fluorite blocks normally contain at least one tetravalent species (Ce4+ Pr4+) but a novel phase has been reported (La,Ln,-,)(Sr -,La,) Cu,(Pb,,5Cu,,5)0, containing only trivalent lanthanides (Ln = Gd Dy Ho Er) in these layers.56 One of the materials examined was superconducting with T = 20K.50 Li Rukang R. K. Kremer and J. Maier Physicu C 1992 200 344. 5' S. Adachi A. Nasa and H. Yarnauchi Physica C 1992 201 403. 52 T. Maeda N. Sakai F. Izumi T. Wada H. Yamauchi H. Asano and S. Tanaka Physica C 1992,193,73. 53 T. Wada A. Nara A. Ichinose H. Yamauchi and S. Tanaka Physica C 1992 192 181. 54 R. J. Caw. J. J. Krajewski H. Takagi. H. W. Zandbergen R.B. Van Dover W. F. Peck Jr.. and B. Hessen Physica C 1992. 191 237. 55 H. W. Zandbergen R. J. Cava J. J. Krajewski and W. F. Peck Jr. Physicu C 1992 192 213. 56 H. Sasakura H. Teraoka K. Nakahigashi S.Minamigawa. and K. Yoshiara Jpn. J. Appl. Phys.. 1992,31. L25. Electronic Conductors including High Temperature Superconductors 401 Nb 00 Figure 3 Cooperative rotations ofthe NbO octahedra in (Nd,Ce),Sr,Cu,NbO,,.The rotations are about an axis perpendicular to the NbO layers Superconductivity in La -,Pb,CuO, 0.5 I x I 0.6 has been reported (T = 15K) following annealing treatments at 450°C in oxygen at 20-40 bar.57 It has also been suggested that Cr can replace Pb in (Tl,Pb)Sr,CuO to yield superconducting phases with similar critical temperature^,^^ e.g. (Tl,,,Cr,~,)Sr,CuO has T = 4&50 K. An interesting claim for superconductivity in a new cubic phase has been made.59 The composition was reported to be ~~o,6~~bo,33~ao~,~~r~~57~a2,1~u3,25~lo~~~o,6~ with a unit cell size of 6.04 A and T = 117 K. A two-step synthesis was used PbSr,Ca,Cu,O was prepared and the additional components were then added and the mixture pelletized and heated at 86&870"C for 10 to 20 minutes.Superconductors Containing Carbonate Groups.-The parent carbonate phase Sr,CuO,(CO,) has been re-examined in pure form using neutron powder diffraction and electron microscopy.60 The original suggestion6' for ordering of the CO groups within the layers was confirmed but ordering between adjacent layers was found to double the unit-cell size perpendicular to the layers Figure 4. The structures of S~B~CUO,(CO,)~~ and Srl,,Ba,,,Cu0,(C0,)63 have been shown to be similar but have a more disordered arrangement of CO orientations possibly due to the random distribution of Sr and Ba ions.62 Superconductivity in this mixed Sr/Ba system was subsequently reported following synthetic conditions aimed at introducing some 57 A.Maignan C. Michel M. Hervieu J. Provost D. Groult and B. Raveau Physica C 1992 191 333. 58 Z. Z. Sheng Y. F. Li Y. Q. Tang. Z. Y. Chen and D.0.Pederson Solid State Commun. 1992,83 205. 59 V. E. Volkov A. D. Vasiliev Y.G. Kovalev S.G. Ovchinnikov N. P. Fokina V. K. Chernov and K. S. Aleksandrov JETP Lett. 1992 55 616. 60 Y. Miyazaki H. Yamane T. Kajitani T. Oku K. Hiraga Y. Morii K. Fuchizaki S. Funahashi and T. Hirai Physica C 1992 191 434. 61 T. G.N. Babu D. J. Fish and C. Greaves J. Muter. Chem. 1991 1 677. 62 C. Chaillout Q. Huang R. J. Cava J. Chenavas A. Santoro P. Bordet J. L. Hodeau J. J. Krajewski J. P. Levy M. Marezio and W. F. Peck Jr. Physicu C 1992. 195 335. 63 A. R. Armstrong and P.P. Edwards J. Solid State Chem. 1992 98 432. 402 C. Greaves Cu into the CO layer^.^^.^ The phase Sro,,Bal,lCul,lO,, +6(C03)o.9 presumed to be a p-type superconductor was found to have T = 40 K after treatment in oxygen at 50 bar. The crystal structure of this superconducting phase was examined using neutron diffraction,66 which confirmed the relationship to Sr,CuO,(CO,) but implied a more disordered CO sub-lattice. An infrared and Raman spectroscopy study of Sro,,Bal,,CuO,(CO,) supported the presence of distorted COi- ions in the struc- t~re.~~ n@ n Figure 4 Part of the structure of Sr,CuO,(CO,) showing orientational order of the carbonate groups It has been sho~n~~,~~ that carbonate anions can be introduced into the Cul 'chain' sites of the YBa,Cu,O structure and thereby stabilize the Sr analogue (Yo 6Ca,.JSr (Cuo,6C ,4)0 6. The material appeared semiconducting as pre-pared but became semi-metallic after treatment at 1000"C in oxygen at 50 bars6* An examination using HREM showed local order of the Cu and C atoms such that 40% of the CuO chains were replaced by carbonate groups,69 Figure 5. Superconductivity with T = 63 K was subsequently reported7' in this phase following an HIP anneal at 700 "C for 30 h in a mixture of 99.9% 0,/0.1% CO,. HREM indicated a doubling of the a axis of the YBa,Cu,O structure due to ordering of the CO groups in the basal plane. It was shown'l that the (Y,Ca) layer of this structure could be replaced by a (Y,Ce),O fluorite block to give (Yo,7,Ceo,,7),Sr,Cu,(Cuo~65Co~35)09 which became superconducting at 18 K after high oxygen pressure treatment.64 K. Kinoshita and T. Yarnada Narure (London) 1992. 357 313. 65 K. Kinoshita and T. Yamada Jpn. J. Appl. Phys. 1992 31 L832. 66 F. Izumi K. Kinoshita Y. Matsui K. Yanagisawa T. Ishigaki T. Karniyama T. Yamada and H. Asano Physica C 1992 196 227. 67 T. Mertelj D. Mateev F.C. Matacotta D. Pal P. Stastny P. Nozar Q. Jiang D. Mihailovic and P. Ganguly Solid Stutr Commun. 1992 84 11 15. 68 Y. Miyazaki H. Yamane and T. Hirai Physica C 1992 198 53. 60 Y. Miyazaki H. Yamane. N. Ohnishi T. Kajitani K. Hiraga Y. Morii S. Funahashi and T. Hirai Physicu C 1992 198 7. 70 J. Akimitsu M. Uehara M. Pgawa H. Nakata K. Tomimoto Y. Miyazaki H. Yamane T.Hirai K. Kinoshita and Y. Matsui Physica C 1992 201 320. 71 Y. Miyazaki H. Yamane N. Kobayashi T. Hirai H. Nakata K. Tomimoto and J. Akimitsu. Physica C. 1992 202 162. Electronic Conductors including High Temperature Superconductors Cu(1) Cu(2) CU(1) a Figure5 (a)Thestructure of(Y 8,Ca Ip)Sr,Cu,(Cu 6Co4)07 and (b)its projection along [OlO]. (Reproduced by permission from Physica C 1992 198 7) Halogen-containing Phases.-Iodine intercalation into Bi,Sr,Ca xYxCu20s has ~ been studied7' and found to enhance the two-dimensional features due to expansion along c and to increase the hole density on the superconducting CuO layers due to charge transfer and the formation of 16-. It was suggested that the former resulted in a decrease of 10K in T, whilst the hole density increase caused a change in the dependence of T on x.However in a separate study,73 iodine incorporation was observed to decrease T by 2-10 K in the overdoped region (x < 0.2) consistent with 1'-formation but little change in T was recorded for x > 0.3. Hall coefficient rneasurernent~~~ on phases of this type revealed an increase in hole concentration on the CuO planes due to electron transfer to the I atoms. A study of IBi,Sr,CaCu,O using Raman spectro~copy~~ supported the presence of 13 anions rather than the discrete I-units indicated by structural methods. The structural properties of Pb-doped Bi,Sr,CaCu,O after iodine intercalation have been investigated by HREM.76The change in stacking of the BiO layers was confirmed for the stage-1 72 A.Fujiwara Y. Koika K. Sasaki M. Mochida T. Noji and Y. Saito Physica C 1992 203 411. 73 Y. Muraoka M. Kikuchi N. Ohnishi K. Hiraga R. Suzuki N. Kobayashi and Y. Syono Physica C. 1992 204 65. '' D. Pooke K. Kishio,T. Koga Y. Fukuda N. Sanada M. Nagoshi K. Kitazawa and K. Yamafuji Physica C 1992 198 349. 75 E. Faulques and R. E. Russo Solid Srutr Commun. 1992. 82 531. 76 N. Kijima R. Gronsky X.-D. Xiang W. A. Vareka J. Hou A. Zettl J. L. Corkill and M. L. Cohen. Physica C 1992. 198 309. 404 C. Greaves intercalated material. However iodine bilayers were also observed which provided a new series of compounds with staggered nearest-neighbour BiO layers. An additional study of the possible insertion of iodine into YBa,Cu,O has been reported.,' Superconductivity was found to be restored in YBa,Cu306 following a treatment in iodine at temperatures less than 350°C.The tetragonal phase was transformed into an orthorhombic material with T = 70K. The effects of F-doping in TlSr,CaCu,O have been reported.78 The introduction of F to yield TlSr,CaCu,O -xF was achieved using solid state methods involving SrF, and the critical temperature was reported to increase from 35 K (x = 0) to 50 K (x = 0.5 1.O 1S),It was suggested that the substitution resulted in a decrease in hole density from the value of 0.5 for x = 0. 3 Fullerenes Thin films of K,C, for 0 5 x 2 6 have been studied by Raman spectros~opy.~~ Above 80 "C evidence was found for the formation of phases with x = 1,2 and 4in addition to the x = 0 and x = 3 phases.Below 80"C the compound with x = 1 transformed to compositions with x = 0 and x = 3. Using high pressure techniques on K3C6 and Rb,C6, the correlation between T and the unit cell size a has been extended" to cover the ranges T = 6-30 K and a = 13.9-14.5 A. High quality transport data have been reported on single crystals of K3C6, and very sharp resistive transitions (200mK) observed" at 19.8 K. ESR measurements on K,C60 have been interpreted in terms of transitions within states bound to the c6 molecules.82 The g-factor varied with x due to partial occupancy of the cation interstices and a single signal was obtained (y = 2.002) for x = 3. In a similar study of cS,c60 three ESR lines were attributed to different charged states of the c6 molecules.83 The absorptions were still apparent below T (29K) suggesting that the active spins were not the conduction electrons responsible for superconductivity.A detailed study of electron and phonon states in A,C60 superconductors by Schluter et suggested that the superconductivity arises from a favourable combination of high phonon frequencies and the existence of two different energy scales to optimize coupling. If correct such a mechanism would allow a maximum T of about 30 K in these systems. Raman scattering from ultra-thin RbXC6 films,85 and the measured isotope effect exponent (ct = 0.37 & 0.05 in T K 1/Ma)86for Rb3C6, using 75% substitution of I3C for I2C were thought to provide support for the model of Schluter et However using a similar substitution much larger isotope effects have been reported for K,C6 (x = 1.3 0.2)87 and Rb3C, (ct = 2.1 " M.Mokhtari C. Perrin 0. Pena and M. Sergent Physica C 1992 202 141. 78 Z. Y. Chen Z. Z. Sheng Y. Q. Tang Y. F. Li and D. 0.Pederson SoM Stare Commun. 1992. 83 895. 79 J. Winter and H. Kuzmany Solid State Commun. 1992 84. 935. 80 0.Zhou G. B. M. Vaughan Q. Zhu J. E. Fischer P. A. Heiney N. Constel. J. P. McCauley Jr. and A. B. Smith 111. Science 1992 255 833. X.-D. Xiang J.G. Hou G. Briceno W. A. Vareka R. Mostovoy A. Zettl V. H. Crespi and M. L. Cohen Science 1992. 256,1190. 82 P. Byszewski R. Jablonski and R. Diduszko Sohf State Cornrnun. 1992 83 879. 83 N. Kinoshita. Y. Tanaka. M. Tokumoto and S.Matsumiya Sdid State Commun.. 1992 83 883. 84 M. Schluter M. Lannoo. M. Needels. G.A. Baraff and D. Tomanek Phys. Rev. Lett.. 1992 68 526. 85 M.G. Mitch S. J. Chase and J.S. Lannin Phys. Rev. Lett. 1992 68 883. 86 A. P. Ramirez A. R. Kortan. M. J. Rosseinski. S. J. Duclos A.M. Mujsce R. C. Haddon D. W. Murphy A.V. Makhija S. M. Zahurak and K. B. Lyons Phys. Rev. Lett.. 1992 68 1058. " A.A. Zakhidov K. Imaeda D. M. Petty K. Yakushi H. Inokuchi I. Ikemoto S. Suzuki and Y. Achiba Phys. Lett. A. 1992 164 355. Electronic Conductors including High Temperature Superconductors -+ 0.25 and r = 1.4 & 0.5).87*88 It has been suggestedE7 that the large values for 2 support an intramolecular vibronic pairing mechanism. The synthesis and characterization of Na,C60 phases have been reported.89 The phases were not superconducting and the structure of Na,C,,- was shown to have a face-centred C, lattice with Na in tetrahedral sites and Na clusters centred on the octahedral sites Figure 6.Na2AC6 (A = K Rb Cs)89*90 and Li,CsC, superconduc-tor~~~ have also been synthesized with T = 10-12K. The reason for the absence of superconductivity in Li,C, and NaxC60 has been addressed by a photoemission and inverse photoemission study.” The results show significant differences in the distribution of electronic states in these materials compared with the superconducting K,C,O and Rb,C, systems. The results of an X-ray diffraction study of A,CsC, and ACs,C, (A = Na K Rb)92 and a 133Cs NMR investigation93 of CS,Rb,-,C60 are consistent with cation ordering in accordance with ionic radii considerations.For example Na,CsC, has an ordered arrangement of Cs and Na in octahedral and tetrahedral sites respectively. 0 Tetrahedral Na 0 Na in Na4 cluster Figure 6 The Na sites in the structure of Na,C,,. The Na tetrahedral cluster is centred around an octahedral site of the C, lattice. Superconductivity with T = 8 K has been reported9 for Ca,C,,. Ca intercalates into the face-centred C, lattice but near the Ca :C, ratio of 5 1 a simple cubic phase MH T.W. Ebbesen J.S. Tsai K. Tanigaki J. Tabuchi Y. Shimakawa Y. Kubo I. Hirosawa and J. Mizuk Nature (London),1992 355 620. n9 M. J. Rosseinski D. W. Murphy R. M. Fleming R. Tycko A. P. Ramirez T. Siegrist. G. Dabbagh and S.E. Barrett. Name (London). 1992. 356.416. 90 K. Tanigaki I. Hirosawa T. W. Ebbesen J. Mizuki. Y. Shimakawa. Y. Kubo. J. S. Tsai. and S. Kuroshima Nature (London),1992 356,419. 91 C. Gu. F. Stepniak D. M. Pokier M. B. Jost P. J. Benning Y. Chen T. R. Ohno J. L. Martins J. H. Weaver J. Fure and R. E. Smalley. Phys. Rei?.B. 1992. 45. 6348. 92 I. Hirosawa K. Tanigaki. J. Mizuki. T.N. Ebbesen. Y. Shimakawa. Y. Kubo and S. Kuroshima. Solid State Commun. 1992 82. 979. 9.3 Y. Maniwa K. Mizoguchi K. Kuma K. Tanigaki T. W. Ebbesen S. Saito J. Mizuki J. S. Tsai and Y. Kubo Solid State Commun. 1992 82. 783. 94 A. R. Kortan N. Kopylov. S. Glarum. E. hl. Gyorgy A. P. Ramirez R. M. Fleming. F. A. Thiel. and R. C. Haddon Nature (London),1992. 355.529. 406 C. Greaves was formed. Ca clusters centred on the octahedral sites were suggested to exist similar to those inferred in Na6C60. Due to the divalent nature of Ca it has been re~ognized’~.’~ that the superconductivity is unlikely to relate to the same type of charge donation to the c60 molecules as in K3C6,. Conductivity9’ and photoemis- sion96,97 results have been interpreted in terms of electron donation from Ca to C, such that the t, band the conduction band in K3C60 is full and the next highest band oft, symmetry is partly filled. Superconductivity has also been reported in Ba6C60 (body-centred cubic a = 11.171 A T = 7 K)98 and Sn,C6 (T onset at 37 K).” Iodine intercalation into c60has been shown to form C,,I with a trigonal layer structure consisting of alternate c60 and I as shown in Figure 7.The 1-1 distance is consistent with uncharged I species and suggests little charge transfer between the I and c60 units. Figure 7 (a) Basal plane projection of the structure of C6,14. The large circles represent the C, molecules and the small circles I atoms. (b) Three dimensional view showing the layer nature of the structure. (Reproduced by permission from Nature (London) 1992 355 712) 4 Other Electronic Conductors RESrGaCuO (RE = La Pr Nd) phases have been reported”’ with the brownmil- lerite structure which is perovskite-related with alternating layers of Cu06 octahedra 95 R.C. Haddon G.P. Kochanski A.F. Hebard A.T. Fiory and R.C. Morris Science 1992 258 1636. 96 G. K. Wertheim D.N. E. Buchanan and J. E. Rowe Science 1992 258 1638. 97 Y. Chen D. M. Poirier M. B. Jost C. Gu T. R. Ohno J. L. Martins J. H. Weaver L. P. F. Chibante and R.E. Smalley Phys. Rev. B 1992 46,7961. 98 A. R. Kortan N. Kopylov S. Glarum E. M. Gyorgy A. P. Ramirez R. M. Fleming 0.Zhou F.A. Thiel P. L. Trevor and R. C. Haddon Nature (London) 1992 360,566. 99 Z. Gu J. Qian Z. Jin X. Zhou S. Feng W. Zhou and X. Zhu Soiid Stute Commun. 1992 82 167. loo Q. Zhu D. E. Cox J. E. Fischer K. Kniaz A. R. McGhie and 0.Zhou Nature (London) 1992,355,712. G. Roth P. Adelmann R. Knitter S. Massing and T. Wolf J. Solid Stute Chem. 1992 99 376. Electronic Conductors including High Temperature Superconductors and GaO tetrahedra. The materials were semiconducting and doping to induce superconductivity was unsuccessful.Pure YBaCo -,CuXO5 +d has been syn-thesizedlo2 for 0.3 Ix I1. The structure is related to that of YBa,Cu,O but with the chain CuO and one BaO layer missing. Two Ba analogues of Bi,Sr,CaCu,O, Bi,Ba,NdCu,O and Bi,Ba,+,La -xCu208 have been rep~rted,''~~'~~ but due to the required co-substitutions of Nd or La for Ca the materials are semiconducting. Another phase related to Bi,Sr,CaCu,O, Bi,Ca -,La,Co20s has also been A reported to be semicond~cting.'~~ neutron powder diffraction study of the semiconductors YSr,Cu,CoO and (Y ,-,Ca,)Sr,Cu,CoO has revealed a structural similarity to YSr,Cu,GaO, but unlike this last material the 0 atoms in the Co planes are disordered.'06 The phases (Nd,Ce),Sr,Cu,MO (M = Al Co Ga) have been reported"' with structures related to YSr,Cu,GaO, but with (Nd,Ce),O fluorite blocks substituted for the Y layers.The lack of superconductivity was attributed to the difficulty of introducing holes. Metallic conductivity in the Ruddlesden-Popper phases Ba,PbJOlo and reduced Can+ 1Ti0,03n+ -b has been ~tudied.''~~'~~ In Ca3Ti,0 a metal-insulator transition was ob~erved''~ at 70 K. Sr,RhO, which appears to be metallic below 150K,has been reported"' and its structure is similar to that of La,CuO (tilted Rho octahedra). The transport properties of La -,Srx CrO have been determined' '' as a function of x. LaCrO is a p-type semiconductor and the conductivity was found to increase with x up to x = 0.2 but decreased at high values of x especially for x > 0.75 due to oxygen vacancy formation.The new orthorhombic phase AgTaS has been reported112 to be an n-type semiconductor with a layer structure comprising layers of trigonal prismatic Ta which interleave octahedrally coordinated Ag. The new misfit layer structures (BiS) ,,,CrS, (BiSe),,,,NbSe, and (BiSe),,,,TaSe have been described.' 13*114 The Cr phase appears similar to (LaS),,,,CrS and the Nb and Ta materials are analogous to similar sulfide phases. The Se-containing compounds displayed metallic properties consistent with mixed hole and electron conduction on the NbSe and TaSe layers."4 No significant electron transfer from the BiSe to the NbSe (or TaSe,) layers was indicated. L. Barbey. N. Nguyen V. Caignaert M. Hervieu and B.Raveau Mater. Res. Bull. 1992 27 295. Io3 N. Naumov Y. Kotlyarov P. Samoilov and V. Fedorov Physica C 1992 193 217. lo4 A.Q. Pham H. Hervieu C. Michel and B. Raveau Physica C 1992 199. 321 H. Yoshikawa H. Hidaka J. Sugiyama K. Nakao and H. Yamauchi. Physica C 1992 203 144. Q. Huang R.J. Cava. A. Santoro J. J. Krajewski. and W. F. Peck Jr.. Physica C 1992. 193. 196. lo' R. J. Cava H. W. Zandbergen J.J. Krajewski W. F. Peck. Jr. B. Hessen R. B. Van Dover and S.-W. Cheong Physica C 1992 198 27. W. T. Fu and R. B. Helmholdt Mafer. Res. Bull. 1992 27 1371. 109 I. Kim M. Itoh and T. Nakamura J. Solid State Chem. 1992 101 77. 'lo T. Shimura M. Itoh and T. Nakamura J. Solid State Chem. 1992 98 198. 'I1 P.S. Devi and M. Subba Rao J. Solid State Chem.1992 98 237. '" H. Wada M. Onoda and H. Nozaki J. Solid State Chem. 1992 97 29. 'I3 A. Lafond P. Fragnand M. Evain and 4. Meerschaut Mater. Res. Bull. 1992 27 705. W. Y.Zhou A. Meetsma J. L. de Boer and G. A. Wiegers. Mater. Res. Bull. 1992 27. 563.
ISSN:0260-1818
DOI:10.1039/IC9928900393
出版商:RSC
年代:1992
数据来源: RSC
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22. |
Chapter 22. New compounds and structures |
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Annual Reports Section "A" (Inorganic Chemistry),
Volume 89,
Issue 1,
1992,
Page 409-424
J. T. S. Irvine,
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摘要:
22 New Compounds and Structures By J.T.S. IRVINE Department of Chemistry University of Aberdeen Meston Walk Aberdeen AB9 2UE UK 1 Introduction The aim of this review is to highlight new and exciting phases and structures that have been reported in 1992. It is hoped both to reflect current trends in solid state chemistry and to provide some insight into future advances in this important area. The scope of this review is limited to inorganic materials with reasonably defined composition and structure. New compounds formed solely by solid-solution formation have not been reported. The organization of this review is based on both structural and chemical aspects. Division is largely by periodic classification with the primary split being between oxides and non-oxides.Oxides are further sub-divided into transition metal oxides main group oxides and important structural families. Where overlap occurs classifica- tion has been made to maximize the coherence of the current year's report. 2 Overview The number of new phases and structures reported in the last year reflects the continued high level of activity in solid state chemistry. There are some perceptible changes in emphasis; for instance there is a clear increase in activity in non-oxide chemistry particularly in halide nitride and chalcogenide chemistry. Activity in the area of cuprates has decreased somewhat; however this appears to be just a temporary lull. Low-dimensional structures and the perovskite structure continue to be key areas of interest.3 Transition Metal Oxides Vanadates and Titanates.-Two new hexavanadates SrV,O ,and NaV,O which are isostructural with Ba,Ti,Fe,O ,,and hence structurally related to magnetoplum- bite have been reported.' A new bismuth magnesium vanadate BiMg,VO, with Mg in an unusual five-fold geometry has been synthesized. The structure of BiMg,VO may be viewed as consisting of chains of edge-shared BiO groups and corner-shared MgO square pyramids. These chains are connected through.VO tetrahedra and uia ' Y. Kanke K. Kato E. Takayama-Muromachi and M. Isobe Acta Crystallogr. Sect. C 1992,48 1376. * J. Huang and A. W. Sleight J. Solid State Chern.. 1992 100 170. 409 410 J. T.S. lrvine edge-sharing of the MgO groups Figure 1. A bismuth strontium vanadate containing both orthovanadate and pyrovanadate groups has also been rep~rted.~ C a a’ Figure 1 Structure of BiMg,VO (Reproduced by permission from J.Solid State Chem. 1992 100 170) Several new metal vanadates with formula M,V,O have been reported. A high-pressure form of Mn,V,O with the pyrochlore structure has been ~repared.~ A high-temperature form of strontium pyrovanadate containing two types of V,O unit has also been reported. No V,O groups were found in the structure of ThV,O, instead the structure was observed to contain both independent VO groups and infinite chains of corner-shared VO tetrahedra Figure 2.6 The hydrogen analogue of the lithium titanate ramsdellite phase H2Ti30, has been prepared by simple proton exchange.’ The structure of the new phase NaGaTi,O has been shown to be related to that of Na,Ti,O , consisting of a framework of NaO and GaO octahedra which form tunnels accommodating the Na ions.’ A new titanate phase which exists over a range of stoichiometry Ba3xLi,x+,,Ti8 -2x-y016 0.32 < x < 0.40 and 0 < y < 0.2 with a structure closely related to the Priderite member of the Hollandite family has been characterized.’ J.Huang and A. W. Sleight. J. Solid Stute Chem. 1992 97 228. M. A. Subramanian Mat. Res. Bull. 1992 27 939. J. Huang and A. W. Sleight Mat. Res. Bull. 1992 27 581. S. Launay P. Mahe M. Quaton and F. Robert J. Solid State Chem. 1992 97 305. ’ A. LeBail and J. L. Fourquet Mat. Res. Bull. 1992 27. 75. ’ Y. Michiue. M. Watanabe Y. Kitami and Y.Fujiki. Acta Crystallogr.. Sect. C 1992 48 607. ’C. Suckut R.A. Howie A. R. West and L. M. Torres-Martinez. J. Muter. Chem. 1992 2 993 New Compounds and Structures 41 1 ..... Th ..... 2(VO3)O ..... Th ..... V04 ..... vo4 _....Th ..... 2(V03) ..... Th ..... vo4 ..... vo4 ..... Th Figure 2 Projection of structure qfThV,O along [Ool] (Reproduced by permission from J. Solid State Chem. 1992 97 305) Cuprates.-Although interest in superconducting cuprates has decreased from its highpoint in the late 80s there is still intense interest in cuprate perovskites and perovskite intergrowth phases. Some of the most interesting chemistry has been in the development of novel oxygen-deficient perovskites. Ba,La,Cu,Sn,O is a new oxygen deficient quadruple perovskite whose average structure Figure 3 can be described by a tetragonal cell; however because of rotational ordering of SnO octahedra about c a long range modulation is also observed.' A number of rare-earth strontium gallium cuprates e.g.LaSrGaCuO, exhibiting the well-known oxygen deficient perovskite-related Brownmillerite structure have also been reported. Another new perovskite YBaCoCuO, has a similar formula; however its structure which is analogous to YBaFeCuO, contains both B-cations in square pyramidal coordination instead of having one B-cation in octahedral geometry and the other in tetrahedral geometry as occurs in Brownmillerite. l2 Rouillon et a!. have prepared PbBaSrYCu,O with a structure built up from triple M.T.Anderson K. R. Poeppelmeier. J.-P. Zhang H.-J. Fan and L. D. Marks Muter. Chmi.. 1992. 4. 1305. G. Roth P. Adelmann R. Knitter S. Massing. and Th. Wolf J. Solid State Chem. 1992. 99. 376. '2 L. Barbey N. Nguyen V. Caignaert H. Hervieu and B. Raveau Mat. Res. Bull. 1992 27 295. 412 J. T.S.irvine perovskite and single rocksalt layers.13 Rouillon et ul. have also determined the structure of PbBa,,,Sr ,,PrCeCu,O, finding it to be a perfectly ordered intergrowth of single and double oxygen-deficient perovskite layers with single rocksalt and double fluorite type layers. l4 A new layered cuprate (Y,Ce),SrFeO, containing a triple fluorite layer has been reported.' The Thorium analogue of the fluorite related Ce-223 superconductor La,Ba ,,,Th,,,,Cu,O +y has also been prepared.' Figure 3 Poljihedrul representation of the structurr of Ba,La,Cu,Sn,O ; large spheres Ba; medium spheres La; smallest spheres 0 uacancies; octahedra SnO ;and square pyramids CuO (Reproduced by permission from Mater.Chem. 1992 4 1312) A copper oxycarbonate containing infinite CuO layers Sr ,,Ba,,,CuO,(CO,) has been synthesized and its structure determined.' Other First Row Transition Metal Oxides.-An oxygen-deficient perovskite La,LiMnO,.,, with some of the manganese apparently in the (v)oxidation state has been reported.' The hypomanganate RbBaMnO, which is also MnV has been prepared and its structure found to be isotypic with fi-K2SO4.l9A new layered 13 T. Rouillon V. Caignaert. M. Hervieu. C. Michel. D. Groult and B.Raveau J. Solid State Chem. 1992,97. 56. 14 T. Rouillon V. Caignaert. C. Michel M. Herbieu D. Groult,and B. Raveau. J. SoM State Chem. 1992,97 19. 15 E. M. Kopnin A. V. Mironov L. M. Kovba L. G. Akselrud I.G. Muttik and V. V. Moschalkov J. Solid State Chem. 1992. 100. 30. 16 L. Rukang T. Kaibin Q. Yitai. and C. Zuyao. Mur. Rrs. Bull. 1992 27 349. 17 A. R. Armstrong and P. P. Edwards J. Solid Stute Chem. 1092 98 432. 18 G. Demazeau E. 0.Oh-Kim J.-H. Choy. and P. Hagenmuller. J. Solid Srute Chem.. 1992 101. 221. 19 D. Fischer and R. Hoppe J. Solid Stute Chrm. 1992 96 7. New Compounds and Structures compound (Fe,Mn)Ta(O,)O, with the metals in an unusual trigonal prismatic coordination has been preparede2' Reduction of lanthanum strontium nickelates with the K,NiF structure has been found to give rise to phases retaining an oxygen-deficient K2NiF structure with most of the Ni in the + 1 oxidation state e.g.SrLaNi0,,,.2' A low-temperature modification of LiCoO has been prepared by reaction of the carbonates this modification has a similar layered structure to the high-temperature form; however because of the occurrence of some Co atoms in the Li layer the electrochemical properties are significantly different .22 Second and Third Row Transition Metal Oxides.-A new lanthanum molybdate La4Mo2OI1 has been found to be isostructural with Nd,Re,O,,; the structure is based on the packing of quasi-linear chains of Mo,O units and La atoms Figure 4.23 A new cation-ordered derivative of the rutile structure has been observed for COR~O,.~ Figure 4 Structure of La,Mo,O ,; smallest spheres Mo.(Reproduced by permission from Acta Crystallogr.. Sect. C. 1992. 48 1915) A series of new hexagonal perovskites Ba,Ru,MO, (M = Li Na Mg Zn) has been synthesized2' and the structures of the Na and Li members of this series refined. In both cases all the face-sharing octahedral sites are occupied by Ru; however in the structure of the Na member Ru and Na are 1 1 ordered over the corner-sharing octahedral sites giving an 8-H structure Figure 5 whereas in the Li member the more usual 6-H structure with Li and Ru disordered over the corner-sharing sites is found. D. Shuiquan Z. Honghui and H. Jinling J. Solid Srurcj Chetn.. 1992. 98 40.21 M. Crespin. C. Landron P. Odier J. M. Bassat P. Mouron. and J. Choisnet J. Solid Srute Chem.. 1992. 100. 281. z2 R. J. Gummow M. M. Thackeray W. I. F. David. and S. Hull Mat. Rrs. Bull.. 1992. 27. 327. 23 P. Gall and P. Gougeon Actu Crj.xtullopr. Sect. C 1997 48. 1915. '' W. H. Baur W. Joswig G. Pieper and I). Kassner. J. Solid Srurr Chem. 1992. 99. 207. 2s P. D. Battle. S. H. Kim and A. V. Powcli J. Solid Srtrrr Ch~m..1992. 101. 161. 414 J. T.S.Irvine A number of copper(u)/ruthenium(v) compounds of La and Sr Sr,LaRuCu + (n= 1,2,3),exhibiting structures ranging from perovskite via the Ruddleston-Popper A3B20 to the K,NiF structures have been reported.26 Two more Ru Ruddles- ton-Popper phases Sr,FeRuO and Sr,FeRuO, have also been reported., as have two new Sc Ruddleston-Popper phases SrLaScO and S~L~,SC,O,.~' Figure 5 The 8H-perovskite structure of Ba,Ru,NaO 2.Lightly hatched octahedra contain Na atoms hatched octahedra contain Ru and circles are Ba (Reproduced by permission from J. Solid State Chem. 1992 101 161) 4 Perovskites Perovskites and perovskite-related structures have already featured heavily in the previous section and will again be covered in the bismuthate section. Here we mainly focus on mixed-perovskite phases where it is difficult to define a primary functional species. Two new ordered cubic double perovskites Sr,Fel"BiVO and Ba,PrPtO, have Two been re~orted.~~,~' new antiferromagnetic perovskite-related materials SrLaFeSnO and SrLaNiSbO, have also been prepared.j' Two new oxygen-deficient perovskites with Co replacing Cu in the Cu0,-plane sites in the YBa,Cu,O structure LaBa,CoCu,O,, and LaBa,Co,CuO, have been reported., A new series of hexagonal perovskites ALa,Ti,RuO, (A = Ca Sr Ba) isostructural with 26 M.P. Attfield P. D. Battle S. K. Bollen S.H. Kim A. V. Powell and M. Workman J.Solid State Chem.. 1992 % 344. 21 P. D. Battle S. K. Bollen and A.V. Powell J. Solid State Chem. 1992 99 267. 28 I.-S. Kim H. Kawaji M. Itoh and T. Nakamura Mat. Res. Bull. 1992 27 1193. 29 S. H. Byeon T. Nakamura M. Itoh and M. Matsuo Mat. Res. Bull. 1992 27 1065. 30 U. Almador C.J. D. Hetherington E. Moran and M. A. Alario-Franco J. Solid State Chem. 1992,96 132. 31 M. P. Attfield P. D. Battle S. K. Bollen T. C. Gibb and R.J. Whitehead J. Solid State Chem. 1992,100 37. 32 M.S. Hegde K. M. Satyalakshmi S. Ramesh N.Y. Vasanthacharya and J. Gopalkrishnan Mar. Res. Bull. 1992. 27 1099. New Compounds and Structures Ba,Nb,O,, have been ~haracterized.~~ The crystal structure is of the 5-H polytype with an hccch sequence along the c-axis Figure 6. Figure 6 The SH-perouskite structure of CaLa,Ti,RuO (Reproduced by permission from Mat. Res. Bull. 1992 27 931) 5 Main Group Oxides Berates.-A novel orthoborate with a non-centrosymmetric structure based on a three-dimensional framework of ZnO tetrahedra and BO triangles BaZn (BO,), has been ~ynthesized.~ Sr,(BO,),Cl has been found to have an intricate framework structure based on SrO,Cl, SrO,Cl, SrO, and BO groups., The structure of LiBa,B,O, has been found to be based on a novel (B,0,,)5- unit,composed of three BO triangles and two BO tetrahedra.36 Silicates and Germanates.-LiBSiO has been prepared hydrothermally ;the resulting structure can be described as cristobalite-like with Li occupying tetrahedral sites.,’ The crystal structure of a new lithium alumino-silicate and a series of Ga/Ge analogues Li,ABO (A = Al Ga; B = Si Ge) have been determined.38 This structure is based on a hexagonal close-packed array of oxygen atoms with cations disordered over one set of tetrahedral sites and can be described either as a cristobalite-like sheet structure or as a wurtzite superstructure.Two silicate structures containing four-membered rings of SO tetrahedra have 33 N.Bontchev F. Weilt and J. Darriet Mat. Res. Bull. 1992 27 931. 34 R. W. Smith and D. A. Keszler J. Solid State Chem. 1992. 100 325. 35 T. Alekel and D. A. Keszler Acta Crysrallogr. Sect. C. 1992 48 1382. 36 H. Qingzhen L. Shaofang D. Guiqin and L. Jingkui Acta Crystnllogr. Sect. C 1992 48 1576. 37 J. B. Parise and T. E. Gier Chem. Mater. 1992 4 1065. 38 J. M. S. Skakle J. G. Fletcher A. R. Honie and A. R. West. J. Solid State Chem. 1992 98 33. 416 J. T.S. Zruine been described. K,(NbO),Si,O, has a tetragonal structure based on chains of NbO octahedra linked together by Si,O ,single rings.39 BaCuSi,Olo has been prepared by two sets of worker^.^^,^* Both groups found that the structure consisted of rings of four linked SiO tetrahedra and was isotypic with mineral Gillespite BaFeSi,O ".Phosphates and Arsenates.-A series of lan thanide caesium europium(i1) phosphates CsEuLn(PO,) (Ln = La Ce. Pr. Eu Th) exhibiting a rhabdophane hexagonal structure have been prepared., The Nasicon-related Cu' compound CuZr,( has been reported.43 Quite a number of vanadium and niobium phosphate compounds have been reported. These include Ca(VO),(PO,),. which crystallizes in a non-centrosymmetric point group and shows some similarity in structure to the important non-linear optical material KTiOP0,.44 Another oxophosphate is CaNb,P,O ,,the structure of which contains double layers of zig-zag corner-sharing chains of NbO octahedra connected by layers of PO tetrahedra and Ca ions Figure 7.45 A new vanadium phosphate BaV,P,Olo with a tunnel structure in a (V,P,O,,) framework has been isolated;, another barium vanadium phosphate has also been reported Ba(VO,)PO, with a Figure 7 Structure of CaNb2P20,, showing mixed fiame\t'ork of double-layered zig-zag NbO chains and corner-shared phosphate groups (Reproduced by permission from J.Solid Stair Chem. 1992 98 174) 3'1 M. P. Crosnier D. Guyomard. A. Verbaere. Y. Piffard and M. Tournoux J. Solid Sture Chem. 1992.98 128. 4" H.C. Lin F.L. Liao and S. L. Wang Actu Crysfullogr.. Sect. C 1992 48 1299. 41 J. Janczak and R. Kubiak Actu C'rj.stalloyr.. Sect. C. 1992 48 1299. 42 G. Wu. M. Jansen and K. Konigstein J. Solid State Chem. 1992 98. 210. 43 I. Bussereau M. S. Belkhira. P. Gravereau R. Boireau J. L. Soubeyroux.R. Olazcuaga and G. Le Flem. Actu Crystullogr. Sect. C. 1992 48 1741. 44 K. H. Lii. B. R. Church H. Y. Lang and S. L. Wang J. Solid Sfnfc. Chem.. 1992 99 72. 45 D. L. Serra and S.-J. Hwu. J. Solid Srure Chem.. 1992. 98 174. 4h A. Grandin J. Chardin M. M. Borel A. Leclaire and B. Raveau .I. Solid Srute Chem. 1992. 99. 297. New Compounds and Structures structure based on layers of phosphate tetrahedra and edge-shared bioctahedra of distorted VO Two novel niobium phosphate bronzes K,Nb,P,SiO, and Bao,8,Rb,Nb8P,0,, and the Langbenite K 1P18073 have been A new mixed-valence vanadium phosphate KV,P,O 7 containing intersecting six-sided and Brownmillerite zig-zag tunnels has been ~repared,~ and a tetravalent vanadium diphosphate Na,VP,O, has been reported.52 Two new cyclophosphate salts of silver have been reported.Ag,NaP802,- (N0,),.4H20 contains the P80; ring anion5 and Ag4K,P,,0,,~10H,0 contains the PlOO~~- anion Figure 8., W d 0 0 0 Figure8 Projection along b of the structure of Ag,K,P,oO,,~lOH,O.In increasing order ofsize the circles represent siluer atoms potassium atoms and water molecules (Reproduced by permission from J. Solid State Chem. 1992 97 299) The structure of a novel vanadyl(1v) orthophosphate hydrate (VO3)(PO,),-9Hz0 has been solved showing it to be a corrugated layered structure consisting of large ‘squares’ of (VO,-PO,-) moieties with water molecules located in the open cells Figure A new phosphate hydrate Nio,,VOP0,~l~H20 has been prepared hydr~thermally.~~ Bismuthates and P1umbates.-The crystal structure of CaBi,O has been deter- mined.57 Unlike many of the ternary bismuthates in the series containing the bismuth cuprate superconductor system the alkaline-earth ions are found in the same layers as the bismuth ions occupying every third cation position when viewed along b Figure 10.Crystals of the cubic perovskite phase KBiO have been prepared by electrolysis of molten KOH containing Bi,O,.” A number of new Bi” phases {LiSr,BiO, NaSr,BiO, NaBa,BiO,) {Li6KBi06 Li,RbBiO,) and { Li,Ba,Bi,O >,exhibiting 47 H.Y. Kang S. L. Wang and K. H. Lii Acta Cr-vstallogr. Sect. C. 1992 48. 975. 4x A. Leclaire M. M. Borel J. Chardon A. Grandin and B. Raveau Acta Crystallogr. Sect. C. 1992.48 1744.4y C. Gueho M. M. Borel A. Grandin A. Leclaire and B. Raveau Actu Crystallogr. Sect. C 1992.48 2066. 50 A. Benmoussa M. M. Borel A. Grandin. 4. Leclaire and B. Raveau. J. Solid Stare Chem. 1992.97. 314. 51 L. Benhamada. A. Grandin M. M. Borel A. Leclaire and B. Raveau. J. Solid State Chem.. 1992.97 131. 52 L. Benhamada A. Grandin M. M. Borel. A. Leclaire and B. Borel J. Solid State Chem. 1992 101 154. 53 M. T. Averbuch-Pouchot and A. Durif Acta Crystallogr.. Sect. C. 1992. 48 1173. 54 M.T. Averbuch-Pouchot A. Dunf and 1J. Schulke J. Solid Stare Chem.. 1992 97 299. 5s B. G. Teller P. Blum E. Kostiner and J. A. Hriljac. J. Solid Stute Chern. 1992. 97 10. s6 K. H. Lii and L. F. Mao J. Solid State Chem. 1992 96. 436. 57 T. A. M. Haemers D. J. W. Haemers.D. J. W. Ijdo and R. B. Helmholdt Mar. Rex Bull.. 1992.27 1243. sH S. Kodialam V.C. Korthius R.-D. Hoffmann and A. W. Sleight. Mat. Res. Bull. 1992. 27 1379. 418 1.T.S. Irvine Figure 9 Representation of the structure of (VO),(PO4),*9H,O;jfilled spheres PO tetrahedra; open ellipsoids VO octahedra (Reproduced by permission from J. Solid State Chem. 1992 97 10) Figure 10 Projection of crystal structure of'CaBi,O along b (Reproduced by permission from Mat. Res. Bull. 1992 27 1243) three distinct structure types each of which contain perovskite-derived units have been prepared by hydroxide flux The structure of Li2Ba,Bi20 1,Figure 11 is based on zig-zagged chains of corner-sharing BiO octahedra running parallel to b. Two new plumbate pyrochlores the red insulating Bi,Pb,O and the rhombohedrally distorted black metallic TI2Pb20, have been prepared by high-pressure oxygen synthesis.,' A new mixed-valence Aurivillius-type phase Bi,V .5Sb,.50 ',,,has been reported.61 A number of bismuth-containing oxychlorides have been reported.The structure of BiSr,O,Cl is made up from layers stacked in the sequence Cl/Sr-O/Bi-Sr-O-Cl/ Sr-O/Cl; the Bi-Sr-0-C1 is unusual among bismuth oxyhalides in having both oxide and halide in the same layer. The analogous BiCa,O,Cl is also reported.,' A new '' V. A. Carlson and A. M. Stacy J. Solid State Chrm. 1992 96 332. M. A. Subrarnanian A. K. Ganguli and A. W. Sleight Mat. Res. Bull. 1992 27 799. 61 0.Joubert A. Jouanneaux M. Ganne and M. Tourneaux Mat. Res. Bull. 1992 27.154. 62 J. Huang and A. W. Sleight J. Solid State Chrm. 1992 96,154. New Compounds and Structures 8 LI 0 Ba 8 Bi 00 Figure 11 Structure of Li,Ba,Bi,O viewed down b (Reproduced by permission from J. Solid State Chem. 1992 96 332) Sillen-type phase Bil,7Ca2,704-yC14 and the related Bi,,,Ca, ,CuO -,,C1, which contains an additional CuO sheet have been reported., Oxysalts of Sulfur and Selenium.-The crystal structures of K,Co(Se03) and LaHSe,O have been determined.64,65 The diselenite CoSe20 has been found to be isomorphous with ZnSe,O and MnSe,0,.66 The structure of the mixed-valent tantalum oxysulfide La,Ta,S,O has been found to bear resemblance to that of CaTa,O, with a similar packing arrangement of TaO bi-octahedra; alternating short and long Ta-Ta distances indicate some metal-metal bonding Figure 12.67A novel lithium Nasicon-type phase based on sulfate and selenate groups Lix{M(~~)xM(~~~)l-,,(SeO4)?} has been reported.68 -x(so4)3 6 Non-oxide compounds Carbides.-Novel Scandium carbides Sc,TC4 (T = Ru Ru Os Or Ir) with the Sc,CoC structure have been prepared.69 63 W.J. Zhu Y.Z. Huang J.K. Liang and Z.X. Zhao Mat. Res. Bull. 1992. 27. 885. b4 K. Wildner. Acta Crystallogr. Sect. C 1992 48. 410. h5 R. Morris W. T. A. Harrison G. D. Stucky and A. K. Cheetham Acru Crystallogr.,Sect. C 1992,48 1182. 66 W.T. Harrison A.V. P. McManus and A. K. Cheetham Acta Crystallogr. Sect. C 1992 48. 412. " T. D. Brennan and J. A. Ibers J. Solid Srate Chem. 1992. 98 82. bx P.R. Slater and C. Greaves J. Muter. Chem. 1992 2 1267. h9 R.-D. Hoffmann R. Pottgen and W. Jeitschko J. Solid State Chem. 1992 99. 134. 420 J. T.S. Irvine Figure 12 Unit cell ofLa,Ta,S,O uiewed down c (Reproduced by permission from J. Solid State Chem. 1992 98 82) Nitrides.-A series of antiperovskite nitrides Ca,MN (M = P As Bi Ge Sn Pb) have been ~repared;~’ unusually the formal valence of Ge Sn and Pb is + 3. Li,NbN has been found to exhibit an ordered antifluorite-type structure with each octant of the cubic unit cell containing a distorted Li,Nb cube.71 The structure of Ca,VN has been found to be based on sheets of VN anion^.^' Pnictides.-Novel ternary pnictide Zintl phases containing Zi -dumbells Na,M,Z (M = Sr Eu; Z = P As) have been reported.73 Sulfides.-Two new rare-earth sulfides have been reported BaSm,S crystallizes with the CaFe,O structure7 and CaYb,S crystallizes with the Y 3S4 str~cture.,~ LaPbCuS has been found to have a structure closely related to cr-La,S with seven-coordinate La and Pb atoms disordered unequally over two sites and tetrahedral Cu forming corner-sharing chains.76 A new tantalum sulfide with a structure based on TaS chains has been reported., A new lead sulfide related to Robinsonite Pb,Sb,S,, built up from chains of square pyramidal (Pb,Sb)S groups has been ~haracterized.~’ ’O M.Y. Chern D. A. Vennos and F. G. Disalvo J. Solid Stute Chem. 1992. 96 415. ” D. A. Vennos and F. G. Disalvo Acta Crystallogr.,Sect. C 1992 48 610. l2 D. A. Vennos and F.J.Disalvo J. Solid State Chem. 1992 98 318. 73 W. Honle J. Lin M. Hartweg and H.6. von Schnering J. Solid Stute Chrm. 1992. 97 1 l4 J. D. Carpenter and S.-J. Hwu Acru Crystallogr. Sect. C 1992 48 1164. 75 J. D. Carpenter and S.-J. Hwu. J. Sdid Stare Chem. 1992 97 332. l6 T. D. Brennan and J. A. Ihers. J. Solid State Chrm. 1992. 97 377. ” H. Wada M. Onoda and H. Nozaki. J. Solid Stute Chem. 1992 97 29. ” A. Skowron I. D. Brown and R. J. D. Tilley J. Solid State Chew.. 1992 97 199. New Compounds and Structures 421 Three new quaternary sulfides made up of layers of metal-centred tetrahedra separated by potassium ions KGaSnS, KInGeS, and KGaGeS, have been rep~rted.’~ A new misfit layer structure (BiS) ,,,CrS2 made up from rocksalt BiS layers and a CrS layer of edge-sharing CrS octahedra has been reported.80 Cha1cogenides.-Two new selenide misfit layer compounds (BiSe) ,NbSe and (BiSe),,,,TaSe, have also been reported.81 CaYbInSe and its sulfur analogue both with the olivine structure have been reported.82 The zirconium chalcogenides KCuZrQ (Q = S Se Te) have been found to present a layered-type structure8 and the structure of EuZrSe has been found to contain columns of double edge-sharing octahedra linked together by Eu bicapped trigonal prisms.s4 BaNb,,,Se has been found to present the BaVS structure type.85 K3CU3Nb2Se8 and its Ta and S analogues have been found8 to have structures containing one-dimensional triple chains (Cu,Nb,Sei -) and three new compounds with the Eu,,,Nb,Se structure type where Eu has been substituted by Pb Sn and Sr have been reported.87 Two new ternary transition metal tellurides with a layered Cd1,-related structure NbIrTe and TaIrTe, have been reported Figure 13.88A new member of the Nb,MTe, series Nb,GeTe, has been prepared.89 A new layered telluride with an unusual Ta-Fe bonded network TaFe,,,,Te, has been reported.” The structure (Figure 14) can be Figure 13 View of the structure of NbIrTe down a (Reproduced by permission from J.Solid State Chem. 1992 97 366) ’’ P. Wu Y.-J. Lu and J.A. Ibers J. Solid State Chem. 1992 97 383. A. Lafond P. Fragnaud M. Evain and A. Meerschaut Mat. Res. Bull. 1992 27 705. ‘I M.Y. Zhou A. Meetsrna J. L. de Boer and G.A. Wiegers Mat. Res. Bull. 1992 27 563. R2 J.D. Carpenter and S.-J.Hwu Chem. Muter. 1992 4 1368. 83 M.F. Mansuetto P.M. Keane and J. A. Ibers J. Solid State Chem. 1992 101 257. x4 A. Mar and J. A. Ibers Acta Crystallogr. Sect. C 1992 48 771. 85 B.-L. Chen. G. Saghi-Szabo B. Eichorn J.-L. Peng and R. Greene Mat. Res. Bull. 1992 27 1241. 86 Y.-J. Liu and J.A. Ibers J. Solid State Chem. 1992 98 312. *’ T. D. Brennan and J.A. Ibers Mat. Res. Bull. 1992. 27 231. 88 A. Mar and J.A. Ibers J. Solid State Chem. 1992. 97 366. ’’)J. Li and P. J. Carroll Mat. Res. Bull. 1992 27 1073. yo M. E. Badding J. Li F. J. Disalvo. W. Zhou. and P. P. Edwards J. Solid State Chem. 1992 100. 313. 422 J. T.S.Irvine Figure 14 View of the structure ofTaFe,,,,Te down b; dotted circles Ta; hatched circles Fe; partially hatched circles partial Fe occupation; and open circles Te (Reproduced by permission from J.Solid State Chem. 1992 100 313) viewed as a Fe/Ta/Te network sandwiched between tellurium layers. KErTe adopts the a-NaFeO structure an ordered NaCl superstructure.” Halides.-Most of the new non-molecular halide structures reported in 1992 were fluorides. A new tetragonal form of AlF has been reported;92 the layers in this structure are closely related to those in chiolite indeed Na,Ca,Al,F, may be considered as a stuffed polytype. LiInF has been found to present a new structure type consisting of layers of corner-sharing InF octahedra linked by perpendicular chains of LiF edge-sharing octahedra.’ A new layer-type fluoride structure based on layers of Mn3F11 with Mn in an unusual seven-fold coordination interleaved by Na and Ba ions NaBa,Mn,F 1 has been rep~rted.’~ Na,MnF has been found to be essentially isostructural with cryolite A showing only very weak Jahn-Teller di~tortion.~~new cubic perovskite NaBaLiNiF, with Na and Ba disordered over the B-sites has been rep~rted.~ The indium Weberite Na,NiInF has been synthesized and its structure shown to consist of 91 P.M. Keane and J.A. Ibers Acta Crysrullogr.. Sect. C 1992 48 1301. 92 A. Le Bail J. L. Fourquet and U. Bendrup J. Solid Scare Chem. 1992 100 151. 93 P. Gravereau J.P. Charninade T. Gaewdang J. Grannec. M. Pouchard and P. Hagenmuller Acta Crystallogr. Sect. C 1992 48 769. 94 J. Darriet M. Ducau M. Feist A. Tressaud. and P. Hagenmuller J. Solid Stute Chem.1992 98 379. 95 U. Englich W. Massa. and A. Tressaud Acta Crystallogr.. Sect. C 1992. 48. 6. 96 M. Ducau K. S. Suh J. Senegas and J. Darriet. Mat. Res. Bull. 1992 27 11 15. New Compounds and Structures 423 parallel chains of corner-sharing NiF octahedra linked by InF octahedra Figure 15.97The crystal structure of the cobalt Weberite Na,CoAlF is closely related with the CoF chains running parallel in double layers; however between double layers chain directions run at about 60" to each other thus the structure may be considered as intermediate between the orthorhombic Weberite and the trigonal N~M~IA~F,.~~ Figure 15 Perpsective view of Na,NiInF, NiF octahedra ure less heudy shaded than InF octahedra (Reproduced by permission from J.Solid State Chern. 1992 98 121) Two new anion excess Re0,-type structures have been reported PrZr,F ,99 and Pr,Zr,F A number of alkali metal fluoroniobates(Iv) MNb,.,,F, have been prepared;"' these fluoroniobates are isostructural with the alkaline earth hexa- fluoroniobates(rv) ANbF, with 0.25 Nb atoms replacing 0.25 alkali metal atoms which move onto an interstitial site. Both VNbF and VZrF have been found to have a three-dimensional structure built up from corner-sharing Nb/ZrF octahedra related to LiSbF,."* The structure of KYF has been reported to be a fluorite-related superstructure. lo3 New salts of the one-dimensional chain-cation (Ag-F-). AgFBF, AgFAuF, and AgFAuF, have been prepared.lo4 AgFBF has a linear cationic chain but with two slightly different Ag-F interatomic distances.lo4 The crystal structure of Hg,Sb,Br has been solved and can be described as containing (Hg,Sb4)4+ shells and (HgBr,)4 octahedral anions.' O5 ~ A new luminescent oxyfluoride BaNbOF, with a structure closely related to 97 G.Frenzen. W. Massa. D. Babel N. Rucaud. J. Grannec A. Tressaud and P. Hagenmuller. J. Solid State Chem. 1992 98 121. yn P. Gravereau A. Boireau J. M. Dance L. Trut and A. Tressaud. Acra C'rystallogr. Sect. C 1992.48.2108. 99 J. P. Laval and A. Abaouz J. Solid Stare Cheni.. 1992 96,324. 100 J. P. Laval and A. Abaouz J. Solid State Chrm. 1992. 100. 90. 101 D. Bizot J. Chassing L. Legras M. 9. De Bournonville and M. Quarton J. Solid State Chem. 1992,97 150. 102 T. Le Mercier J.Chassaing. D. Bizot. and M. Quarton. Mat. RKS.Bull.. 1992 27 259. 103 Y. Le Fur. K. M. Khaidukov. and S. Aleonard Acta Crystallogr. Sect. C 1992 48 978. 104 W. J. Casteel G. Lucier. R. Hagiwara H. Borrmann and N. Rartlett d. Solid State Chem. 1992. 96 84. 10s A. V. Shevelkov E.V. Dikarev and 9. A. Popovkin. J. Solid State Chem. 1992. 98 133. 424 J. T.S. Irvine KSbF, has been reported.lo6 A new acentric oxyfluoride Ba,TiOF, has been reported.lo7 Its structure is built up from TiO,F octahedra which form kinked chains running along the c axis Figure 16. 0 0 Figure 16 View of the structure of Ba,TiOF showing the trans chains ofTiO,F octahedra (Reproduced by permission from J. Solid State Chem. 1992 99 355) lo6 A.M. Srivasta and J.F. Ackerman Muter. Chem. 1992 4 1011. lo' M. P. Crosnier and J. L. Fourquet J. Solid Stare Chem. 1992 99,355.
ISSN:0260-1818
DOI:10.1039/IC9928900409
出版商:RSC
年代:1992
数据来源: RSC
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Chapter 23. Magnetism |
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Annual Reports Section "A" (Inorganic Chemistry),
Volume 89,
Issue 1,
1992,
Page 425-452
A. Harrison,
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23 Magnetism By A. HARRISON Department of Chemistry University of Edinburgh The King's Buildings West Mains Road Edinburgh EH9 3JJ UK S. J. CLARKE Inorganic Chemistry Laboratory University of Oxford South Parks Road Oxford OX1 3QR UK 1 Introduction This review has a similar form to that of previous years. It is primarily concerned with insulating magnets that show cooperative magnet properties through the influence of superexchange. It does not cover work on metallic elements and intermetallic alloys in any detail,'-5 despite the current focus on heavy-fermion materials6-* such as UM,Si (where M is a transition metal such as Ni9 or Ru") or UBe,,," and on the complex magnetic structure of lanthanide' 2-25 and actinide26 metals and compounds. It does D.Gignoux in 'Materials Science and Technology Vol. 3A Electronic and Magnetic Properties of Metals and Ceramics ed. K. Heinz and J. Buschow VCH Weinheim Germany. 1992 Vol. 3A p. 367. N. H. Duc T. D. Hien P. E. Brommer and J. J. M. Franse J. Magn. Magn. Mar. 1992 104107 1252. V. Sechovsky and L. Havela J. Magn. Magn. Mat. 1992 104-107 7. R. Mueller M. Kuckel and H. U. Schuster J. Alloys Compd. 1991 176 167. B. Johansson L. Nordstroem 0.Eriksson and M. S. S. Brooks Phys. Scr. 1991 T39. 100. ' S. B. Palmer 'Proceedings of the International Conference on Magnetism (Edinburgh) Symposium on Heavy Fermions' J. Magn. Magn. Mat. 1992 108 1. A. De Visser J.J. M. Franse and J. Flouquet J. Magn. Magn. Mat. 1992 108. 15. D.T. Adroja and S. K. Malik J. Magn. Magn.Mat. 1992 100 126. L. Rebelsky H. Lin M. W. Mcelfresh M. F. Collins J. D. Garrett. W. J. L. Buyers and M. S. Torikachvili Physica B 1992 180. 43. lo A. P. Ramirez P. Coleman P. Chandra E. Bruck A.A. Menovsky. Z. Fisk and E. Bucher Phys. Rev. Lett. 1992 68 2680. " A. Devisser N. H. Vandijk K. Bakker J. J. M. Franse A. Lacerda. J. Flouquet Z. Fisk and J. L. Smith Phys. Rev. 8 1992 45 2962. l2 R. M. Moon and R. M. Nicklow J. May. Map. Mar. 1992 100 139. l3 B. Lebech and J. Wolny J. Magn. Magti. Mat. 1992 104-107 1501. l4 E. M. Forgan S.L. Lee W.G. Marshall and D. Fort J. Magn. Mugn. Mat.. 1992 104107. 913. Is J. Jensen and A.R. Mackintosh J. Magn. Magn. Mat. 1992 104-107. 1481. l6 D. A. Jehan D.F. McMorrow. R.A. Cowley and G. J. Mclntyre Europhys.Left. 1992 17 553. I' D. F. McMorrow C. Patterson H. Godfrin. and D.A. Jehan Physica B 1992 180 165. '*M.O. Steinitz D. A. Tindall and M. Kahrizi J. Magn. Magn. Mat. 1992. 104107 1531. l9 H. Lin M. F. Collins T. M. Holden and W. Wei. Phys. Rev. B 1992 45. 2873. *' H. Lin M. F. Collins T. M. Holden and W. Wei J. Magn. Magn. Mat. 1992 104-107 151 1. 21 R.S. Eccleston and S. B. Palmer J. Phys. Cond. Matt.. 1992 4 37. 22 P. M. Gehring L. Rebelsky D. Gibbs and G. Shirane Phys. Rev. B 1992 45 243. 23 C. C. Tang W. G. Stirling D. L. Jones C. C. Wilson P. W. Haycock A. J. Rollason A. H. Thomas. and D. Fort J. Map. Magn. Mat. 1992. 103 86. 24 D. Gibbs J. Magn. Magn. Mat. 1992 104107 1489. 25 E.M. Forgan J. Magn. Magn. Mat. 1992 104107 1485. 26 G. H. Lander and G.Aeppli J. Magn. Magn. Mat. 1991 100 151. 425 426 A. Harrison and S.J. Clarke not consider in detail the nitrogen interstitial corn pound^^^.^^ of iron-lanthanide metal alloys of the form R,Fe ,N such materials and in particular those in which R = Sm show a dramatic increase in T as the nitrogen content increases leading to new permanent magnets whose energy product may exceed that of Nd-Fe-B magnets. The review also ignores much of the remarkable work on thin films that has recently provided model systems to enrich our understanding of exchange mechanisms in metals as well as new materials for recording media in particular those that show giant magnetore~istance.~~ These fields have recently been covered well in the proceedings of international conferences and recent reviews .6930-34 W e will not consider nuclear magnetism despite the fascinating ~ork~~,~~ at pK temperatures on the ordering of nuclear moments in Cu and Ag the antiferromagnetic structures that result from competition between dipolar and RKKY interactions change to ferromagnetic structures at negative-spin temperatures.Throughout the review the isotropic exchange constant J for the coupling between a spin Si and its neighbours Sj will be defined such that the Hamiltonian X for the interaction is x = -J c S;S <ij> Where the sum is taken over all exchange pairs <ij> . The magnitude of J will be expressed in Kelvin as J/k, where k is Boltzmann’s constant. In one- or two-dimensional magnets J denotes the exchange within chains or planes respectively and J’ the exchange between them.The layout of the review is as follows. First there is an account of important meetings reviews and books followed by outlines of advances in experimental and theoretical techniques. New compounds and experimental results will then be described organized according to the type of compound with a broad division into cooperative ionic materials and molecular materials. Within the former category compounds are divided into chain-like (lD) planar (2D),or isotropic (3D)materials and ranked in order of the atomic number of the principal magnetic ion within each subgroup. 2 Major Meetings Books and General Reviews The triennial International Conference on Magnetism (ICM)was held in Edinburgh in 1991 and its proceedings published in 1992.30 It is tempting to direct the reader towards those proceedings and finish the review here.However a large proportion of the contents now appear dated. Further the Conference publicized few new materials because it had a strong bias towards physical measurements and theory and catered primarily for physicists. We hope to redress the balance in sections 5 and 6 of this review. The ICM meeting was accompanied by a meeting on neutron scattering which 21 J.D.M. Coey Phys. Scr. 1991 T39 21. 28 J.M.D. Coey H. Sun and D. P. F. Hurley J. Magn. Magn. Mut. 1991 101 310. 29 R.L. White I.E.E.E. Trans. Magn. 1992 28 2482. 30 S. R. Palmer ‘International Conference on Magnetism (Edinburgh)’.J. Magn. Magn. Mut. 1992 104107 1. 31 A.J. Freeman ‘Magnetism in the Nineties’ J. Magn. Magn. Mat. 1991 100 1. 32 R. W. Chantrell and K. Ogrady J. Phys. D:Appl. Phys. 1992 25 1. 33 A. J. Freeman and R. Q. Wu J. Magn. Map. Mar. 1992 104 107 I. 34 F.J. Cadieu Phys. Thin Films 1992 16 145. 35 P. J. Hakonen K. K. Nummila R.T. Vuorinen and S. Yin J. Magn. Mugn. Mar. 1992 104107 903. 36 P. J. Hakonen K. K. Nurnrnila R. T. Vuorinen and 0.V. Lounasrnaa. Phys. Rec. Lerr. 1992 68,365. Magnetism 427 had a large contribution from workers on magnetism,37 as well as a meeting on heavy-fermionic materials.6 The Journal of Magnetism and Magnetic Materials celebrated its 100th issue with a series of reviews of events over the 17 years since the journal was launched and some speculation about the developments that might occur in the rest of this de~ade.~' Applied magnetism has been the subject of large European38 and Internati~nal~~ meetings.Books on magnetism this year include works on transition metal compounds40 and lanthanide~,~' and amorphous metals and alloys,43 and on on random rnagnet~"~ permanent magnetic materials44 and application^.^^ A further volume of the Landolt-Bornstein Tables has been issued covering inorganic compounds based on transition elements. It describes binary oxides that do not have the spinel garnet or perovskite structure trirutile and pyrochlore oxides hexagonal ferrites and RFe,04 compounds where R is In Sc Y or a lanthanide element.46 3 Experimental Methods The development of experimental techniques has probably been most marked in the area of thin-film and surface magnetism.This is partly due to the intense commercial pressures to produce new devices and partly due to the academic interest in using such systems to model fundamental magnetism. The most spectacular advances have been in the direct imaging of magnetic surfaces at an atomic level using scanning-tunnelling microscopic (STM) technique^.^^,^^ The conventional STM probe may be replaced by a ferromagnetic material such as CrO which sensitizes the electron tunnelling probability to the spin-polarization of the surface being scanned. Probe tips of Fe which are sharp at an atomic length scale have allowed the imaging of the (001) surface of Fe30 and demonstrated the presence of a Wigner glass.Advances in the application of neutron scattering to magnetic problems have been summarized in the proceedings of the triennial International Conference on Neutron S~attering.~~ Over the past few years the value of the technique has been demonstrated through the contribution it has made in unravelling the static and dynamic behaviour of moments in high-temperature superconducting (high- T,) and heavy fermionic 31 K. A. McEwan W. G. Stirling A. D. Taylor. and C. C. Wilson 'Proceedings of the International Conference on Neutron Scattering (Oxford 1991)' Physica E. 1992 18@181 1. 38 S. Kobe and S. Roth 'Proceedings of the 4th European Meeting on Magnetic Materials and Applications' J. May. Map. Mat. 1991 101 I.39 S. Suzuki 'Proceedings of the International Magnetics Conference (Intermag '92)' IEEE 7ran.s. Mayn. 1991 28 I. 40 A. Kotani and N. Suzuki 'Recent Advances in Magnetism of Transition Metal Compounds' World Scientific Singapore. 1992. 41 J. Jensen and A. Macintosh. 'Rare Earth Magnetism Structures and Excitations' International Series of Monographs on Physics OUP Oxford 1991 Vol. 81. 42 D. H. Ryan 'Recent Progress in Random Magnets' World Scientific Singapore 1992. 43 J. A. Fernandez-Baca and W. Y. Ching. 'Magnetism of Amorphous Metals and Alloys' World Scientific. Singapore 1992. 44 S. G. Sankar 'Permanent Magnetic Materials' World Scientific. Singapore 1992. 45 F. Leccdbue and J. L. Sanchez 'Magnetism Magnetic Materials and their Applications Proceedings of the International Workshop Havana'.IOP 1992. 4h 0. Madelung 'Magnetic Properties of Nonmetallic Inorganic Compounds Based on Transition Elements'. Landolt-Bornstein Numerical Data and Functional Relationships in Science and Technology. New Series Springer 1992. Vol. III/27 g. 47 R. Wiesendanger I. V. Shvets D. Burgler. G. Tarrach H. J. Guntherodt. J. M. D. Coey and S. Graser Science 1992 255 583. 4R R. Wiesendanger I. V. Shvets. D. Burgler G. Tarrach H.J. Guntherodt and J. M. D. Coey 2.Phys. B 1992 86. 1. 428 A. Harrison and S. J. Clarke materials in applications to thin-film magnetism and in the determination of the complex spin structures of actinide metals and compounds. A new time-of-flight neutron spectrometer installed at ISIS in the UK and called MART has started to produce spin-wave dispersion curves up to several hundred meV with good spatial and energy res~lution.~~ The analysis of neutron scattering data for disordered magnetic materials may be aided with a reverse Monte Carlo technique similar to those used to elucidate density correlations in structurally disordered material^.^' The study of actinide and lanthanide magnetism and also of thin films and magnetic multilayers is the major beneficiary of advances in magnetic X-ray scattering method^.^' The technique takes various forms.Diffraction experiments with or without the X-ray energy tuned to an atomic absorption edge provides information about the separate contributions of spin and orbital angular momentum to the magnetization about the magnetic character of core to valence electronic transitions and about relative orientations of moment^.^*.^^^^^ The circular dichroism of soft X-rays scattered from surfaces also provides a probe of the magnetic polarization of a surface.Recent experiments involving the Compton scattering of circularly polarized light from the ferromagnet HoF indicate that such measurements probe the spin magnetization which is at variance with the predictions of recent theoretical work.55 Muon spin rotation and relaxation measurements are becoming more common in the wake of the publicity given by prominent experiments on high-T superconduc- and the work by theorists who relate magnetic phenomena to observables in pSR experimen ts.60-6 Advances in various types of susceptibility and magnetization measurements have been reviewed by various authors; perhaps the most significant recent trend is the increased awareness of the low cost and versatility of AC technique^.^^-^* 49 D.Welz M. Arai M. Nishi M. Kohgi and Y. Endoh Physica B 1992 18&181 147. 50 D.A. Keen and R.L. McGreevy J. Phys. Cond. Mutt.. 1991 3 7383. 51 G. H. Lander and W. G. Stirling Phys. Scr. 1992 T45 15. 52 D.B. McWhan J. R. Hastings C. C. Kao and D. P. Siddons. Rev. Sci.Instrum. 1992 63 1404. 53 V. Nunez P. J. Brown J. B. Forsyth and F. Tasset Physica B 1991 174,60. 54 M. J. Cooper E. Zukowski S. P. Collins D. N. Timms F. Itoh and H. Sakurai J. Phys. Cond. Mutt. 1992 4,L399. 55 S. W. Lovesey Phys. Scr..1991 44. 51. 56 C.E. Gough Springer Proc. Phps. (Exot. At. Condens. Mutter) 1992 59.259. 57 H.Keller Springer Proc. Phys. (Exct. At. Condens. Mutter) 1992 59 191. 58 E. M. Forgan Springer Proc. Phys. (Exct. At. Condens. Matter) 1992. 59,285. 59 C. Bucci Sol. State Commun. 1992 84 191. ‘O Y. Aoyama and M. Tanaka Phys. Stat. Sol. B 1992 171,K107. 61 S.W. Lovesey. Hyperfine Int. 1992 72,389. 62 R. Saito H. Kamimura and K. Nagamine Physica C 1991 185,1217. 63 T. Yamazaki Kotai Butsuri. 1991 26,688. 64 Q.Y. Chen in ‘Magnetic Susceptibility of Superconductors and Other Spin Systems (Proc. Off. Nav. Res. Workshop’ ed. R. A. Hein T. L. Francavilla and D. H. Liebenberg Plenum New York 1991 p. 81. 65 A. M. Campbell in ‘Magnetic Susceptibility of Superconductors and Other Spin Systems (Proc.Off. Nav. Res. Workshop)’,ed. R. A. Hein T. L. Francavilla and D. H. Liebenberg Plenum New York 1991 p. 129. ‘‘ F. Gomory in ‘Magnetic Susceptibility of Superconductors and Other Spin Systems (Proc. Off. Nav. Res. Workshop)’ ed. R. A. Hein T. L. Francavilla and D. H. Liebenberg Plenum New York 1991 p. 289. ” J. H. Claasen in ‘Magnetic Susceptibility ofSuperconductors and Other Spin Systems (Proc. Off. Nav. Res. Workshop)’ ed. R. A. Hein T. L. Francavilla and D. H. Liebenberg Plenum New York 1991 p. 405. 68 G. Williams in ‘Magnetic Susceptibility of Superconductors and Other Spin Systems (Proc. Off. Nav. Res. Workshop)’ ed. R. A. Hein T. L. Francavilla. and D. H. Liebenberg Plenum New York 1991 p. 475. Magnetism 429 The sample environment is an important component of many magnetic experiments and tempera- the provision of high pressures in AC susceptibility rneas~rements~~”~ tures of the order of 10-9K for susceptibility and neutron scattering measure- ment~~’.~~ have been described.4 Theoretical Work For the past few years experimentalists and theorists have worked closely on low-dimensional low-moment magnets with various degrees of magnetic frustra- ti~n.~’ The initial stimulus for this work was provided by the magnetic properties of the high-T,ceramics which are S = 3square Heisenberg antiferromagnets with competing first second and third nearest-neighbour antiferromagnetic interactions J, J, and J,. It was initially believed that their magnetic ground state is a quantum spin fluid or a Resonating Valence Bond state but a classical ground state is now favoured albeit with a significantly reduced ordered moment recent work has consolidated this belief.72 These cuprates are also very sensitive towards dilution by holes which place frustrating ferromagnetic bonds in the lattice.The mobility of the holes has been shown to disrupt the ground state f~rther,~,,~~ softening and damping spin-waves and increasing nuclear spin relaxation rates for the constituent atoms. The spin fluctuations in low-moment frustrated magnets seem to have an energy scale that is set by the temperature rather than by microscopic factors such as the exchange energy. It has been shown that this behaviour is to be expected of a magnet that lies near the boundary between classical ordered and quantum disordered phases as it is cooled from the phase at higher temperatures which is termed the quantum critical state.75 Models for high-T materials have been made more elaborate by the addition of more complex four-spin cyclic exchange interactions around the square plaquettes.Such terms which are known to occur in the Hubbard model produce a variety of collinear canted and dimerized phases,7h depending on their values relative to J and J,. There has been a healthy debate for some years now about the role of low-energy magnetic fluctuations in the coupling of charge carriers in the high- T superconduc-tors and it had previously been believed that the strength of the coupling was too weak to account for the relatively high value of T,.Recent calculations indicate that it is very important to take full consideration of the frequency and momentum distribution of the quasiparticle interaction. When this is done the predicted value for T,rises to be of the same order as the experimental value. There is a prediction that if this mechanism is responsible for the coupling the paired state must have d, -yz symmetry.77 It has also been shown that the fluctuations must be about the commensurate wave vector rather than the incommensurate vector otherwise the coupling mechanism is s~ppressed.~~ h9 ‘Magnetic Susceptibility of Superconductors and Other Spin Systems (Proc. Off. Nav. Res. Workshop)’ ed. R. A. Hein T. L. Francavilla and D. H. Liebenberg.Plenum New York. 1991. ’” ‘Frontiers of High Pressure Research’. ed. S. Klotz. J. S. Schilling. and P. Mueller NATO AS1 Series B Plenum 1991 Vol. 286 p. 473. ” B.I. Halperin J. Magn. Muyn. Mut.. 1992 104-107. 761. 72 H.Q. Lin and D. K. Campbell Phys. Ret’.Letr. 1992 69 2415. ’’ J. M. F. Gunn M. J. Godfrey and B. D. Simons J. Map. Mayn. Mut. 1992. 104107. 465. 74 I. R. Pimentel and R. Orbach Phjs. Re?. B,1992 46 2920. 75 S. Sachdev and J. Ye Phys. Rec. Lett. 1992 69 2411. 76 A. Chubukov E. Gagliano and C. Balseiro Phys. Rev. €3 1992. 45 7889. 77 P. Monthoux and D. Pines. Phjs. Rrr. Lett. 1992 69 961. ” A.V. Chubukov Ph-vs. Rev. B 1992 46 5588. A. Harrison and S. J. Clarke The most likely candidate for a magnet with a non-classical ground state that is also realized in nature is the Kagome antiferromagnet whose lattice is depicted in Figure l(a).The classical case with a variety of first second and third neighbour exchange interactions has been studied th~roughly’~ and it looks as though one of two Nee1 states may form at low temperatures. For J2 > J the so-called q = 0 state depicted in Figure 1(b) is favoured while the J3 x 43phase depicted in Figure 1(c) is stabilized for Figure 1 (a) The Kagome latrice and two dtferent spin arrays (b)the q = 0 state and (c) the J3 x J3 state J < J,. Small amounts of diamagnetic impurity will rapidly disrupt the ordered ground state and produce spin-glass phases. Calculations for n-component vector spins (n = 1 2 and 3 correspond to Ising XY and Heisenberg magnets respectively) indicate that the Ising magnet is disordered at T = 0.80Monte Carlo simulations and spin-wave calculations for the classical case indicate that thermal fluctuations favour spin configurations that are coplanar and select a ‘hidden’ type of spin order in which the order parameter is a correlated twist in the spins and is termed a spin nematic.81 There is a different manifestation of ‘order from disorder’ when the effect of quantum fluctuations on the ground state of such a magnet is con~idered.~~.~~ Quantum fluctuations lift the degeneracy of the classical ground state and restore long-range order at T = 0 even when J = 0.A new energy scale for the spin-wave velocity is produced which is a factor S-1’3 smaller than that predicted by conventional spin-wave theory.The heat capacity is predicted to adopt the form C(T)-(T/JS)2-S213at low temperatures in agreement with experimental observation^.^^ When the spins are small there is a quantum disordered ground state and no magnetic long-range order.83** The triangular Heisenberg antiferromagnet with nearest-neighbour or next-nearest- neighbour exchange also continues to attract theoretical attention. The concensus appears to lie with an ordered ground state for the S = 4case,83,85-86 though the ordered moment is thought to be very low. Thermal fluctuations also provide an ordering influence in the classical Ising-Heisenberg case quadratic fluctuations 79 A. B. Harris C. Kallin and A. J. Berlinsky Phys. Rev. B 1992 45 2899.8o D.A. Huse and A. D. Rutenberg Phys. Rev. B 1992 45 7536. ” J.T. Chalker P.C. W. Holdsworth and E. F. Shender Phys. Rev. Lett. 1992 68 855. 82 A. Chubukov Phys. Rev. Lett. 1992 69 832. 83 S. Sachdev Phys. Rev. B 1992 45 12377. ‘4 A. P. Ramirez G. P. Espinosa and A. S. Cooper Phys. Rev. B 1992 45 2505. ‘5 R. R. P. Singh and D.A. Huse Phys. Rer. Lett. 1992 68 1766. 86 B. Bernu C. Lhuillier and L. Pierre Phys. Rev. Lett. 1992. 69 2590. Magnetism 431 preserve the continuous ground state degeneracy but higher-order terms particularly with long wavelengths lift this degenera~y.~~ The pyrochlore lattice (Figure 2) has been described as a three-dimensional form of the Kagome lattice and the frustration produces only short-range order.This has been observed experimentallys8 and predicted from mean-field calculations and Monte Carlo simulation^.^^ The form of the powder neutron diffraction profiles for the magnetic scattering for this class of magnet as well as Kagome and rhombohedra1 cases has been simulated for a variety of temperatures. The diffuse scattering profiles could be matched with experimental profiles for certain values of exchange constants providing a method for their determination.” Figure 2 The pyrochlore lattice represented by uertex-sharing tetrahedra with the magnetic atoms at eiiery vertex Theoretical work on 1D magnets continues to be dominated by Haldane’s conjecture7’ and the study of the dynamic and static properties of pure and dilute 1D S = 1 antiferromagnets.Theory for ESR measurements on diamagnetically dilute forms of the magnet treats the broken chain ends as species with S = $ and adequately treats measurements on NENP (see section 5 under nickel compo~ndsj.~~ The magnetic excitations at the Brillouin zone centre (Q = 0) as opposed to the antiferromagnetic wavevector (Q = n) where the singlet-triplet gap is usually measured are predicted to give rise to a rounded peak in the structure factor S(Q,w) at an energy just above the two-magnon threshold.92 Spin-wave dispersion in 1D antiferromagnets such as the hexagonal perovskites CsNiC1 and RbNiCI, in which there is also frustration between the magnetic chains has been recognized to conform badly to linear spin-wave theory. New treatments of spin-wave dispersion using a Lagrangian formalism predict an additional longitudinal mode parasitic to the transverse modes and this accounts for some of the anomalous beha~iour.~,.~~ ’’ Q.Sheng and C. L. Henley J. Phys. Cond. Matt.. 1992 4. 2937. 88 B. D. Gaulin J. N. Reimers T. E. Mason. J. E. Greedan and Z. Tun Phys. Rev. Lett. 1992 69 3244. 89 J.N. Reimers Phys. Rev. B 1992. 45 7287 90 J.N. Reimers Phys. Rep. B 1992 46 193. 9’ P. P. Mitra B.I. Halperin and I. Affleck. Phys. Rev. B 1992 45 5299. 92 I. Affleck and R.A. Weston Phys. Rec. B 1992,45 4667. y3 M. L. Plumer and A. Caille Phys. Rev. Left. 1992 68,1042. 94 I. Affleck and G.F. Wellman Phys. Rev. B 1992 46 8934. 432 A. Harrison and S.J. Clarke The theory of magnetic X-ray scattering" and of muon spin-rotation and relaxation in fluctuating magnetic systems has been as has the theory of inelastic neutron spectroscopy for PrI*l and Tm"' which provides a probe for the magnetic wavef~nction.'~ The role of double exchange9' in magnetic solids has been reviewed and attention has been drawn to a special case of the Dzyaloshinsky-Moriya intera~tion.~~ When frustration is present the weak ferromagnetic moment that would arise from antisymmetric exchange adopts a unique orientation.Symmetric and antisymmetric exchange are shown to be important in determining the complex spin structure of the monophosphides of Mn and Fe and the monoarsenides of Cr and Mn.99 Work on the theory of magnetic interactions in molecular species is mainly concerned with the search for better organic ferromagnets,' O0 and is divided between work on nitronyl nitroxides' O3 and charge-transfer salts containing metallo- cene~.'~~-'~~ Magnetic interactions in three-centre four-electron clusters,'07~'08 in several types of iron-sulphur clusters,'09 and in manganese cubane clusters' lo have also been considered.Theoretical work on spin-glasses and random-field magnets' '' is not as prominent as it used to be. Reviews of aspects of spin-glasses have been produced covering re-entrant systems,' '' stretched-exponential relaxation for long-range processes in disordered materials,' ' and applications to neural networks.' l4 Monte Carlo simulations continue to be added to the repertoire of theorists though some would argue that the technique could be classed as an experimental one.' '' Progress stems partly from the rapid improvement in computer hardware and installation of algorithms on vector processors,' ' though this may create new problems in the form of the failure of random number generators to maintain randomness in long simulations.* ' There have also been improvements to algorithms problems concerning non-ergodicity have afflicted simulations of spin-glasses for some 95 M. J. Cooper Acta Phys. Pol. A 1992 82 137. 96 E. Balcar and S. W. Lovesey J. Phys. Cond. Matt. 1992. 4. 2271. 97 G. Blondin. S. Borshch and J.J. Girerd. Comments Inorg. Chem. 1992 12 315. 98 L. Shekhtman 0.Entin-Wohlman and A. Aharony Phys. Re].. Lett. 1992 69. 836. ')'J. Sjoestrom J.Phys. Cond. Mutt. 1992 4 5723. loo T. P. Radhakrishnan Curr. Sci. 1992 62 669. I01 K. Yamaguchi M. Okumura. J. Maki T. Noro. H. Namimoto. M. Nakano T. Fueno and K. Nakasuji. Chem. Phys. Lett.. 1992 190 353. lo' K. Yamaguchi M. Okumura and M. Nakano Chem. Phys. Lett. 1992. 191 237. lo' R.N. Musin P.V. Schastnev and S.A. Malinovskaya Inorg. Chem.. 1992 31. 41 18. A. L. Tchougreeff and I. A. Misurkin. Phys. Rev. B 1992. 46 5357. Io5 A. L. Tchougreeff J. Chrm. Phys. 1992 96 6026. 106 K. Yamaguchi. M. Okumura T. Kawamura T. Noro. and K. Nakasuji Mol. Cryst. Liq. Crq'st. Sci. Techno/. A. 1992 218 229. J. R. Hart A. K. Rappe. S.M. Gorun and T. H. Upton J. Phys. Chrm. 1992. 96 6255. lo' J.R. Ilart. A. K. Rappe S. M. Gorun and T. H. Upton. J. Phys. Chem.1992 96 6264. 109 L. C. Noodleman and A. David Adc. Inorg. Chem.. 1992 38 423. E.A. Schmitt L. Noodleman. E. J. Baerends and D. N. Hendrickson J. Am. Chem. Soc. 1992 114,6109 'I1 D.P. Belanger and A.P. Young J. Map. Matn. Mat. 1991 100 272. 112 I. A. Campbell and S. Senoussi. Phil. Mug. R 1992. 65. 1267. 'I3 J. Souletie Phil. Mug. B. 1992. 65. 1311. D. Sherrington M. Wong and A. Rau Phil. Mq. B 1992 65 1303. 'The Monte Carlo Method in Condensed Matter Physics'. ed. K. Binder Topics in Applied Physics Springer Berlin 1992 Vol. 71. '" D.P. Landau in 'The Monte Carlo Method in Condensed Matter Physics'. ed. K. Binder. Topics in Applied Physics Springer Berlin. 1992. Vol. 71. p. 23. 'I7 A.M. Ferrenberg. D. P. Landau and Y. J. Wong. Phys. Rrr. Ixtt..1992. 69. 3382. Mag net ism 433 time and new work should facilitate extension of simulations to lower tempera- tures,' '* and reduce relaxation times.' ' Improvements have been made to techniques for randomly disordered solids allowing faster determination of transition tempera- tures and critical exponents.12' A new algorithm has been developed to tackle the problem of trying to perform simulations for incommensurate magnetic structures while applying reasonable boundary conditions.' 5 Cooperative Magnetism in Ionic Solids Onedimensional Magnets.-The majority of work in this area still concerns Haldane's Conjecture and is described under chain-like compounds of nickel.' 22 There are few new materials even among the organic chain compounds discussed in section 6.Vanadium. RbVBr has a slightly distorted CsNiC1 structure and shows two long-range magnetic-ordering transitions on cooling.' 23 The first appears to have a collinear ferrimagnetic alignment of moments parallel to the chain axis with a small perpendicular ferromagnetic component that is attributed to a Dzyaloshinsky-Moriya interaction; the second shows a large hysteresis and is believed to be to a triangular structure with no ferromagnetic component. A new polymorph of LiVOPO has been synthesized and shown to contain vertex-sharing chains of VO octahedra crosslinked through PO bridges.' 24 The magnetic susceptibility was treated with the Bonner- Fisher model for a 1D S = 4 Heisenberg antiferromagnet. Corner-sharing VO chains are also found' 25 in the 1D antiferromagnet VO(H,AsO,),.Chromium. The quasi 1D antiferromagnet tetramethylammonium chromium(1r) trichloride has a transition to a 3D ordered state at T = 5.8K.12 Manganese. Over the past few years the hexagonal perovskite CsMnBr has provided a model hexagonal antiferrornagnet for the study of the new type of ordered magnetic phase that is expected when frustration and continuous (i.e.not Ising) spin symmetry are combined. The transition between the paramagnetic and chiral phases is tetracritical because the application of a magnetic field to the hexagonal basal plane produces an intermediate spin-flop phase. Measurements of the spin dynamics at the tetracritical point indicate that the critical exponent z adopts a value close to that for a conventional antiferrornagnet.' 27 Other workers have considered the effect of tilting the applied field away from the basal plane.'28 The introduction of a small in-plane lattice distortion upsets the balance of exchange forces within the plane.Such an effect occurs in RbMnBr and leads to an incommensurate magnetic structure which has been studied through linear birefringence measurements. '29 'I8 B. A. Berg and T. Celik Phys. RcL..Lett.. 1992 69 2292. 'Iy S. Liang Phys. Rev. Lett. 1992. 69 2145 120 A. J. F. de Souza and F.G. Brady Moreira Europhys. Lett.. 1992 17 491. 12' W. M. Saslow M. Gabay and W. M. Zhang Phys. Rev. Lett.. 1992 68. 3627. L22 K. Kakurai. Physicu B. 1992. 180 153. lZ3 H. Tanaka T. Kato K. Iio and K. Nagata.J. Phys. Soc. Japan 1992 61 3292. 124 K. H. Lii C. H. Li C. Y. Cheng. and S.L. Wang J. Solid State Chem. 1991 95,352. 12s P. Amoros A. Beltranporter G. Villeneuve. and D. Beltranporter Eur. J. Solid State Inory. Chem.. 1992 29. 257. 12h C. Bellitto L. P. Regnault and J. P. Kenard J. Magn. Mayn. Mut. 1991 102 116. 127 T.E. Mason. Y.S. Yang M.F. Collins B.D. Gaulin K.N. Clausen and A. Harrison J. Mayn. Magn. Mat.. 1992. 104-107. 197. I28 S. I. Abarzhi. A. N. Bazhan L. A. Prozorova and I.A. Zaliznyak J. Phys. Cod. Matt. 1992 4. 3307. 120 T. Kato. K. Iio T. Hoshino. T. Mitsui and H. Tanaka. J. Phys. Soc. Japan 1992. 61 275. 434 A. Harrison and S.J. Clarke Chains of vertex-sharing MnF octahedra are found13* in the new 1D S = 2 antiferromagnet Tl,MnF,-H,O; below TN= 27 1 K,3D antiferromagnetic order sets in.TIMnF,-H,O is a new 1D antiferr~magnet.'~~ It contains zig-zag chains of alternating MnF octahedra and Mn(H,O),F sharing trans corners; magnetic susceptibility data may be fitted to an isotropic Heisenberg model with S = 2 and J = -3.9K. The small value of exchange is attributed to the relatively small Mn-F-Mn bridging angle of 138'. The isomorphous compounds MnXO,.D,O (X = P As) behave as Curie-Weiss paramagnets at high temperatures and order antiferromagnetically at 33 and 24K with ordered moments of 3.52(5) and 3.54(5)pB for the X = P and As compounds respectively.'32 Their structure may be regarded from a magnetic viewpoint as based on chains of Mn-0-Mn units. Axially-distorted MnO octahedra are linked through their vertices to form zig-zag chains which in turn are linked through the phosphate groups to form a 3D network.The compound MnMn(CDTA)-7H20 (CDTA is the tetra anion of trans-cyclo- hexane-1 ,2-diarnine-N,N,N',Nf-tetraacetic acid) contains chains of dimeric manganese molecules connected through carbolate bridges (J as depicted in Figure 3;'33 Mna--Mna--Mna--ana--J1 Figure 3 Exchange pathways in MnMn(CDTA).7H20 alternatively it may be regarded as a chain of exchange-coupled triangles which share corners. Magnetic susceptibility measurements were successfully interpreted with a frustrated chain model with sites a and b connected through three different exchange constants. MnCu(obze)(H,O) [obze = oxamido(N-benzoato-N'-ethanoato) and MnCu(pbaOH)(H,O) (pbaOH = 2-hydroxy-1,3-propylenebis(oxamato)]behave as ferrimagnets.34 Antiferromagnetic exchange propagates through 0-carboxylato bridges to produce values for T,of 4.6and 30K for the two materials the latter being a record for a molecular-based magnet. Iron. The hexagonal perovskites AFeX (A = Rb NH, Cs and T1; X = CI Br) provide good examples of induced moment magnets. The isolated Fe" ions have a singlet ground state but exchange with neighbouring ions may mix in a low-lying excited doublet to produce a moment if the ratio of exchange to singlet-doublet 130 P. Nunez A. Tressaud J. Darriet. P. Hagenmuller G. Hahn,G. Frenzen W. Massa D. Babel,A. Boireau. and J. L. Soubeyroux Inory. Chem. 1992 31. 170. 13' P.Nunez A. Tressaud F. Hahn W. Massa D. Babel A. Boireau and J. L. Soubeyroux Phys. Stuf.Solidi 1991 127. 505. 132 M.A.G. Aranda J. P. Attfield S. Bruque and F. Palacio. J. Muter. Chem. 1992 2. 501. 133 J. J. Borras-Almenar E. Coronado J. C. Gallart R. Georges and C. J. Gomez-Garcia J. Magn. Magn. Mut. 1992 104-107 835. 134 E. Codjovi. P. Bergerat K. Nakatani P. Yu and 0.Kahn J. Mugn. Mugn. Mat. 1992. 104107. 2103. Magnetism 435 splitting is sufficiently large or if an external magnetic field is applied. The relation between structure and magnetism has been reviewed135 and the dispersion of magnetic excitations in RbFeBr has been used to test theories of excitations in this class of magnet.' 36 A variety of effective Hamiltonians have been tested against quadrupole- splitting data taken from Mossbauer measurements for AFeX (A = Rb Cs; X = C1 Br).'37 CsFeBr remains a singlet ground-state material down to zero Kelvin'38 but long-range magnetic order may be induced by a magnetic field of 4.1 T.'39 The dispersion of spin-waves in the 1D Heisenberg antiferromagnet KFeS has been measured out to the Brillouin zone boundary energy of 221(4)meV using the new time-of-flight spectrometer MAR1 at ISIS.14' This value is far greater than that obtained from extrapolation of measurements taken with a conventional spectrometer at lower energies nearer the zone centre.TlFeS is a 1D Heisenberg antiferromagnet with a small degree of dimerization within the chain of low-spin Fe"' ions.141 Careful neutron and SQUID magnetometry measurements on single crystals indicate no evidence for singlet formation within the dimeric units and that the moments are greatly reduced through covalency.Cobalt. CsCoX (X = C1 Br) continues to provide a good model S = $ Ising antiferrornagnet.l4' The role of solitons in and between the different ordered phases of pure and diamagnetically-doped samples has been studied by neutron scattering 143 muon or ' spin rela~ation,'~~~~~~ or high-field differential magneti~ation,'~~ magneto-optical measurements. 47 The pseudo 1D Ising antiferromagnetic [(CH,),NH]Co -.Ni,CI shows a transition to 3D long-range canted antiferromag- netic order'48 with a critical exponent /3 = 0.306. Compounds doped with Ni" were also studied in the belief that a re-entrant spin-glass phase might be found at low temperatures and intermediate compositions but no clear evidence of such a phase could be found.Co2(EDTA).6H,O and CoCu(EDTA)-6H20 are two of a series of compounds with general formula MM'(EDTA).6H20 which contain zigzag chains of alternating hydrated and chelated -M(H,O),O,-M'(EDTA)-. EPR measurements of Co-doped compounds in which MM' = (Zn) and the bimetallic compound with MM' = CoCu provide estimates of the g-tensors of both metal ions and indicate that there is dimerization of Co-Cu exchange coupled pairs within the chains.' 50 135 D. Visser and A. Harrison J. Magn. Magn. Mat. 1992 116 80. 136 A. Harrison and D. Visser J. Phys. C 1992 4 6977. 13' V. H. McCann J.A. Laban and N. Sheen Hyperfine Int.1992 71 1363. 13' B. Schmid B. Dorner D. Visser and M. Steiner Z. Phys. B. 1992 86 257. 139 B. Schmid B. Dorner D. Visser and M. Steiner J. Mugn. Map. Mat. 1992 104107 771. I4O D. Web M. Kohgi Y. Endoh M. Nishi and M. Arai Phys. Rw. B 1992 45 2319. I4l D. Welz and M. Nishi. Phys. Reu. B 1992 45 9806. 14' J.A. Laban and V.H. McCann Hyperjine Int. 1992 71 1367. 143 K. Okuda S. Noguchi K. Konishi H. Deguchi and K. Takeda J. Map. Magn. Mat. 1992 104-107 817. '44 M. Mekata S.Onoe H. Kuriyama B. J. Sternleib Y. Uemura and K. Nagamine J. Magn. Map.Mat. 1992. 104-107 825. 145 T. Kohmoto,T. Goto S. Maegawa N. Fujiwara Y. Fukuda M. Kunitomo,and M. Mekata Phys. Lett.A 1992 167 493. 146 H. Hori H. Mikami M. Date Y. Ajiro and N. Mori J. Magn. Magn.Mat. 1992 104107 815. 14' H. Hori H. Mikami and M. Date Physica B 1992 177 363. 148 T. Bruckel W. Prandl and K. Hagdorn J. Magn. Map. Mat. 1992. 104107 1629. '49 E. Coronado J. Chrrn. Phys. 1991 88. 2167. J.J. Borras-Almenar E. Coronado. D. Gatteschi and C. Zanchini Inorg. Chem. 1992 31. 294. 436 A. Harrison and S. J. Clarke A new double-chain compound has been ~repared'~' in the form of CO(OH)(NO,).H,O.~~~ Susceptibility measurements indicate that the coupling between S = $ Ising spins may be described in terms of two nearest-neighbour in-chain antiferromagnetic exchange constants J = 22.8 K and J = 9.75 K; interchain exchange of the order of 0.2 K leads to 3D magnetic long-range order below about 2.5 K. Nickel. Chain-like compounds of Ni" continue to provide the most extensive source of model materials with which to test Haldane's Conjecture it has been proposed that 1D Heisenberg antiferromagnets composed of integral spins have a non-classical ground state and excitations.The effect becomes more pronounced as the moment decreases hence the interest in S = 1 1D antiferromagnets with small single-ion anisotropy. The majority of work concerns Ni(C2H,N,),N0,C104 (NENP) and the related materials Ni(C3HloN2),(C104) (NINO) Ni(C,HloN,),N,(C104) (NINAZ) and Me,NNi- (NO,) (TMNIN)." The application of a strong magnetic field (-10T) to single crystals of NENP and NINO closes the gap in energy between the ground state and the first excited state and provides a value for both the Haldane gap and crystal field parameters.' 53 Similar measurements on TMNIN and NINAZ provide estimates of their gap energy.'54 NENP has been the subject of inelastic neutron scattering measurements of the magnetic correlation length'" and its response to applied magnetic fields'56 as well as magnetic susceptibility,'" heat capacity,'58 ESR,'59,'60 and muon spin relaxation measurements of the fluctuations in the magnetic moments.'61*'62 These appear to confirm that the excitations are to a state with S = 1 and also that when the magnetic chains are broken the free ends behave as though the moments on Nil' have S = $.This last result which is also difficult to understand with a classical picture of localized moments coupled through exchange forces confirms the belief that the moment of S = 1 on a localized Ni" site is best regarded as the symmetric part of two species with S = 4.'63,164 The application of Haldane's theory to CsNiC1 and RbNiC1 runs into difficulties on account of their 1D character.16sp' 69 Detailed neutron scattering measurements of S.Angelov M. Drillon E. Zhecheva R. Stoyanova M. Belaiche A. Derory. and A. Herr Inorg. Chrm. 1992 31 1514. L52 K. Kindo T. Takeuchi T. Yosida and M. Date Physica B 1992 177 381. 153 T. Takeuchi H. Hori T. Yosida Y. Akio. K. Katsurnata. J. P. Renard. V. Gadet M. Verdaguer and M. Date J. Phys. SOC.Japan 1992 61 3251. 154 T. Takeuchi H. Hori T. Yosida. A. Yamagishi K. Katsurnata J. P. Renard V. Gadet M. Verdaguer and M. Date J. Phys. SOC.Japan 1992 61 3262. Is5 L.P. Regnault J. Rossat-Mignod and J. P. Renard J. Magn. Magn. Mar.. 1992. 104107 869. L. P. Regnault C. Vettier J. Rossat-Mignod and J. P. Renard Physica B. 1992 18Q-181 188. 15' 0.Golinelli T. Jolicoeur. and R. Lacaze Phys. Reu. B 1992. 45 9798. 158 T. Kobayashi Y. Tabuchi K. Amaya Y. Ajiro,T. Yosida and M. Date,J. Phys. Soc.Jupan 1992.61 1772. 159 L. C. Brunel T. M. Brill I. Zaliznyak J. P. Boucher and J. P. Renard Phys. Reu. Lett. 1992 69 1699. 160 M. Hagiwara and K. Katsurnata. J. Phys. Soc. Japan. 1992 61. 1481. 16' B. J. Sternlieb L. P. Le G.M. Luke W. D. Wu Y. J. Uernura T. M. Riseman J. H. Brewer Y. Ajiro and M. Mekata J. Map. Magn. Mat. 1992 104-107 801. 162 M. Motokawa H. Nojiri K. Nishiyama K. Nagamine and T. Yosida. Physica B 1992 177 389.I63 M. Hagiwara K. Katsumata J.P. Renard. I. Affleck and B. I. Halperin J. Magn. Map Mat. 1992 104107 839. 164 M. Hagiwara K. Katsumata. H. Hori T. Takeuchi M. Date A. Yamagishi J. P. Renard and I. Affleck Physica B 1992 177 386. 165 L. S. Carnpana A. Caramico D'Auria F. Esposito U. Esposito and G. Kamieniarx Phys. R~G. B.. 1992 45 5035. K. Nakajima,K. Kakurai H. Hiraka,H.Tanaka K. Ito,and Y. End0h.J. Phys. Soc.Japun,1992,61,3355. Magnetism 437 the excitations in CsNiC1 in an applied magnetic field have been used to deduce which components of the spins fluctuate in the various dispersion curves and although in agreement with Affleck's extension of Haldane's theory to coupled chains a more conventional interpretation cannot be ruled out.A comparison between these and the non-integral-spin antiferromagnet CsMnI has been made with aid of quasi-elastic neutron scattering measurements of the dependence on temperature of the magnetic correlation length. It indicates that there is a difference between the two types of magnets with the integral-spin materials showing a finite correlation length at T = 0.170 Hexagonal perovskites of the form ANiX (A = Rb Cs; X = F C1 Br) provide models for the study of magnetic phase transitions in frustrated magnets' 73 and of solitons.' 74 CsNiI shows a magnetic susceptibility that indicates itinerant electrons rather than localized spins.' 74 The lanthanide nickelates Ln,BaNiO (Ln = Y Nd-Gd and Dy-Tm) contain isolated chains of flattened NiO octahedra.Magnetic susceptibility measurements on compounds with Ln = Nd Eu Dy and Ho indicate 1D behaviour involving Ni" above room temperature and 3D ordering at temperatures between 10K and 44K depending on Ln. '75 Chain-like structures containing Ni-0-0-Ni exchange path- ways are found in NiSb,O and susceptibility data could be fitted to a 1D Heisenberg model with J -45 K.'75 Copper. The ID S = $ Heisenberg antiferromagnet KCuF has been studied by high-energy inelastic neutron scattering measurements.' 76 These show that even the gross features of the dispersion of magnetic excitations can only be described with a model that takes account of quantum effects. Magnetic susceptibility measurements on salts derived from CuX (X = C1 Br) indicate various types of low-dimensional magnetism CuCl,.DMSO appears to be a 1D S = 5 Heisenberg ferr~magnet,"~ (piperazinium),CuCl,.CH,OH may be a weak 1D antiferrornagnet as is (1,2- dimethylpyridinium),Cu,Br, which is composed of trimers of moments with ferromagnetic exchange within trimers and antiferromagnetic coupling between them.'78 Zig-zag chains of Cu" ions are found in the new 1D ferromagnet CuL(H,O) (H,L = 1,3-dimethyl-5-((2-carboxyphenyl)azo)barbituric acid).' 79 The high-ir superconducting ceramic YBa,Cu,O contains both layers and +X chains of coupled moments on Cu".The magnetic properties of Ca,CuO, which 16' M. Enderle K. Kakurai M. Steiner and B. Dorner Physica B 1992 18(t-181. 233. IhHM. Enderle K. Kakurai M. Steiner and H. Weinfurter. J. Mayn.Mayn. Mat. 1992 104-107 809. I69 W. J. L. Buyers Z. Tun A. Harrison J.A. Rayne and R. M. Nicklow Physicu B 1992 180 181 222. "" K. Kakurai K. Nakajima Y. Endoh K. Iio H. Tanaka and M. Steiner. J. Mayn. Mayn. Mar. 1992 104-107 857. 171 Y. Oohara. K. Lo H. Tanaka and K. Nagata J. Phys. Soc. Japan 1991. 60. 4280. "'S. Maegawa T. Kohrnoto T. Goto and N. Fujiwara. Phys. Rw. B 1992 44. 12617. T. Mitsui. K. Abe and K. Lo J. Magn. Map Mat. 1992. 104-107 819. T. Delica W.J. M. DeJonge K. Kopinga H. Leschke and H. Mikeska J. Magn. Mayn. Mat. 1992. 104107 795. R. Saez-Puche. J.M. Coronado. J. M. Martin-Llorente and I. Rasines. Mat. Chrm. Phys. 1992,31 151. I76 S. E. Nagler D.A.Tennant R.A. Cowley T.G. Perring and S. K. Satija. Phys. Reu. B 1991.44. 12361. li' K.Ravindran and J. E. Drumheller J. Mugn. Magn. Mat. 1992 104-107. 833. T. E. Grigereit Y. Liu P. Zhou J. E. Drumheller. A. Bonomartini-Corradi M. R. Bond H. Place and R. D. Willett J. Map. Magn. Mat. 1992 104-107 831. ''' E. Colacio J. M. Dominguez-Vera J. P. Costes R. Kivekas J. P. Laurent. J. Ruiz. and M. Sundberp. Inory. Chem. 1992 31 774. A. Harrison and S. J. Clarke contains a similar type of chain of coupled moments have been interpreted using a 1D Heisenberg antiferromagnetic model which indicates no magnetic moments; the same scientists studied Li2Cu04 which has Cu-0,-Cu chains with 90" exchange angles and show that it contains ferromagnetically coupled chains of moments which freeze to 3D antiferromagnetic order below 9.3 K.'" Two-dimensional Magnets.-Much of the interest in 2D systems in recent years has centred around the layered cuprate ceramic superconductors and associated with this the possibility of attaining a quantum ground state in a frustrated low-moment system such as a triangular or Kagome lattice as discussed in section 4.Titanium. NaTiO remains the most promising candidate for an S = triangular Heisenberg antiferromagnet but is dogged by difficulties in sample preparation. Recent work suggests that the pure material undergoes a magnetic phase transition at 260 K but there is no evidence for long-range antiferromagnetic order. la' Chromium.The garnet SrCr,Ga -,O remains the only Kagome system that has been investigated in any detail,a4 but has the disadvantage of incomplete occupancy of the Kagome planes.Heat capacity measurements indicate an unusual dependence on temperature ofthe form T2,which corresponds to the predictions of theoretical work.82 Rb,Cr,Mn -,Cl is a mixed easy-axis-easy-plane and mixed ferro-antiferromag- netic material which has been studied for several years as a spin-glass. Raman182 and FIR' 83 measurements confirm ferromagnetic long-range order for chromium-rich compositions; antiferromagnetic Mn-Cr exchange and long-range easy-plane antifer- romagnetism occur only at very low chromium concentrations (x < 0.05).Competi-tion between 2D and 3D ordering is observed near the ferro- to paramagnetic transition for a sample of composition x = 0.8; as expected 2D order changes to 3D order on cooling followed by a reversion to a 2D ordered phase on further cooling.' 84 A new example of an insulating ferromagnet (PhCH2NH3)2CrBr3~,T,,7 has been prepared:18' it crystallizes in the K2NiF structure and has a Curie temperature of 51 K.Manganese. Antiferromagnetic resonance measurements on the 2D easy-plane anti- ferromagnet Rb2MnCI4 indicate that there is a phase transition to an orthorhombic structure accompanied by a transition to a multi rather than single domain antiferromagnetic structure.Ia6 Mn(HCO0),.2((H2N),CO) is one of a series of isomorphous compounds of the form M(HCOO),-2((H2N)CO) which provide good model square antiferromagnets with a large ratio (JIJ').Work on samples with M = Mn Fe Co and Ni have been reported to have Nee1 temperatures of 3.77 K (Mn) 7.9 K (Fe) 6.34 K (Co) and 15 K (Ni).la7 lB0 K.Okuda S. Noguchi K. Konishi H. Deguchi and K. Takeda J. Magn. Magn. Mat. 1992 104107 817. l'' K. Takeda K. Miyake and K. Hirakawa J. Phys. SOC.Japan 1992,61. 2156. lB2 A. T. Abdalian C. Dugautier P. Moch and B. Briat Phase Trans. 1991 33 177. T. Grieb T. Pabst A. Kieslich J. Linder H. Rauschrnann K. Strobel W. Treutmann and R. Geick J. Phys. Cond. Matt. 1991 3 9751. D. Sieger W. Schmidt H. Tietza-Jaensch R. Geick P. Schweiss W. Treutmann and H. Godfrin J. Magn. Magn. Mat. 1992 104107 895. lB5G. Staulo and C. Bellitto J. Mater. Chem. 1991 1 915. '" H. Greb T. Pabst M. Rothaler. A. A. Mukhin A. Y. Pronin K. Strobel and R. Geick J. Phys. Cond. Matt. 1992 4 2281. K. Yamagata T.Abe Y. Higuchi H. Deguchi K. Takeda K. Kaneko H. Nojiri and M. Motokawa J. Magn. Magn. Mat. 1992 104-107 803. Mag net ism 439 Layered titanates containing manganese and other transition ions are among many such materials prepared in anticipation of spin-glass properties. Ni,Mn -,TiO combines NiTiO and MnTiO in which the transition ions have different directions of single-ion anisotropy that combined with exchange frustration leads to re-entrant spin-glass phases and modified antiferromagnetic phases.' 88 In Fe -,Mn,TiO, transition ions in the parent compounds have similar single-ion anisotropies both having Ising moments but the details of the exchange differ producing spin-glass behaviour in mixed compounds.' 89*190 TlMnF is a 2D antiferromagnet which undergoes 3D ordering at 4.2K.19' New work on KMnF and RbMnF using powder neutron diffra~tion'~ indicates that these compounds have antiferromagnetic ordering temperatures of 6.6 K and 3.9 K respectively.Iron. In Lu,Fe,O, there appears to be two types of antiferromagnetic ordering at 60 and 230K corresponding to the ordering of different layers in the struct~re.'~~ The mixed-valence compound a-Fe,(PO,)O possesses ferromagnetic sheets which are coupled antiferromagnetically . 94 Cobalt. Single-crystal neutron diffraction from the helical antiferrornagnet CoI indicates that there is a first-order magnetic phase transition at 9.4K below the established ordering transition of 11.O K.'95There was however no detectable change in the spin structure below this transition.Nickel. There has been much interest in nickel analogues of the high T superconduc-tors such as La,NiO, Nd,NiO,. and Pr,NiO, both in relation to the unusual magnetic and electronic properties of the cuprates and in their own right as antiferromagnets with a rich variety of spin structures. La,NiO orders antiferromagnetically at 325 K and undergoes a structural phase transition at 185K which is accompanied by the appearance of a ferromagnetic moment due to canting of the spins out of the antiferromagnetic layers.' 96,197 Both J and J' are much smaller than in the corresponding cuprates and the nickelate is more three-dimensional (J'IJ)is 5 x compared with 2 x for the corresponding cuprates. When La is progressively replaced by Sr the material is transformed from an antiferromagnetic insulator to a metallic state as may be demonstrated by the steady reduction in internal field in '39La NMR and NQR measurement^.'^^ This change is accompanied by the replacement of commensurate antiferromagnetic order with the wavevector (n,n)by incommensurate correlations centred at Q = (ni-Sn,n 2 Sn) and (n& dn n T dn) with 6 -0.16 for x = 0.2 in La2-xSrxNi0,+,.The length- '*' A. Ito H. Kawano H. Yoshizawa and K. Motoya J. Magn. Magn. Mar. 1992. 104-107 1637. A. Ito S. Ebii H.A. Katori and T. Goto J. Mayn. Mayn. Mat. 1992. 104-107 1635. 190 H.A. Katori T. Goto S. Ebii and A. 110. J. Magn. Magn. Mat. 1992. 104107. 1639. 19' P. Nunez A. Tressaud J. Grannec P.Hagenmuller W. Massa D. Babe1,A.Boireau and J.L. Soubeyroux 2.Anorg. Allg. Chern. 1992 609 71. 19' M.C. Moron F. Palacio and J. Rodriguez-Carvajal Physica B 1992 180 125. 193 J. Iida M. Tanaka and S. Funahashi J. Magn. Magn. Mat. 1992 104-107 827. 194 M. Ijjaali G. Malaman C. Gleitzer G.J Long and F. Grandjean J. Phys. Cond. Matt. 1991 3,9597. 19' M. Mekata H. Kuriyama Y. Ajiro. S. Mitsuda and H. Yoshizawa. J. Magn. Mugn. Mat. 1992,104-107 859. 196 K. Yamada T. Omata K. Nakajima S. Hosoya. T. Sumida and Y. Endoh. Physica C 1992 191 15. 19' X. Batlle X. Obradors. M. J. Sayagues M. Vallet and J. Gonzalez-Calbet J. Phys.:Cond. Matt. 1992.4. 487. 198 Y. Furukawa and S. Wada. J. Phys. Soc. Japan 1992. 61 1182. 440 A. Harrison and S. J. Clarke scale of the correlations is equal to the average separation of the Sr atoms.’99 This should be contrasted with the cuprates in which the incommensurate correlations are centred at Q = (n n +6n)and (n& 6n,n).The microscopic influence of the dopant is still unclear.DC and AC susceptibility measurements show the existence of five different magnetic phase transitions in Nd,NiO in an applied magnetic field.200 Pr,NiO shows a structural phase transition at 117K which signals the emergence of a ferromagnetic moment as with the La compound.201 Copper.Work on layered copper compounds continues to be dominated by the high-Tc superconducting ceramics their parent compounds and related cuprates. As was discussed in section 4,much of the inspiration for this work lies in the belief that there may still be some causal link between the magnetic fluctuations and the superconduct- ing behaviour of these materials.The field is not quite as active as in past years but its greater maturity has lead to a steady flow of significant results. We wish to draw the reader’s attention to a small collection of findings that are primarily concerned with the nature of the magnetic fluctuations in materials derived from La,CuO and YBa2Cu,0,. It is now well established that the magnetic fluctuations in the normal state of La,-,Sr,CuO are centred at incommensurate wave-vectors Q = (n n _+ 6n) and (n+ dn n) with 6 -x; inelastic neutron scattering measurements of samples with x = 0.14 and 0.15 indicate that the structure factor S(Q,w) for paramagnetic fluctuations peak in Q as expe~ted,’~’,~~~ but differ in their observations of the energy and temperature dependence.The first set of workers observed a peak in S(Q,w) at T when the sample is cooled for energy transfer down to 4meV; they argued that the pairing energy is very much less than 3.5kTCand comparable to the energy of the incommensurate fluctuations. The onset of superconductivity seems to suppress the fluctuations though the correlation length does not change with temperature. The second set of workers observed no maximum in S(Q,o)at T, but rather a rise on cooling to T followed by a levelling-off. In both cases there is a clear discrepancy with NMR measurements that probe the antiferromagnetic fluctuations at zero energy. Recent improvements to the theory of the coupling between the various nuclear moments and the fluctuations allow an extension to be made to finite frequencies but the data still require a temperature-dependent antiferromagnetic correlation length that is appreciably longer than that measured with neutrons.204 Spin-wave dispersion measurements on superconducting samples of YBa,Cu,O + show an energy gap E which rises relative to T as x increases the ratio EG/T is very small for x -0.1 and rises to the asymptotic value 3.5 as x increases to 0.92 though it 199 S.M.Hayden G. H. Lander J. Zarestky P. J. Brown C. Stassis. P. Metcalf and J. M. Honig Phys. Rec. Lett.. 1992 68 1061. X. Batlle B. Martinez X. Obradors M. Pernet. M. Vallet. J. Gonzalez-Calvet and J. Alonso. J. Mugn.Magn. Mat. 1992 104-107 918. 20 1 M. T. Fernandez-Diaz J. L. Martinez J. Rodriguez-Carvajal P. Odier. G. Fillion J. Beille B. Barbara and M. Cyrot Physica C 1991 185189 1225. 202 T. E. Mason G. Aeppli and H.A. Mook Phys. Rev. Lett. 1992 68 1414. ’03 T. R. Thurston P. M. Gehring G. Shirane R. J. Birgeneau K. A. Kastner Y. Endoh M. Matsuda K. Yamada H. Kojima and I. Tanaka Phys. Rev. B 1992. 46 9128. ’04 A. J. Millis and H. Monien Phys. Re[>.E. 1992 45 3059. Magnet ism 441 remains considerably smaller than the ratio of the superconducting charge gap 2A to kTc.205 The layered salt Cu(HC002),.4H20 has been recognized for some years to be a S = '2 square Heisenberg antiferromagnet. Recently attention was drawn to its suitability to test advances in the theory of this class of magnet as applied to high-T superconducting cuprates.It provides certain advantages over the cuprates as a model magnet it is relatively easy to grow large pure single crystals that when deuterated are suitable for inelastic neutron scattering measurements; the in-plane exchange is much smaller than in the cuprates so certain magnetic properties such as the spin-wave dispersion may be measured more easily.206 A neutron scattering study of the critical exponents for the long-range ordering transition at 16.5 K showed a cross-over in b from a value of 0.23(1) to 0.32(2) at the reduced temperature of 0.06K.207The dependence of the magnetic correlation length on temperature in the paramagnetic phase was fitted to the expression derived by Chakravarty Halperin and Nelson for this class of magnet and the exchange constant shown to be -89(3)K which compares with a value of -72 K derived from susceptibility measurements.On doping with a concentration x of the diamagnetic ions Mg2 or Zn2 +,T was seen to fall off + with x in a similar manner to La2Cul -xZnx04 and other non-Ising 2D antiferromag- nets.208 Three-dimensional Magnets.-Once again the technological importance of ferrites and garnets drives research in magnetism to such an extent that articles on these materials greatly outnumber those on the remainder of materials that cannot sensibly be regarded as low-dimensional. There are no comprehensive reviews this year and we have incorporated work on the fundamental properties of such materials throughout this section.The magnetic properties of diluted magnetic semiconductors also receive considerable attention in the form of and individual papers cited below. Vanadium. VNbF is built from corner-sharing VF and NbF octahedra in a similar manner to LiSbF,. Superexchange between Nb" and V" leads to a ferrimagnetic transition at T = 3 K." Chromium. The magnetic structure of Cr2F has been determined by powder neutron The magnetic space group C2/c is the same as the crystal space group and at variance with previous predictions leading to a revision of the superexchange mechanism. The first-order paramagnetic to antiferromagnetic transition in Cr,O has been studied by linear birefringence213 and the critical exponent shown to be 0.355.The role of magnetostriction and the response of the magnetic properties to pressure changes has been deduced for the NiAs-structure semiconductors CrTe -xSex (x = 0.2-0.4).214 Exchange interactions in a wide range of chromium spinels and their 205 J. Rossat-Mignod L. P. Regnault P. Bourges C. Vettier P. Burlet. and J. Y. Henry Phys. Scr. 1992 T45. 74. 206 A. Harrison S.J. Clarke T. E. Mason. and D. Visser J. Magn. Magn. Mat. 1992 104-107 557. '"'S.J. Clarke A. Harrison T. E. Mason G.J. Mcintyre and D. Visser. J. Phys.:Cond. Matt. 1992.4. L71. 'Ox S. J. Clarke and A. Harrison J. Phys. Cond. Mutt. 1992 4. 6217. 'OY W.J. M. Dejonge and H. J. M. Swagten J. Magn. Magn. Mat. 1992 100 322. 210 A. Twardowski Phys. Scr. 1991 T39 124. T.Lemercier J. Chassaing D. Bizot and M. Quarton Mat. Res. Bull. 1992 27 259. '" P. Lacorre G. Ferey and J. Pannetier J. Solid State Chem. 1992 96.227. *I3 R. V. Pisarev B. B. Krichevtsov and V. V. Pavlov Phase Trans. 1991 37 63. 214 H. Yoshida T. Kaneko M. Yuzuri Y. Adachi T. Kanomata and T. Suzuki J. Magn. Magn. Mat.. 1992 104-107 1983. 442 A. Harrison and S.J. Clarke sulfur and selenium analogues have been reviewed. l5This type of compound provides a wide range of helimagnet canted and glassy spin structures thiospinels related to CuCr,S and doped with Ge Sb and Gd,210*216*217 based and selenium spinels218-220 on ZnCr,Se or CdCr,Se have produced such magnetic phases. The thiospinel Zn,Cd -xCr2S4 shows a transition from ferromagnetic221 to spin-glass behaviour as x is increased from 0 and substituent ions alter the ratio of nearest and next-nearest exchange interactions.222 Finally the ,'Te Mossbauer spectrum of Cr -,Fe,TeO (x = 0.4-1.5) indicates that the replacement of chromium by iron produces an imbalance in the exchange interaction through Te which in turn leads to a magnetic hyperfine field there.,' Manganese.MnF has been the subject of magneto-optical studies of exciton-magnon sidebands for some years and the tradition continues with work on the dephasing of large wave-vector magnons through intersublattice transitions,, and the manner in which magnons diffuse through the solid.225 The diamagnetically doped compound Mn,,,Zn,,,F still excites interest because it is a random-field Ising magnet.226 The bimetallic salt [Cr(H,0)(NH3),][FeC16] is composed of a network of ordered coordination polyhedra centred on high-spin Fe"' (S= 3)and Cr"' (S = $) and linked by ionic forces and H-b~nds.,,~ Antiferromagnetic exchange produces several ferrimagnetic phases at low temperatures.CuMnO has been prepared by heating a mixture of CuO and MnO under pressures of up to 50 kbar and shown to be a ferrimagnet containing Mn" and Mn'" with a Nee1 temperature of 235 5 2K.,,* Magnetic semiconductors containing manganese have been prepared as thin MnTe is stabilized in a zinc blende rather than a NiAs structure when grown epitaxially on GaAs or in strained MnTe/ZnTe superlattices and has been the subject of a study of the influence of strain on the magnetic order.23 Spin-glass transitions in the diluted magnetic semiconductor (Zn -,Mnx),As2 have been observed for samples with x = 0.10 and 0.13 at the unusually high temperature of 200 One method of producing frustrated magnetic 2'5 S.Juszczyk. J. Map. Magn. Mat. 1992. 112. 449. 216 R. K. Gubaidullin R.A. Sadykov T.G. Aminov and E. V. Amerikova Neorg. Mat. 1992 28 1377. '" K. P. Belov L. I. Koroleva N. P. Pislyakova E.A. Amerikova G.G. Shabunina and T.G. Aminov Inorg. Mat. 1991 27 1873. 218 H. Rej A. Bombik J. Kusz A. Oles M. Pinot and J. Warczewski J. Magn. Map. Mat. 1992. 111.47. 219 J. Krok-Kowalski J. Warczewski T. Mydlarz A. Pacyna A. Bombik J. Kopyczok and I. Okonska-Kozlowska J. Magn. Map. Mat. 1992 111 50. 220 Y. H. Kim S. M. Bhagat M.A. Manheimer S. Tyagi L. Maksymowicz and M. Lubecka IEEE Trans. Magn. 1992 28 3195. 221 S. Pouget M. Alba N. Fanjat and M. Nogues Physicu B 1992 180-181 244. 222 M. Nogues D. Fiorani J. Tejada. J. L. Dormann. S. Sayouri A.M. Testa and E. Agostinelli J. Magn. Magn. Mat. 1992. 10k107 1641. "' F. Berry and C.D. Gibbs Hyperfine Int. 1991 67 513. 224 M. L. J. Hollman A. F. M. Arts and H. W. De Wijn J. Magn. Magn. Mat. 1992 104-107 1063. 225 L. D. Rotter W. M. Dennis and W.M. Yen Phys. Rev. B 1991 44,11 806. 226 F.C. Montenegro J.C.O. De Jesus F. L.A. Machado E. Montarroyos and S.M. Rezende J. Magn. Magn. Mar. 1992 104107 277. 227 M.C. Moron F. Palacio J. Pons and J. Casabo J. Map. Magn. Mat. 1992 114. 243. "' I. 0.Troyanchuk A. A. Shemyakov and V. K. Prokopenko Fiz.Tverd. Tela 1991. 33 964. 22y K. Ando K. Takahashi and T. Okuda J. Map. Mayn. Mat. 1992. 104-107 993. 230 T. M. Gielbultowicz P. Klosowski J.J. Rhyne N. Samarth L. Hong and J. K. Furdyna Physicu B 1992 18@ 181 485. 23' P. Klosowski T.M. Giebultowicz N. Samarth H. Luo J.K. Furdyna and J.J. Rhyne J. Magn. Magn. Mat. 1992 104-107 1795. 232 A.V. Lashkul E. Lahderanta. R. Laiho and V.S. Zachvalinskiy Phys. Rev. B 1992 46 6251. Magnetism 443 structures that has not been applied to inorganic solids very much is the use of a glassy host material :measurements on manganese aluminosilicates clearly indicate spin-glass transition^.^^^'^^^ When Ising spins are added as in Mn,Ho,Al -.T(Si04)3 (x = 0-0.05),a second ordering transition is observed in low-field measurements of the imaginary part of the magnetic s~sceptibility.~~~ The two transitions are believed to correspond to separate ordering of the Ising and the Heisenberg moments with the possibility of an intermediate semi-spin-glass phase.Iron.One polymorph of FeF adopts a pyrochlore structure which may be described as a network of edge-sharing FeF tetrahedra (Figure 2). The topological frustration is believed to place the material in a new magnetic universality class leading to an unusual value for the critical exponent fi of 0.18(2) as measured by powder neutron difli-action. Complementary Monte Carlo simulations confirm this value and produce estimates for other critical exponents v = 0.38(2) y = l.l(l) and a = 0.6(1).236 Compounds of iron and fluorine feature prominently in a review on fluorinated bronzes of divalent and trivalent 3d transition metal ions and new frustrated iron compounds.237 The nature of the ferrimagnetic transition at T -88 K in the Weberite material Na2NiFeF7 has been studied further by Mossbauer spectroscopy measure- ments which indicate that the net moment points along the a axis.238 Similar measurements on (NH,),FeCI ,.H,O suggest that previous work on the relation between structure and magnetism in this material is wrong and indicates that the a axis is an easy axis.239 Neutron diffraction measurements have revealed the magnetic structures of a number of iron compounds.Fe,Na,(PO,) is a fast-iron conductor which is a member of the NASICON family and has a structure based on vertex-sharing FeO and PO polyhedra.When Fe-0-P-0-Fe superexchange is combined with the lattice topology a frustrated structure with a weak ferromagnetic component is The orthoferrite BiFeO has been shown to have a cycloidal spiral structure241 with a pitch of 620A and a short-range canted antiferromagnetic structure is found in a series of Li-Zn ferrites.,, The Mg-Zn ferrites Zn,Mg _,Fe2O4 show a transition from ferri- (x < 0.5) to antiferromagnetic behaviour (x = 1) uia a randomly canted phase and re-entrant spin-glass beha~iour.~, Work on other spinels and thiospinels includes GdFe,O, Fe,,,Cu,~,Rh,S, and the Verway transition in Fe,0,.244-248 A high (S = 2) to low (S = 1) spin transition may be produced in CaFeO when 233 M.U.Rana T. Abbas and M.A. Chaudhry. Mod. Phys. Lett. B 1991 5 1669. 234 C. Bellouard M. Hennion I. Mirebeau and B. Hennion J. Magn. Magn. Mat. 1992 104-107. 1627. 235 K. Hinrichs K. Herz K. Knorr H. J. May J. Pohl and W. Prandl. J. Magn. Magn. Mat. 1992 104-107 1676. 236 J.N. Reimers. J. E. Greedan and M. Bjorgvinsson Phys. Rev. B 1992. 45 7295. 237 G. Ferey ‘Mixed Valency Systems Applications to Chemistry Physics and Biology’. NATO ASI SeriesC. 1991 Vol. 343. 238 G. R. Thompson. Q.A. Pankhurst and C. E. Johnson J. Magn. Magn. Mat. 1992 104-107 893. 239 S.R. Brown and I. Hall J. Magn. Map. Mat. 1992 104-107. 921. 240 N. Fanjat and J. L. Soubeyroux J. Mayn. Magn. Mat. 1992 10.5107 933. 24 1 I. Sosnowska M. Loewenhaupt W. I. F. David and R. M. Ibberson.Physica B 1992 18&181 117. 242 Y. Chen and R.Y. He J. Magn. Mayn. Mat. 1992. 116 231. 243 M. Nogues J. L. Dormann J. Teillet and G. Villers J. Magn. Magn. Mat.. 1992 104-107 415. 244 A.N. Thakur K. Gaur and H. B. Lal J. Mat. Sci. Lert. 1992 11 496. 245 R. Plumier M. Sougi. and J. L. Soubeyroux J. Alloys Compd. 1992 178 51. 246 R. Aragon Phys. Rev. B 1992 46,5328 24’ R. Aragon Phys. Rev. B 1992 46,5334 24H 2. Inglot K. P. Lieb M. Uhrmacher. T. Wenzel and D. Wiarda Z. Phys. B. 1992 87 323. 444 A. Harrison and S.J. Clarke 30 GPa pressure is applied and is related to the transition from localized to itinerant electron behavio~r.~~~ Magnetic susceptibility studies of Fe,V,O 3 FeVMoO, and F~,V,MO,O~~ between 76 K and room temperature indicate that even well above the Nee1 temperature there is appreciable antiferromagnetic ordering due to the strong Fe"'-O-Fe"' e~change.~"A new low-temperature Morin transition is observed in r-Fe,O, in addition to the normal transition after irradiation with neutrons in a reactor.The result is interpreted in terms of a change in single-ion anisotropy through radiation damage.251 Neutron and susceptibility studies of Cr,Fe -xVO solid solutions (x = 0.25,0.5,0.75)reveal some ordering of the Cr"' and Fe"' ions over two types of octahedral sites with more Cr"' in the more regular site.252 Frustrated antiferromagnetic exchange produces a magnetic spiral structure that propagates along the monoclinic axis for low concentrations of Cr"'; at higher concentration increased frustration suppresses long-range order.The application of Mossbauer spectroscopy to the study of magnetic order in mixed metal oxides has been reviewed with an emphasis on spin-glass behaviour in compounds of iron.253 The technique has been applied to the cubic perovskite Sr,FeTiO -,and revealed a spin-glass freezing transition at about 20 K which is believed to be a consequence of the structural disorder of the B-site cations and the mixed (III)-(IV) oxidation states of iron.254 Magnetic order with both spin-glass and long-range antiferromagnetic character is observed255 through l1 9Sn and 57Fe Mossbauer studies of the perovskite SrLaFeSnO,. Cobalt. Spin-glass behaviour resulting from competition between ferro- and anti- ferromagnetic exchange has been observed in CoCI,.H,O below 7 K.256 A spin-glass transition has been detected in BaCo,Ti,O, through the observation of a sharp anomaly in the DC susceptibility at Tf= 13.6K and a divergence of the field-cooled and zero-field-cooled s~sceptibility.~ 57 A detailed analysis of the imagin- ary part of the AC susceptibility is best interpreted when it is assumed that a true phase transition occurs at T,.Cobalt iodine boracite Co,B,O 3I has been shown by neutron diffraction to have a canted antiferromagnetic structure.258 FTTR measurements of the magnetic excitations in Co,Si04 and Fe2Si0 were combined with a knowledge of the canted antiferromagnet spin structure to produce a model for the exchange interactions and anisotropy constants and thence an explanation259 for the high-field behaviour of Co2Si0,.Co,TiO shows a para- to ferrimagnetic transition at 55 K and an anomaly in the specific heat at 49 K. The latter transition has been shown to correspond to a random anisotropy phase arising from the random lattice distortions that occur 249 M. Takano S. Nasu. T. Abe K. Yamamoto S. Endo Y.Takeda and J. B. Goodenough. Phvs. Rer:.Lett. 1991. 67 3267. M. Kurzawa. J. Mat. Sci.. 1992 27. 1361. 251 0.F. Bakkaloglu 0.Nikolov and M. F. Thomas J. Phys. Cond. Muff.,1992 4. 7839. 252 J. P. Attfield. A. K. Cheetham. D.C. Johnson and T. Novet. J. Muter. Chem.. 1991 I. 867. 253 F.J. Berry J. F. Marco. M. I. Sarson. and M. R. Smith Hyperfine Int. 1991 66 25. 2s4 T. C. Gibb P. D. Battle S. K. Bollen and R.J. Whitehead J. Muter. Chem.. 1992 2 11 1. 255 T . c . G'ibb J. Muter. Chem. 1992 2 415. 256 G.C. Defotis. R.V. Chamberlain W. R.A. Jdrvis. and D.J. Krovich. J. Magn. Magn. Mat. 1992 104-107. 1603. "' A. Labarta. X. Batlle B. Martinez. and X. Obradors Phys. Rer. B. 1992. 46 8994. "' M. Clin H. Schmid P. Schobinger and P. Fischer. Phuse Trans.. 1991 33. 149. 25y C. Brotzeller H. Jaitner. B. Hock 0.Neumann R. Geick. W. Treutmann. S.Hosoya and H. Kato. J. Muyn. A4ugn. Mat. 1992. 104-107 949. Magnet ism 445 through the large charge difference between Co" and Measurements on Co,O indicate that an anomaly in the thermal expansion of the lattice at 600K is due to a low-high spin transition.261 A comparison has been made between the antiferromagnetic Co-Co exchange in Zn -,Co,S and Zn _,Co,Se (x = 0.0055-0.063) and found to be stronger in the selenide than the sulfide and three times stronger than in the Mn analogues.262 Heat capacity measurements on Zn,-,Co,S were interpreted with the aid of a model in which magnetic exchange beyond nearest neighbours fell off with the separation Y in A as -30r-6.3 K 263 Nickel.NiO attracts attention as a simple fcc Heisenberg antiferr~magnet.~~~.~~' Measurements on the diamagnetically dilute compounds Ni _,Mg,O indicate a similar reduction in TN with x as observed in Co,-,Mg,O for (1 -x)> 0.32. Measurement of the superparamagnetism of fine particles of NiO ( 5 100nm in size) indicate that it is due to lattice imperfections at the surface rather than to non-stoichiometry and provides a method of determining particle size in this Spin-waves in NiO have been measured through Raman spectroscopy and sharp low-frequency excitations attributed to surface and bulk one-magnon excita- tion~.~~' The orthorhombic perovskites PrNiO and NdNiO display a metal ~ insulator transition that is accompanied by an abrupt 3D magnetic ordering transition of moments on Ni with an ordered moment 11 -0.9pp and an unprecedented commensurate spin-density wave with Q = (112 0 1,'2).268 Molybdenum.The pyrochlores Ln Mo207,where R is a lanthanide ion have attracted attention over the past few years on account of the high frustration involving both Mo" and Ln"' moments. Work on the Y Sm and Gd compounds indicate spin-glass transitions at 18 68 and 55 K respectively.269 Ruthenium.Spin-glass behaviour is believed to occur in Sr,FeRuO and Sr,FeRuO below 23 and 11 K respectively and is attributed to the competition that arises between Ru"' and Fe"' in nearest- and next-nearest-neighbour sites."' Lanthanides. The spin dynamics of the fcc type-I1 antiferromagnet CeAs with S = 4 have been studied by elastic inelastic and diffuse critical neutron scattering.'? Successful interpretation of the data requires the presence of significant anisotropic nearest-neighbour exchange as well as next-nearest-neighbour exchange. BaPrO is a cubic perovskite with an orthorhombic distortion. Below 1 1.7(2) K there is a continuous and reversible antiferromagnetic ordering of the moments with a 260 G.Gavoille. J. Hunsch and S. Koutani. J. Mayn. Muin. Mur.. 1991 102 283. Zh' V.A. M. Brabers and A. D. D. Broemme. J. Magn. Mayn. .Mar. 1992 104-107.405. 262 C. Chen W. Gao Z. Qin W. Hu M. Qu and W. Giriat J. Appl. Ph~..s.,1992. 70. 6277. 2h3 H.J.M. Swagten A. Twardowski E.W. Janse. P.J.T. Eggenkamp. and W.J.M. Dejonge J. Mugn. Magn. Mat.. 1992. 104-107. 989. Z64 M. M. Ibrahim Z. Feng J.C. Dean anti M.S. Seehra J. Phys. Cotid. ,Matt.. 1992. 4 7127. "' Z. Feng and M.S. Seehra Ph~s.Rer. B. 1992. 45 2184. 266 J.T. Richardson D. I. Yiagas. B. Turk. K. Forster and M. Twigg. J. .4ppl. Phjs.. 1991 70. 6977. Zh7 D.J. Lockwood M.G. Cottam and J. H. Baskey. J. Mayn. Magpi. Mat.. 1992. 104 107. 1053. 26n J. L. Garcia-Munoz J. Rodriguez-Carvajal.and P. Lacorre. Europhys. Lrrt.. 1992 20. 241. "') N. P. Raju E. Gmelin. and R.K. Kremer Pky.s. Rw. €3 1999. 46. 5405. 270 P. 9.Rattle. S. K. Bollen and A. V. Powell. J. Solid Srurc. Chm. 1992. 99. 267. 271 A. Donni A. Furrer. P. Fischer. F. Hulliger. and S. M. Hayden. J. Muyri. hfuyn. Mur.. 1992. 104- 107. 1 204. 446 A. Harrison and S.J. Clarke low-temperature average moment of 0.35(5)& and a small ferromagnetic compo- nent .2 72.27 3 The magnetic ordering in Nd(OH) has been measured down to 40mK with a SQUID magnetometer but there is no sign of long-range magnetic order;274 frustration in the structure is believed to restrict magnetic correlations to a short range. Europium oxide and sulfide continue to provide simple model ferromagnets to test theoretical work concerning the nature of the magnetic fluctuations near the Curie temperature of a ferr~magnet~~~ and the diamagnetically-dilute derivative Eu -$r,S still provides one of the best model insulating spin-gla~ses.~~~ Heavier chalcogenides are antiferromagnetic careful specific heat measurements on EuTe show a crossover in the critical exponent o! from a very small value (0.0085(30)) to a larger value (0.38(11)) as T is approached from above.277 The crossover is attributed to the influence of weak dipolar forces.GdVO appears to be a tetragonal paramagnet which orders at 2.5 K to produce a simple two-sublattice antiferromagnetic array :278 antiferromagnetic resonance measurements are in accord with the predictions of mean-field theory.CdGd2Se4 shows antiferromagnetic order below 9.5 K driven by both dipolar and exchange force^.^ 79 Magnetic order whose origin is presumed to lie in dipolar interactions has been observed in the trifluoromethane sulfonate salts of Nd Gd Er and Yb and with the exception of the Yb salt appear very similar to the corresponding isostructural lanthanide ethyl salts.280 TbAsO has been shown to possess an incommensurate magnetic structure at low temperatures and the ordering vector has been determined by powder neutron diffraction.281 The magnetic properties of the two-sublattice antiferromagnet DyPO have been probed through the EPR signal of Yb3+ or Er3+ doped into the lattice.282 The exchange field experienced by these ions may be accurately determined and is found not to agree well with the predictions of a model in which there is isotropic exchange between real electron spins on the lanthanide ions.Er203 has been shown to order antiferromagnetically at 3.3 K. BaHo2F8 shows antiferromagnetic order below 1.76K and considerable magnetic 272 N. Rosov J. W. Lynn Q. Lin,G. Cao J. W. O'Reilly P. Pernambuco-Wise and J. E. Crow Phys. Rev. B. 1992 45 982. 273 I. Felner Y. Yeshurun G. Hilscher T. Holubar G. Schaudy U. Yaron 0.Cohen Y. Wolfus E.R. Yacoby. L. Klein F.H. Potter C.S.Rastomjee and R.G. Egdell Phys. Rev. B 1992. 46 9132. 274 G. Helgesen A.T. Skjeltorp and H. Bratsberg 1. Magn. Magn. Mat. 1992 111 5. 275 D. Gorlitz J. Kotzler and T. Lange J. Magn. Magn. Mat. 1992 104-107 339.'16 9. Ozcelik K. Kiymac J. C. Verstelle A. J. Van Duyneveldt and J. A. Mydosh J. Phys. Cond. Matt. 1992 4 6639. 27' E. Scheer J. Wosnitza. H. V. Loehneysen R. Kuersch M. Lang and F. Steglich J. Magn. Magn. Mat. 1992 104-107 175. 278 M. M. Abraham J. M. Baker B. Bleaney J. Z. Pfeffer and M. R. Wells J. Phys. Cond. Matt. 1992 4 5443. 27q E. Mochowska S. Pokrzywnicki and M. Duczmal J. Phys. Cond. Matt. 1992 4 5339. M. R. Roser J.C. Xu and L. R. Corruccini J. Low Temp. Phys. 1991 85 255. 281 W. Kockelmann W. Schafer and G. Will J. Phys. Chem. Solids 1992 53 913. 282 M. M. Abraham J. M. Baker 9.Bleaney A. A.Jenkins P. M. Martineau and J. Z. Pfeffer,Proc. Roy. SOC. London Series A 1991 435 605. 283 Y. J. Tang X. W. Cao J. C. Ho and H. C.Ku Phys. Rev.B 1992 46,1213. Magnetism 447 short-range order at 4.2K.284The magnitude of TNis not consistent with purely dipolar ordering forces and it is deduced that exchange is dominant. Actinides. The magnetic properties of monochalcogenides and monopnictides have been reviewed with emphasis on the nature of the actinide ion which is generally trivalent the role of crystal field and the form of the magnetic exchange.285 One of the success stories of magnetic X-ray scattering has been the elucidation of the magnetic properties of many actinide compounds. Attention has recently turned to Uranium compounds with preliminary measurements286 of the enhanced resonance scattering near the M edges of UO, USb and U,,,,Th,,,,Sb; no enhancement was seen for the scattering from Th.The magnetic susceptibilities of the solid solutions MgyU,-,,O +x indicate an increase in Nee1 temperature and effective moment on U as the oxidation state is raised from (IV) to (v),but not to (vI),on doping.287 Doping with La rather than Mg led to a decrease in effective moment as U was oxidized further to Uv'.288LiUO has an anomalously large magnetic susceptibility relative to the predictions of mean-field and crystal-field calculations which is attributed to ferromagnetic character.289 Inelastic neutron scattering measurements on NpO demonstrate the relation between the crystal field levels of Np" and the ferromagnetic phase transition at 25 K.290 The transition is accompanied by a collective Jahn-Teller distortion of the oxygen sub-lattice.Neptunium chalcogenides crystallize in the rock salt structure. Recent neutron scattering measurements indicate that the sulfide and selenide order at 23 and 38 K respectively to a type-I1 antiferromagnetic structure with inequivalent Np sites.291 This behaviour is considerably more complex than that shown by the uranium or plutonium counterparts which behave as ferromagnets or temperature- independent paramagnets respectively. NpSe shows an antiferromagnetic transition at 38K but the ordered structure has not been determined while NaAs shows antiferromagnetic order below TN= 175 K and a ferrimagnetic phase transition in a magnetic field greater than 6 T. The mixed compounds NaAs-NpSe were made to see if new magnetic phases could be produced.The addition of NpSe leads to an increase in ferromagnetic interactions increased frustration and a reduction in ordered moments. The critical exponents of the incommensurate-commensurate transition in NpAs have been measured by critical scattering experiment^.^'^ 6 Molecular Solids Magnetic Clusters.-Our trawl through this year's literature has netted relatively few examples of work on dimers as compared with previous years. What there is is M. M. Abraham B. Bleaney R. W. Hill M. J. M. Leask R.C. C. Ward and M. R. Wells Proc. Roy. SOC. London Series A 1991 435 159. K. Mattenberger and 0.Vogt Phys. Scr. 1992 T45,103. 2R6 C. C. Tang W.G. Stirling G.H. Lander D. Gibbs W. Herzog P. Carra B. T. Thole K. Mattenberger and 0.Vogt Phys. Rev. B 1992.46,5287. 2M7 Y. Hinatsu J. Solid State Chem. 1991 95 300. Y. Hinatsu J. Solid State Chem. 1991 95 430. Y. Hinatsu T. Fujino and N. Edelstein. J. Solid State Chem. 1992 99,182. 290 G. Amoretti A. Blaise R. Caciuffo D. Di Cola J. M. Forunier M. T. Hutchings G. H. Lander R. Osborn and A. Severing J. Phys. Cond. Mutt. 1992 4 3459. 2y1 A. Blaise M. N. Bouillet F. Bourdarot P. Burlet J. Rebizant J. Rossat-Mignod J. P. Sanchez J.C. Spirlet and 0.Vogt J. Magn. Magn. Mat. 1992 104-107 33. 2y2 D. L. Jones S. Langridge W. G. Stirling G. H. Lander J. Rebizant J. C. Spirlet M. Alba and 0.Vogt Physica B 1992 1W181,88. 448 A. Harrison and S.J. Clarke primarily concerned with dimers of Cu" both horn~nuclear~~~~~~~ and heteronuclear with CoII 304.305 Nil1 305 307 or Gd"1 308,309 Work has also been performed on homo- nuclear dimers of V with both V1v310and a mixed V1ll-V1v dimer,31' Cr312 314 and ~~312,315,316 319 ~i11 ~~~ ~~,317 320 W,3l4 and A u as well as a variety of heteronuclear dimers of first-row transtion-series elements.322 Several of these contribute to our understanding of the relation between sign and strength of exchange and the length and geometry of the exchange bridges.306.312,318,322 One or both of the species in a dimer may also be a radical.Ferromagnetic coupling has been observed between a radical and Gd"' in nitronyl complexes323 and between spins on biradicals coordinated to There is a wide variety of trimeric species that have been the subject of magnetochemical study.Some of these have biological significance as in homonuclear Cu" complexes related to multicopper o~idases,~~~ and the heteronuclear complexes Fe"'-Ni"-Fe"' with M = Zn Cu Ni Co Fe and Mn which may provide models for electron transport in biological species."' The p,-oxide mixed-valance Mn complex 2v3 H. Uekusa S. Ohba. T. Tokii. Y. Muto K. Michinobu S. Husebye 0.W. Steward S.C. Chang and J. P. Rose Acta Cryst. B 1992 48. 650. 294 T.E. Grigereit. J. E. Drumheller. R. Scott. G. Pon and R. D. Willett. J. Mtzgn. Magn. Mat. 1992 104-107. 1981. 205 J. P. Chyn K. J. Shieh J. L. Chou Y. Wang G. H. Lee. and C. P. Chen. J. Chin. Chem. Soc. 1991,38,549. 296 M.T. Garland J. Y. Saillard and E. Spodine J. Cryst. Sprctr. Res.. 1992 22. 467. 297 D.Lelievre L. Bosio J. Simon J. J. Andre. and F. Bensebaa J. Am. Chem. Soc.. 1992 114 4475. 298 A. Tosik. W. Maniukiewicz M. Bukowskastrzyzewska J. Mrozinski. M. P. Sigalas and C. A. Tsipis. Inory. Chim. Acta 1991 190 193. 299 I. Castro J. Sletten. J. Faus. M. Julve Y. Journaux. F. Lloret and S. Alvarez Inory. Chrm.. 1992,31 1889. 300 J. P. Costes. F. Dahan. and J. P. Laurent Inorg. Chrm. 1992. 31 284. 301 L. P. Battaglia. A. B. Corradi. S. Ianelli M. A. Zoroddu. and G. Sanna J. Chrm.Soc. Faraday Trans.. 1991. 87 3863. 302 S.S. Tandon L. K. Thompson. and R. C. Hynes Inorg. Chem.. 1992. 31 2210. 303 S. Wang S. Trepanier. J. C. Zheng. Z. Pang and M. J. Wagner Inory. Chern. 1992 31 21 18. 304 D. Z. Liao S. Juan Z.H. Jiang. S. P. Yan P. Cheng and G.L. Wang Polyhedron 1992 11 2621. 305 A. Escuer. R. Vicente and J. Ribas. Polyhedron 1992. 11 453. 306 A. Escuer. R. Vicente J. Ribas R. Costa and X. Solans. Inory. Chem.. 1992. 31 2627. 307 B. Srinivas N. Arulsamy. and P.S. Zacharias. Polyhedron 1992. 11 21 I. 30x M. Sakamoto. M. Hashimura K. Matsuki. N. Matsumoto K. Inoue. and H. Okawa Bull. Chrm. Soc. Jupun 1991 64 3639. 3nv 0.Guillou. P. Bergerat. 0.Kahn E. Bakalbassis K. Roubekeur P. Batail. and M. Guillot Inory. Chrm. 1992 31. 110. 310 C. W. Hahn P.G. Rasmussen. and J. C. Bayon Inory. Chem. 1992. 31 1963. 31 1 D.B. Sable and W.H. Armstrong. Inorg. Chrm. 1992. 31. 161. 312 A. Niemann U. Bossek K. Wieghardt C. Butzlaff. A. X. Trautwein and B. Nuber Angrw Chrm. 1992.104 345. 313 M. Nakahanada T. Fujihara A. Fuyuhiro. and S. Kaizaki. Inor(/. Chrm.. 1992 31 1315. 314 F.A. Cotton and T. Ren J. Am. Chrm. Soc.. 1992 114 2237. 315 M. Suzuki Y. Hayashi K. Munezawa M. Suenaga. H. Senda. and A. Uehara. Chem. Letr. 1991 1929. 316 S. Pal J. W. Gohdes. W. C.A. Wilisch and W. H. Armstrong Inorg. Chrm. 1992 31. 713. 317 Z. Ding S. Bhattacharya J. K. McCusker P. M. Hagen. D. N. Hendrickson. and C.G. Pierpont. Inory. Chrm. 1992 31,870. 318 M. Mikuriya. Y. Yamato and T. Tokii Chrm. Lett.. 1992. 1571. 314 K. J. Oberhausen J. F. Richardson. R. J. Obrien R. M. Buchanan. J. K. McCusker. R. J. Webb and D. N. Hendrickson Inorg. Chrm.. 1992. 31 1123. 320 A. Escuer R. Vicente. and J. Ribas J. Mayn. Magn. &fur.. 1992 110.181. 321 A. P. Koley S. Purohit. L.S. Prasad S. Ghosh. and P.T. Manoharan. lrrorg. Chem. 1992. 31 305. 3 22 R. Flotzelmann. K. Wieghardt. U. Florke H. J. Haupt. D. C. Weatherburn J. Bonvoisin. G. Blondin and J. J. Girerd J. Am. Chon. Soc.. 1992. 114 I68 1. 323 C. Benelli. A. Caneschi. D. Gatteschi. and L. Pardi. Inory. Chrm.. 1992. 31 741. 324 A. Caneschi A. Dei. and D. Gatteschi. J. Chrm. Soc.. Chem. Commun. 1992. 630. 72s P. Chaudhuri. I. Karpenstein. M. Winter,C. Butzlaff E.Bill. A. X. Trautwein U. Florke. and H. J. Haupt J. Chrrn. Soc. Chem. Commun. 1992 321. 726 E. Bill. C. Butzlaff. A. X. Trautwein H. Winkler M. Winter and P. Chaudhuri Hjlpwfine lnr.. 1991. 68 229. Magnetism 449 [Mn"Mn~10(0,CCH3),(py)3]py has a ground state with a spin rather than the expected value of i,which is believed to arise from spin frustration.327 A trimer of Ni" also exists,328 connected to a polytungstate in [Ni,(H,O),PW lo03,H,0]7-.328 Fer-romagnetic exchange within the trimer produces an overall spin of 3 which is the largest spin ground state yet observed in a heteropolyoxometalate.Finally inelastic neutron scattering measurements have detected magnetic intercluster interactions in the iron trimer compound [Fe"',Fe"O(0,CCD,),(CsD,N)3](CsDsN).329 Biological interest and polyoxometalates feature in higher-nuclearity clusters too. The cubane complex [Mn'VMn~'03Cl,(0,CCH3)3]3-may be used to model the behaviour of the active core of the water-oxidation photosystem II.330 LCAO X calculations predict the correct magnetic ground state and indicate that the spin polarization is important in determining the spin state of the complex.Exchange energies vary between 5and & of those in similar Fe-S clusters. A cubane core of four nickel atoms linked through hydroxy bridges to produce different Ni -0-Ni exchange pathways has been synthesized in the complex [Ni4(OH),(tzdt),(py),].2py (where tzdt = 1,3-thia~olidine-2-thionate).~~ The exchange may be ferro- or antiferromag- netic depending on the geometry of the exchange path. Different types of exchange pathways are also produced in another small group of metal ions in the tetranuclear complex [Cu,(TNLR)(p,-OH),(H20)8](CF3S03), (TNLR = 1,4,6,9-tetrakis((R-2-pyridyl)amino(benzodipyridazine));332 the central rectangle of Cu" ions is linked along the different edgzs and diagonals by a selection of antiferromagnetic exchange constants.The tetranuclear Co" or Cu" complexes [M,(H,O),(PW,O,,),] -and [M,(H,0),(P,W,,0,,)2]'6- contain a rhombus of edge-sharing MO units which are coupled antiferromagneticallj for Cu and ferromagnetically for CO.,,~The exchange in K o[Co,(H,0),(PW,03,),] has been determined by inelastic neutron scattering to be 3 meV.334 Bonding schemes within larger polynuclear transition metal clusters have been elucidated through magnetic susceptibility and ESR measurements on the high nuclearity V cluster compounds K,[Vl ,As,0,,(H20)]~8H,0 and (NH,)[V,,AS~O,~(SO~)].~~~ The data have been interpreted by breaking down the clusters into fragments identifying different exchange pathways and estimating exchange energies.The first cooperative magnets containing C,, i.e. the complex TDAE-C, (where TDAE is tetrakis(dimethylamino)ethylene,C,N,(CH,),) were reported last year. Further work confirms the presence of approximately one unpaired spin per molecule and indicates a transition to a ferromagnetic ordered state at T = 16.7-17.5 K.336.337 327 J. K. McCusker H.G. Jang. S.Wang G. Christou and D. N. Hendrickson. Inory. Chem.. 1993.31. 1874. 328 C. J. Gomez-Garcia E. Coronado and L. Ouahab Anyew. Chrm. Inr. Ed. En<//..1992 31 649. 329 U. A. Jayasooriya R. D. Cannon. C. E. Anson S. K. Arapkoske. R. P. Whitc and G. J. Kearley. J. Chmi. Soc. Chem. Commun. 1992 319. 33" E. A.Schmitt L. Noodleman E. J. Baerends. and D. N. Hendrickson. J. Am. Chem. Soc.. 1992. 114,6109. 33' L. Ballester. E. Coronado A. Gutierrez. A. Monge M. F. Perpinan E. Pinilia. and T. Rico Inory. Chem. 1992 31 2053. 332 S.S. Tandon S.K. Mandal. L. K. Thompson and R.C. Hynes. Inory. Chem. 1992 31. 2215. 333 C.J. GomeT-Garcia E. Coronado and I. J. Rorras-Almenar. Inorcq. Chem.. 1992. 31. 1667. 334 C.J. Gomez-Garcia E. Coronado J.J. Borras-Almenar. M. Aebersold. H. U. Gudel. and H. Mutka. Physicu B 1992 186181 238. 335 A. L. Barra D. Gatteschi L. Pardi A. Muller and J. Doring .I.Am. Chem. Soc. 1992 114 8509. 33b K. Tanaka. A. A. Zakhidov K. Yoshizawa K. Okahara,T. Yamabe. K. Yakushi K. Kikuchi. S. Suzuki. I. Ikemoto. and Y. Achiba. Phys. Lett. A. 1992 164. 221.337 G. Sparn J. D. Thompson P. M. Allemand Q. Li. F. Wudl. K. Holuer. and P. W. Stephens Solid Slurp Commun. 1992 82 719. A. Harrison and S. J. Clarke The application of pressure produces a rapid depression of T,. The analogous C, compound shows no ferromagnetism down to 4.5 K. More exotic clusters may be produced in a molecular beam and an estimate of the magnetization made by measuring their Stern-Gerlach deflection^.^ 38 In this manner the magnetism of Fe,, and Ni,, was studied as a function of rotational and vibrational temperature. Chains Layers and Three-dimensional Magnets.-Most of the work on 1D molecular magnetic materials this year concerns nitroxide radicals such as p-NPNN (p- nitrophenyl nitronyl nitroxide) in its various crystal forms labelled a,p ph,and y.The so-called p form shows bulk ferromagnetism below 0.60K with an entropy change for the transition corresponding to one unpaired spin per radical entity.339 The y form appears to behave as ferromagnetic chains of Heisenberg moments (J -4.3 K)coupled weakly through both ferro- and antiferromagnetic and is metastable relative to the y form.Table 1 contains an entry for p-NPPP as well as several Table 1 Molecular magnets. The structures of some of these materials are given in Figure 4. The acronyms we use are the ones defined by the various authors and are given either in the text in section 6.2 or are as follows NITR = 2-(4-R)-4,4,5,5-tetramethyl-4,5-dihydro-l H-imidazo-line-1-0xyl3 oxide; DEAPNN = 2-(4’-diethylaminophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl 3-N-oxide; m-MPYNN = 2-(3-N-methylpyridinium)-4,4,5,5-tetra-methyl-4,5-dihydro-1H-imidazol-1-oxyl 3-N-oxide; MOTMP = 4-methacryloyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl; ET = bisethylenedithiotetrathiafulvalene; Pc = diphthalo-cyanine; TCNE = tetracyanoethene; TPTA = 2,4,6-triphenoxy- 1,3,5-triazine.FM and AFM stand for ferro- and antiferromagnet(ic) respectively. Material Figure Comments Ref. P-NPNN B form is FM below 0.60 K; ;’ form is 1 D o.h y-NPNN FM with AFM interchain exchange and TN= 0.65 K Cu(hfac),NIT-Me Spin density study by polarized neutron c CuCl,(NIT-+) diffraction shows Cu-NIT-R coupling p-pyridyl nitronyl FM Jlk = 0.27 K d nitroxide DEAPNN 1D AFM with J -~ 2.45K e m-MPYNN(BF,) 2 2D triangular AFM lattice of FM- f I0.28(H20)0.17 coupled dimers of m-MPYNN MOTMP Galvinoxyl radicals 4 (c) 4 (d) ID FM T -0.14K Short-range FM (0 = 4.4K) if prepared by freeze-drying producing different P h ET,Cu[(N(CN),]Cl molecular stacking in crystal structure TN= 45K; weak FM below 22K with moment -(8.10-4)p,/formula unit i ET,KHg(SCN) FM and AFM phases at low tempera- J tures [YPc,]CH,Cl Chains of Pc macrocycles sign of ex- k change depends on relative orienta- tions to produce 1D FM or AFM 338 J.A.Becker and W. A. Deheer Ber. Bunsen-Ger. Phys. Chem. 1992,% 1237. 339 Y. Nakazawa M. Tamura N. Shirakawa D. Shiomi M. Takahashi M. Kinoshita and M. Ishikawa Phys. Rev. B 1992 46 8906. 340 M. Takahashi M. Kinoshita and M. Ishikawa J. Phys.SOC.Japan 1992 61. 3745. Magnetism 451 Material Figure Comments Ref' CFeCPJCTCNEI Product of pyrolysis of T falls as % spinless defects decreases Composed of C and H with -3% N; 1.2-diaminopropane random network of sp2 and sp3 carbon with high-spin areas coupled AFM to give -0.022 p$C Pyrolytic carbon from Samples superparamagnetic and poss- " adamantane ibly FM at low temperature not due to FM oxide "Y. Nakazawa M. Tamura N. Shirakawa I>. Shiomi M. Takahashi M. Kinoshita and M. Ishikawa Phys. Rev. B 1992,468904. 'M.X. Wan H. L. Wang and J.G. Zhao J. Mugn. Mugn. Mat.. 1992. 104-107,2096. 'J. X. Boucherle B. Gillon E. Ressouche P. Rey and J. Schweizer. Physica B 1992,180-181. 135. dK. Awaga T. Inabe and Y.Maruyama Chem. Phys.Lett. 1992.190,349. 'T. Sugano T. Goto and M. Kinoshita Sdid State Commun.. 1991,80 1021. IK. Awaga,T. Inabe Y. Maruyama T. Nakamura,and M.. Matsumoto Chem. Phys. Letr. 1992 195 21. 9H. Sugimoto H. Aota A. Harada Y. Morishima M. Kamachi W. Mori M. Kishita N. Ohmae M. Nakano and M. Sorai Chem. Letr. 1991. 2095. hL.Y.Chiang R. B. Upasani H. S. Sheu D. P. Goshorn and C. H. Lee J. Chem. Soc. Chem. Commun. 1992 959. 'U.Welp S. Fleshler W. K. Kwok G.W. Crabtree K. D. Carlson H. H. Wang U. Geiser J. M. Williams. and V. M. Hitsman Phys. Rev. Letr.,1992,69.840.'5. S. Brooks C.C. Agosta S.J. Klepper M. Tokumoto. N. Kinoshita H. Anzai S. Uji H. Aoki A. S. Perel G.J. Athas and D. A. Howe Phys. Rev. Lett. 1992,69. 156. 'J. L. Paillaud M. Drillon A. Decian J. Fischer R. Weiss R.Poinsot and A. Herr Physicu B. 1991 175 337. 'K. S. Narayan B.G. Morin. J.S. Miller and A.J. Epstein Phys. Rev. B 1992. 46 6195. "K. Murata H. Ushijima H. Ueda and K. Kawaguchi J. Chem. SOC.,Chem. Commun.. 1992 567. "K. Tanaka M. Kobashi H. Sanekata A. Takata T. Yamabe. S. Mizogami K. Kawabata and J. Yamauchi J. Appl. Phys.. 1992 71. 836. derivatives in which p-nitrophenyl is replaced by another organic moiety R. There is little consistency in the way in which different authors devise acronyms for these compounds we use such acronyms in the table and give the full names below and specify R in the caption to Figure 4. (c) (d) Figure 4 Organic radicals in some of the ID molecular magnets referred to in the second column ?f Table 1. The abbreviations are dejned in the text (section 6)or the caption to Table 1.(a) NPNN (h) NIT-K with K = (i) methyl or phenyl (ii) p-pyridyl (iii) 4-diethylaminophenyl (iz:) 3N-methylpyridinium (c) MOTMP (d) galuinovyl There is relatively little work on higher-dimensional molecular magnets if only because it is much harder to devise efficient ferromagnetic exchange pathways in more than one dimension in a molecular crystal. We intend to provide an account of A. Harrison and S. J. Clarke intercalation compounds next year. The amorphous material V(TCNE);y(CH,CI,) (x -2 y -i),which created considerable excitement last year on account of the observation of a spontaneous moment at room temperature has not appeared in the literature for 1992.The amorphous structure and extreme sensitivity towards chemical attack has hindered progress.
ISSN:0260-1818
DOI:10.1039/IC9928900425
出版商:RSC
年代:1992
数据来源: RSC
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Chapter 24. Radiochemistry |
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Annual Reports Section "A" (Inorganic Chemistry),
Volume 89,
Issue 1,
1992,
Page 453-471
D. S. Urch,
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摘要:
24 Radiochemistry By D. S. URCH Chemistry Department Queen Mary and Westfield College Mile End Road London El 4NS UK 1 introduction As in previous years this section of Annud Reports will review recent developments in radiochemistry but exclude those aspects such as radiation chemistry and actinide chemistry where radioactivity is not of primary importance. Nuclear reactions leading to specific isotopes will be considered first followed by a description of chemical reactions induced by recoil atoms and a selection of recent reports on the preparation of labelled molecules. In the final section the increasingly important role of radiochemical procedures in tackling environmental problems both man-made and of natural origin will be reviewed. The spate of international conferences on various aspects of radiochemistry continues unabated ;the 8th international conference on radiopharmaceutical chemis- try,’ the 4th international symposium on the synthesis and applications of isotopically labelled compounds,2 the 4th European symposium on radiopharmacy and radiophar- mace~ticals,~ and the 2nd international conference on methods and applications of radioanalytical ~hemistry,~ as well as national meetings such as the 3rd general congress on nuclear energy held in Brazil.’ Books on basic aspects of nuclear chemistry6,’ on nuclear methods of analysis,8 and on the uses of isotopes in the physical and biomedical sciences’ have also appeared.More specific papers have ‘Proc. Eighth International Symposium on Radiopharmaceutical Chemistry’.ed. W. C. Eckelman and E. R. Squibb. J. Wiley & Sons New York NY USA 1990. ‘Proc. Fourth International Symposium on Synthesis and Applications of Isotopes and Isotopically Labelled Compounds’ ed. E. Buncel and G. W. Kabalka. Elsevier Amsterdam Netherlands 1992. ‘Progress in Radiopharmacy (Proc. Fourth European Symposium on Radiopharmacy and Radiophar- maceutical)’ ed. P. A. Schubiger and G. Westera Kluwer Dordrecht Netherlands 1992. ‘Proc. Second International Conference on Stainless Steel Surface Diffusion-coated with Chromium’ Ahsrracts ed. Ying Sun and T. Hirabayashi American Nuclear Society La Grange Park IL USA. 1991. ’ ‘Proc. Third General Congress on Nuclear Energy’ Associacao Brasileira de Energia Nuclear Rio de Janeiro RJ Brazil 1990.’ K. H. Lieser ‘Introduction to Nuclear Chemistry’ VCH Weinheim Germany 1991. ’ P. Hoffman and K. H. Lieser ‘Methods in Nuclear Chemistry arid Radiochemistry’. VCH Weinheim. Germany 199 1. ’W. D. Ehmann and D. Vance ‘Radiochemistry and Nuclear Methods of Analysis’ J. Wiley & Sons New York NY USA 1991. ’‘Isotopes in the physical and biomedical sciences. Vol. 1. Labelled compounds’ ed. E. Buncel and J. R. Jones Elsevier Science New York. NY USA 1987. 453 454 D.S. Urch reviewed the radiochemistry of ruthenium" and the first fifty years plutonium.' ' This retrospective view is also to be found in the book 'Fifty Years with Nuclear Fission' edited by Behrens and Carlson.12 2 Isotope Production The use of an 11 MeV proton cyclotron for the production of over a hundred different radioisotopes' has been described.The Light Elements.-The concentration of tritiated water on freezing has been investigated14 and a method for the preparation of 'H3H free from ditritium gas using selective adsorption l5 has been described. When 13N is made by the [160(p,ct)'3N] reaction using water as a target,'" the chemical form (nitrate nitrite ammonium etc.) of the radioactive nitrogen is found to vary with pH. If l80enriched water is used then 18Fis also produced by the ['80(p,n)'8F] reaction. A special double cell has been designed l7 to enable both isotopes to be produced separately and simultaneously. A variation can be used with a 26 MeV proton beam' to produce ['50]water in the front cell and either' 3Nor 18F in the rear cell.When ['sO]water is used in the production of "F distillation facilitates" the recovery of the isotopically labelled water. An alternative reaction for the production of 150 is the deuteron irradiation of solid nitrides [14N(d,n)' Optimum procedures for the preparation of ['8F]difluorine gas have been established,2 ' and a method for the production of '8F-anions following the neutron irradiation of lithium aluminate (a double nuclear reaction is involved with recoil tritons as intermediaries) has been described.22 It is interesting to note that 17F has been identified23 as a short-lived impurity in the production of 13N by the proton irradiation of water. 38Kcan be produced by the proton irradiation of either natural or 38Ar enriched argon24 by the [38Ar(p,n)38K] reaction; the optimum beam energy was 12-16 MeV.First-row Transition Elements.-The world-wide availability of cyclotrons has led to their being used for the production of many different isotopes e.g. [48Ti(p,n)48V],25 lo W. W. Schulz S. G. Metcalf and G.S. Barney Radiochernistry of Ruthenium' Nuclear Science Series US Govt. Printing Office Washington DC USA. 1984. 'I G.R. Choppin and B.E. Stout Chrm. Br. 1992 27 1126. l2 'Fifty years with nuclear fission'. ed. J. W. Behrens and A. D. Carlson. American Nuclear Society La Grange Park IL USA 1989. l3 R.J. Nickles ref. 1 116. A.G. Mironov and N.V. Belomestnova Radiokhimiya 1991 33 97. l5 'Proc. 4th Topical Meeting on Tritium Technology in Fission Fusion and Isotopic Applications'.ed. J. L. Maienschein R. S. Hudson R. T. Tsugawa E. M. Fearon P.C. Souers and G. W. Collins US Govt. Printing Office Washington DC USA 1991. J.T. Part B. Nebeling and G. Stoecklin ref. 1 118. R. A. Ferrieri D. L. Alexoff D. J. Schlyer and A. P. Wolf in 'Proc. 4th International Workshop on Targetry and Target Chemistry' US Govt. Printing Office Washington DC USA 1991. '* G. K. Mulholland. M. R. Kilbourn and J. J. Moskwa ref. 1 86. '' T. Chaly D. Bandyopadhyay R. Matacchieri and D. Margouleff Appl. Radiat. Isot. 1992 43 1089. '"J. W. Brodack M. J. Welch. R. E. Shefer and R. E. Klinkowstein ref. 1. 87. J.J. Sunderland O.T. DeJesus 0.Solin and R.J. Nickles ref. 1 89. " (a)J. Jirnenez-Becerril. Ph.D.Thesis University of Toluca Mexico 1990; (b)M. Suehiro T. Sasaki M. Senda H. Toyarna T. Nozaki H. Suzuki. and S.-I. Ishii Appl. Radiat. Isot. 1992 42. 1231. 23 M. Tornai. A. Bishop N. Satyamurthy. and J. Kleck Appl. Radiat. Isnt.. 1992. 43 841. 24 F. Tarkanyi Z. Kovacs S. M. Quairn and G. Stoecklin. ihid. 1992 43 503. 2J M. Gallorini M. Bonardi L. Magon. and E. Sabbioni in 'Proc. 2nd International Conference on Methods and Applications of Radioanalytical Chemistry' Am. Nuclear Soc.. La Grange Park IL. USA. 1991. Radiochemistry 455 [54Cr(p,n)54Mn] [59Co(p,anp)54Mn],26 and 55C0 56C0 56Ni 57Ni 58Ni and 59Ni by the irradiation of iron targets27 with either proton deuteron or alpha particle beams. Proton irradiation of natural zinc or 68Zn-enriched targets initiates the [68Zn(p,2n)67Ga]28reaction.By varying the bombardment conditions both 64Cu and "CU can also be made29 from the same targets. The lighter isotope of copper 62Cu which is being used increasingly in nuclear medicine can most easily be made by the decay of 62Zn; new designs3' for suitable generators have recently been described. Ga-Sr.-The separation of 85As from a stream of recoil fission atoms can be achieved3' by allowing the atoms to thermalize in a gaseous mixture of nitrogen and hydrogen fluoride. Rather more conventional procedures have been described for the production of 73Se from either germanium ["Ge(~y,n)~~Se],~* [70Ge(3He,y)73Se],33or arsenic [75As(p,3n)73Se].32 The lighter positron-emitting isotopes of bromine are now being used extensively in nuclear medicine and can be prepared either by alpha bombard- ment of arsenic targets [75As(a,2n)77Br]34 or by proton irradiation of krypton [78K or 80Kr(p,~)75Br or 77Br].35 Radioactive isotopes of rubidium and strontium can be extracted either by complex formation (" Rb from radiochemical waste)36 or ion-exchange chromatography (89Sr from uranium fission).37 Second-row Transition Metals.-Methods for the preparation and purification of isotopes of yttrium have been described.87Ycan be made38 from cyclotron irradiated strontium and it has been suggested that a generator for this isotope could be based on 87mSr.The heavier isotope 90Y results from the decay of 90Sr and can be ~eparated~~ from both this isotope and its own daughter 90Zr by chromatography.Ion-exchange chromatography has also been used to both 91Yand 95Zr from fission products. 99Mois also present in fission products and many methods have been proposed4' to extract and purify it as a source of technetium e.y. solvent 26 J. M. Lee K. S. Chun and S.D. Yang 'The Development of Cyclotron Radionuclides(II)' Korea Atomic Energy Research Inst. Daeduk Korea 1991. " S. Roesler in 'Workshop on Selected Aspects of Radiochemistry Isotope Preparation Separation Methods Aspects of Radiochemical Methods and Analysis Environmental Protection and Radiochemis- try on the Chemistry of the Fifth Halogen Astatine' Akademie der Wissenschaften. Leipzig Germany 1991 p. 13. ZR J.D. Lee K. S. Jeon S. D. Yang Y. S. Seo S. J. Chae Y.K. Yoon H. Park and Y. Y. Koo 'Production of Cyclotron Radionuclides' Korea Atomic Energy Research Inst. Daeduk Korea 1992. 29 T.E. Boothe E. Tavano and J. Munoz ref. 1 105. (a)J. Zweit J. W. Babich R. J. Ott M. Cox H. L. Sharma R. Goodall and G.A. Potter Eur. J. Nud. Med. 1992,19,418; (b)M. A. Green C. J. Mathias W. H. Margenau J. W. Brodack and M. J. Welch ref. I 92. 31 U. Hickmann N. Greulich N. Trautmann and G. Herrmann Radiochim. Actu 1991 55 57. 32 A. Plenevaux M. Guillaune. C. Brihaye. C. Lemaire and R. Cantineau ref. 1 97. 33 N. Lavi G. Blessing S. M. Quaim and G. Stoecklin ref. 1 99. 34 M. A. V. Bastos Ph.D. Thesis Universidade Federal Rio de Janeiro Brazil 1982. " F. Helus S. Zeisler G. Gschwandtner H. Marx and W. Maier-Borst J. Radioanal. Nud.Chrm. Letters 1992 153 417. 36 W. I. I. Bakker and D. N. Reinhoudt. in 'Proc. Seminar New Separation Chemistry Techniques for ~ Radioactive Waste and Other Specific Applications' ed. L. Cecille M. Casarci and L. Pietrelli Elsevier Applied Science Barking UK 1991 p. 142. 37 (a)K. R. Balasubramanian K. L. N. Rao C. Mathai R. N. Varma V. I. Dhiwar and S. K. Saxena Report 1991/E/O09,Bhabha Atomic Research Centre Bombay India. 1991; (h)T. Oi H. Ogino. and H. Kakihana Sep. Sci. Technol. 1992 27 631. 3R Y.G. Sevast'yanov A.A. Razbash and A.G. Maklachkov Rudiokhimiya. 1990. 32 61. 39 M. L. Dietz and E. P. Horwitz Appl. Radiat. Isot. 1992 43 1093. 40 C.N. Desai in 'Proc. International Symposium on Radiochemistry and Radiation Chemistry (Plutonium ~ 50 Years)' Department of Atomic Energy.Bombay. 1991 paper IT-30. 456 D.S. Urch e~traction,~' Another route to 99Mo is complex formation,42 and ~hromatography.~~ by the neutron irradiation of 98Mo (as zirconium m~lybdate);~~ however as a source of 99mT~ this proved much less satisfactory than 99Mo from other sources. The search for a suitable matrix for the retention of molybdenum from which 99mTc can be eluted continues; a recent suggestion is ~eria.~' Methods for the preparation of lighter isotopes of technetium have been proposed from the proton irradiation of either molybdenum [(nat)M~(p,xn)~'"'Tc or 96Tc]2s or rhodium. In the latter case46 both 96T~ are formed; 97R~ and 97R~ is also made when silver targets are irradiated4' with high energy (100MeV) proton beams.At lower energies lo9Cd is The irradiation of natural silver with deuterons also leads to the formation49 of cadmium isotopes [lo7Agor '09Ag(d,2n)'07Cd or lo9Cd]. However radioactive silver '11 Ag results from the deuteron irradiation of palladium via the positron decay of '''Pd. Methods for its extraction and purification from the palladium target have been de~cribed.~' The bombardment of similar targets with alpha particles results in the formation5' of both silver ('"Ag and lo6"'Ag) and cadmium (11 ""Cd) isotopes. In-Ba.-The radiopharmaceutical potential of indium isotopes has led to the de~elopment~~ of a new route to "'In by the bombardment of natural cadmium targets with 3He ions. '"Sn is initially produced which decays to the positron emitting indium isotope.The short-lived '18Sb(T~,~ 3.5 min) which is used in nuclear medicine as a flow tracer is formed by the decay of ''8Te; this isotope can be easily made by the proton bombardment of antimony itself53 [' 'Sb(p,4n)' '8Te]. Interest in the short- lived positron isotopes of iodine continLies and reactions such as ['24Te(p,2n)' 231]s4 as well as ['24Xe(p,2n)' 23Cs] and ['24Xe(p,pn)' 23Xe],55 which produce precursor isotopes have been thoroughly investigated. A generator for the easy preparation of another short-lived isotope '37"Ba (T',~2.6 min),56 from the decay of '37Cs has been reported. Rare Earths-Lead.-Separation methods based on chromatography or amalgam formation have been described for the preparati~n~~.'~ of 14'La 14'Sm lS2Eu '54E~ '' C.Landesman Ph.D. Thesis CEA Centre d'Etudes de la Vallee du Rhone France 1991. 42 S.K. Das A.G.C. Nair S. M. Deshmukh and S. Prakash ref. 40 paper AR-16. 43 (a) N.D. Vaidya P.R. Unni A.R. Mathakar and M. Subramanian ref. 40 paper AR-17; (h) M.A. El-Absy Radiochim. Acta 1992 55 23. " A. Sanchez-Ocampo and S. Bulbulian Appl. Radial. Isot. 1991 42 1073. 45 D. K. Bhattacharyya and N. C. Dutta ref. 40 paper AR-18. '' L. F. Mausner S. Kurczak and S.C.Srivastava ref. I p. 1. '' 0.Scheibe T. Tenthal A. F. Novgorodov. and D. Schumann ref. 27 p. 12. 48 J. Mengatti E. M. Sgambatti J. B. Sumiya V. Sciani and J. A. Osso Junior in 'Proc. 4th General Congress on Nuclear Energy' Comisslo Nacional de Energia Nuclear RJ.Brazil. 1992. p. 145. 49 X. Long X. Peng F. He and M. Liu. Appl. Radiat. Isot. 1991 42 1234. 50 (a)R. Alberto P. Blaeuenstein 1. Novak-Hofer A. Smith and P. A. Schubiger ihid. 1992,43 869; (h)L. Bizhong L. Qimin W. Yonghui and L. Yuanfang Acta Sci. Nut. Unic. Beijing 1991 27 444. 51 S. Ambe Y.Ohkubo M. Iwamoto and Y. Kobayashi J. Radioanal. Nucl. Chem. Letters 1991,153,235. 52 F. Szelecsenyi Z. Kovacs and F. Tarkanyi ref. 1 p. 95. 53 D. A. Miller S. Sun and J. H. Yi ref. 25 p. 38. 54 S.A. C. Mestnik and J. Mengatti in ref. 17. 55 (a)S. M. Qaim F. Tasrkanyi G. Stoecklin M. Sajjad R. M. Lambrecht and H. Schweikert. ref. 1 p. 100; (h) M. L. Firouzbakht D. J. Schlyer and A. P. Wolf ref. I p. 102. 56 Y. Wang C. Lee and W. Cheng ref. 25 p. 67. 57 B. Sarkar and S.Basu ref. 40 paper AR-25. 58 A. Zeman K. Kratzer J. Stary J. Prasilova Z. Satorie and J. Suran J. Radioanal. Nucl. Chem. Arriclrs. 1991. 149 223. Radiochemistry 457 and 16'Yb. Neutron irradiation of samarium59 and europium6' targets have been reported as useful routes to '53Sm and 53Gd respectively. Neutron irradiation is also the basis for the preparation of 186Re and '"Re (from perrhenate solutions)6' and 1940s(from osmium metal -[1920s(2n,y)'940s]). The osmium isotope can then be used62 in a generator as a source of 1941r (T',~19.2 hr) a powerful beta emitter that is used in radioimmunotherapy. 199A~ has the same use and can be produced63 by multiple neutron capture from natural gold. When gold is subjected to alpha particle irradiation (25 MeV) '"Tl is produced64 [197A~(a,2n)'99Tl] and whilst this isotope is to be preferred for nuclear medicine applications new methods for the preparation of 201T1 following proton b~mbardment~~ of thallium lead or bismuth have been described.However proton bombardment (90MeV) of bismuth can also lead6 to the formation of '03Pb. The heavier isotope of lead (212Pb) can be used6' as a source of 212Bi by 8-decay whilst the bombardment of natural bismuth with helium-3 particles leads to the formation of astatine68 [209Bi(3He,3n)209At]. TransuranicElements.-An improved technique for the infrared laser-induced enrich- ment of 235U (as UF from UF,) has been rep~rted,~' and when this isotope is irradiated with alpha particles traces of 236Pu are formed.70 A new isotope of mendelevium has been rep~rted,~' 3C,3n)253Md] reaction made by the [243Am(1 (cross-section 50 nb).253Md has an estimated half-life of six minutes. Heavy-ion bombardment using l80at 95-100MeV has also been used to prepare isotopes of elements 104(Unq) and 105(Unp) [248Cm(180,5n)26'Unq; zli2 65s] and [249Bk('80,4 or or 262Unp; T~ 27s or 34s].72*73 ,~ 59 L. Shunzhong P. Manfei L. Yuqian L. Zhonglin Z. Changying. Z. Pengji F. Yibei and D. Houfu J. Nucl. Radiochem. 1991 13 233. 6o C. Lee and W. Cheng ref. 25 p. 67. 61 J. L. E. Vanderheyden. F. M. Su and G. J. Ehrhardt 'Soluble Irradiation Targets and Methods for the Production of Radiorhenium' US Patent Document 5 053 186/A Patent and Trademark Office Box 9. Washington DC USA 1991.62 (a)S. Mirzadeh D. E. Rice and F. F. Knapp Appl. Radiat. Isor. 1992,43,689; (h)S. Mirzadeh D. E. Rice and F. F. Knapp Jr. in 'Proc. 9th International Symposium on Radiopharmaceutical Chemistry' US Govt. Printing Office Washington DC USA 1992. h3 K. L. Kolsky L. F. Mausner J. F. Hainfeld G. E. Meinken and S.C. Srivastava ref. 1 p. 218. 64 (a)Z. Dehai G. Changtian K. Anren and D. Houfu J. Nucl. Radiochem.,1991,13,96;(b)D. Zhou D. Xie. F. Liao Y. Zhang and Y. Cao. ref. 25 p. 14. 65 N.G. Zaitseva Ch. Deptula K. S. Khan K. K. Khwan S. Mikolaewsky and V. A. Khalkin,J. Radioanal. Nucl. Chem. Articles 1991. 149 235. 66 L.F. Mausner A. K. DasGupta and S.C. Srivastava ref. 1. p. 114. 67 N. Fang M. Taotao S. Xiuhua and G. Yingxiang J. Nucl. Radiochem.1991 13. 71. 68 Z. Szuecs and F. Szlecsenyi Izot. Tech. Diagn. 1990 33 221. 69 K. Takeuchi Y. Kuga S. Kata and H. Tashiro in 'Proc. 1st JSME/ASME Joint International Conference on Nuclear Engineering' Tokyo 1991 vol. 2 p. 423. '' R. J. Singh S. M. Deshmukh A. Ramaswami S.S. Rattan and S. Prakash ref. 40 p. 2. 71 B. Kadkhodayan K. R. Czerwinski S.A. Kreek N. J. Hannink K. E. Gregorich D. M. Lee M. J. Nurmia D.C. Hoffman R. A. Henderson H. L. Hall and J. D. Leyba Radiochirn. Acta 1992 56 1. '' A. Tuerler K. E.Gregorich D. M. Lee M. J. Nurmia K. R. Czerwinski N. J. Hannink R. A. Henderson C. D. Kacher B. Kadkhodayan S. A. Kreek J. D. Leyba D. C. Hoffman H. W. Gaeggeler D.T. Jost A. Weber J. Kovacs U. W. Scherer J. V. Kratz M. Gober H. P. Zimmermann M.Schaedel W. Bruechle E. Schimpf and H. Barth ref. 25 p. 53. 73 H. P. Zimmermann M. K. Gober J. V. Kratz M. Schaedal W. Bruechle E. Schimpf K. E. Gregorich A. Tuerler K. R. Czerwinski N. J. Hannink B. Kadkhodayan D. M. Lee M. J. Nurmia D.C. Hoffman H. W. Gaeggeler D. T. Jost J. Kovacs U. W. Scherer and A. Weber 'Chemical properties of element 105 in aqueous solution back extraction from triisooctyl amine into 0.5M HCI' Report GS1-92-26 Ges. fur Schwerionenforschung mbH Darmstadt Germany 1992. 458 D.S. Urch 3 Chemical Effects of Nuclear Transformations The energy liberated in a nuclear reaction is many orders of magnitude greater than that required to initiate a chemical reaction. Ions and other particles produced as a result of nuclear transformations must therefore engage in thousands of destructive collisions before they can react chemically and stand a chance of remaining bound.Even so the reactions that they initiate may well be characterized by a high activation energy and be quite different from conventional reactions. Recent advances in such ‘hot-atom’ reactions have been reviewed in depth in a new book edited by Adloff et ~21.~~ Hot-atom reactions are now appreciated to be of wide-spread importance in such diverse areas as cosmo- and geochemistry in nuclear medicine in understanding the environmental chemistry of radioactive waste and in determining the fate of fission atoms in nuclear reactors. In this section recent advances in understanding the primary chemical reactions of recoil atoms (a term which must be understood to include ions and electronically excited species) will be considered.Light Elements.-Whilst the broad outlines of recoil tritium chemistry are well established interest continues in the isotope effect that can be observed in the reaction between ‘hot’ tritium atoms and hydrogen or deuterium atoms. The simplest example is when the reaction is with dihydrogen or dideuterium. Here an isotope effect measured as k(HT)/k(DT) is observed75 which can be enhanced to seven by carrying out the reaction in the presence of xenon and with a very low comcommitant dose or reduced to unity by greatly increasing the y dose. Recoil “C chemistry with cyclohexane benzene and hexamethylbenzene has been investigated recently7 and the labelled products rationalized in terms of known insertion and addition reactions of carbon atoms and methyne radicals in various spin states.The reactions of recoil 3N atoms with both organic and inorganic substrates in all phases have been reviewed:77 it is necessary to postulate that the nitrogen atoms are present in both ground (4S) and electronically excited states (’D & ’P) in order to rationalize the observed chemistry. The Halogens.-Mueller and his co-workers have carried out a series of interesting and elegant experiments in which recoil chlorine (38Cl) and recoil bromine (82Br) were allowed to react with hexahalogeno complexes of either osmium or osmium and tin. The structures of the complexes were chosen to prohibit the formation of specific labelled isomers by direct substitution.The observation of such isomers thus indicated the presence of other labelling reaction pathways and permitted their relative importance to be measured. The systems studied were K,[S~C~,]-K,[OSB~,],~~ all isomers of K2[OSF,C16-,] (n = 2 3 4),79and K2[OSBr,]-K2[OSC16],80 the latter with recoil bromine. In this way it was possible to estimate that about 5% of the labelled product was due to the non-rupture of the bond to the atom which underwent ’’ ‘Handbook of Hot Atom Chemistry’ ed. J.-P. Adloff P. P. Gaspar M. Imamura A. G. Maddock. T. Matsuura H. Sano and K. Yoshihara Kodansha Tokyo Japan and VCH New York USA 1992. ” T. Miyazaki Y. Fujitani M. Shibata K. Fueki N. M. Masaki Y. Aratono M. Saeki and E. Tachikawa Bull.Chem. Soc. Jpn. 1992. 65 735. l6 G. A. Brinkman P. Kuipers G.A. J. Leurs and L. Linder Appl. Radiat. [sot. 1991 42 1123. 77 G.A. Brinkman ibid. 1991 42 1133. ’’ (a)H. Mueller and 1. Hagenlocher Rudiochim Acta 1992,56,73;(h)H. Muellerand J. Hagenlocher ref. 25 p. 8. 79 H. Mueller and P. Obergfell ref. 25 p. 7. H. Mueller and P. Obergfell Rudiochim Acta 1991 55 199. Radiochemistry 459 the nuclear reaction (or that the atom was recaptured at its original site). The commonest reaction was found to be of the simple billiard-ball type in which the recoil atom replaced the impacted atom (about 50%).It was also observed that this reaction often (about 30%)proceeded with the rupture of at least one other bond in the struck complex.Other reactions of recoil bromine that have been studied recently have been with bromomethanes" (charged plate method) and with barium bromates2 (annealing). The reaction of recoil astatine (211At) with benzoic acid in which isomers of astatinebenzoic acid are formed has been inve~tigated.~~ Recoil Metal Atoms.-In a series of experiments that nicely complements Mueller's work with ligand atom substitution by recoil atoms Yoshihara has studied the replacement of the central atom in a transition metal complex by a recoil atom -chromiums4 or ruthenium.85 As with Mueller's work specific isomers have been selected to inhibit the formation of particular labelled products. The systems studied have all been tris(p-diketonate) complexes (Al Cr Fe Co Ru). Ligand to central-atom bond strength was found to be one of the important factors in facilitating the replacement of that atom by the recoil atom.The fate of recoil cobalt in mixed cobalt-chromium and cobalt-iron thiocyanate complexes has been studieds6 by observing changes in overall 'retention' during annealing; the importance of charged species in the reactions of recoil 56Mn with potassium permanganate has been demonstrateds7 using the charged plate technique. The recoil atom chemistry of uranium (239U)and neptunium (238Np) has been investigated88 for a wide range of chemical systems and initial oxidation states by means of the (n,;)) reaction. Such studies provide basic information to help understand the environmental fate of these atoms. 4 Labelled Compounds With the increasing use of short-lived positron emitting isotopes in nuclear medicine more automated procedures are being reported.For the most part they rely on personal computers and vary in the tasks they can perform from data colle~tion,~~ robot control,90 and the remote operation of an autosynthe~izer,~~ overall to radiopharmaceutical contr01,'~ and from target preparation to product packaging. Automatic routine quality control of labelled materials for nuclear medicine is also vital and recent publications have described methods for monitoring radioactive gases93 and a remote control system for the preparation of 3-N-([2'-'8F]fluoro-" S. P. Mishra and M. R.Zaman ref. 40 paper RC-43. S. P. Mishra and A. B. R. Tripathi. ref. 40,paper RC-45.83 Z. Syuch U.V. Norseev D. D. K'yung and L. Vasharosh Radiokhirniya 1991 33 64. 84 T. Sekine and K. Yoshihara Radiochim Actu. 1991 55 65. '' T. Sekine I. Kaneko and K. Yoshihara ibid. 1991 55 71. R.M. Mahfouz Bull. Soc. Chirn. Fr. 1991 128 435. Hi S. P. Mishra and J. Singh ref. 40 paper RC-41. M. Kadri. J. J. Schleiffer and J. P. Adloff. Radiounal. Nucl. Chem. Letters 1991 154. 139. *' D.T. Jost and D. Vermuelen Trans. Nucl. Sci. 1992 39 186. 90 G. Appelquist. C. Bohm H. Eriksson. C. Halldin S. Stone-Elander ref. 1 p. 163. 91 A. L. Feliu ref. I p. 165. 92 R. Verbruggen C. Dom B. Georges. M. Ghyoot Y. Jongen. J. L. Morelle. M. Cogneau. C. Sernal and A. Luxen ref. I. p. 162. 93 M.S.Berridge E. H. Cassidy and J. Koziorowski Appl. Radiar. Isot.1992 43 1055. 460 D. S. Urch ethy1)~piperone.~~ In the latter example HPLC is used to monitor product purity; the same procedure is applied to [18F]-labelled deoxyaldohe~oses,~~ ~-[6-l 8F]fluoro- DOPA and [l'C]-labelled compound^.^^ Chromatographic methods have also been re~ommended~~ for determining the purity of technetium-labelled radiopharmaceuti- cals The use of photochemical methods in the preparation of labelled compounds has been reviewedg8 and a new report has shown that ultrasoundg9 may be used both to reduce reaction times and temperatures and to increase product yields in labelling procedures. New labelling methods for individual isotopes will be considered below. Tritium.-Methods whereby tritium-labelled steroids may be prepared have been reviewed."' A new general method for producing tritium-labelled compounds is to bombard'" them with a tritium ion beam.A range of labelled products is formed so that careful purification is necessary. Very high specific activities can be obtained by this method (ca. 40GBqmmolK'). Another new method but for the production of multiply labelled compounds is the use of pertritiated methyl cations in the gas phase. When these cations react with triethylamine vapour' O2 labelled triethylamine together with n- and isopropyldiethylamines is formed. A more conventional procedure and certainly the easiest is exposure to tritium gas. The efficiency of the exchange reaction can be enhanced by heating the gas with a hot tungsten wire (as in the preparation of [3H]pantethine)'03 and by use of a solid catalyst.Mannitol complex alcohols,' O4 and polysaccharides '05 as well as u-amino acidslo6 have been labelled in this way. A comparison of specific solid catalysts has shown' O7 that better yields of labelled ATP (adenosine-5-triphosphate)are obtained when palladium mounted on barium sulfate is used in preference to palladium oxide. Tritium gas can also be used as a reducing agent to produce labelled species. Recent applications of this method have included the preparation of [4,4-3H,]-)~-aminobutyric acid,'" tritiated threonine,' O9 prostaglandin methyl esters,' lo and 2'-deoxy-2',2'-difluorocytidinehydrochloride.' ' When tritium gas reacts with meth-94 A. Plenevaux R. Cantineau C. Lemaire and M. Guillaume ref.I p. 391. 95 F. Oberdorfer and K. Kemper ref. 1 p. 196. 96 V. W. Pike M. J. Kensett D.R. Turton S.L. Waters and D. J. Silvester ref. I p. 281. 97 (a)M. W. Billinghurst D. N. Abrams and J. Dupont Appl. Rudiat. [sot.,1992,43 1045; (h)J. Gerse and J. Berces ref. 25 p. 62; (c) H. J. Ding and S.J. Yeh Appl. Radiat. Isot. 1992. 43 1013. 98 M. Joshida ref. 9 p. 52. 99 C. Le Breton C. Crouzel S. Bonnot and C. Prenant. ref. 1 p. 176. loo M. Cabell ref. 9 p. 71. Z. Nianbao S. Shugang and Y. Fuzeng 'A new technique for ion beam tritium labelling' paper No. 00410. China Nuclear Information Centre Beijing BJ China 1990. lo2 V. V. Leonov V. D. Nefedov E. N. Sinotova and V. K. Kapustin Rudiokhimiya. 1991 33 70. G.A. Badun and Eh. S. Filatov ihid.1991 33 75. G. P. Akulov E.V. Snetkova Ju. L. Kaminski B. K. Kudelin and V.L. Efimova J. Labelled Compd. Radiopharm 1991 29 1351. (a)G. P. Akulov Ju. L. Kaminski N.A. Korsakova and B. K. Kudelin ibid. 1992 31 227; (h) G. P. Akulov E.V. Snetkova Yu. L. Kaminskij B. K. Kudelin and V. L. Efimova Radiokhimiya 1991,33 74. lo6 (a) Yu.A. Zolotarev V.S. Kozic D.A. Zaitsev E. M. Dorokhova and N.F. Myasoedov J. Labelled Compd. Radiopharm. 1991 29 507 (b)Yu.A. Zolotarev V.S. Kozic E. M. Dorokhova V. Yu. Tatur S.G. Rozenberg and N. F. Myasoedov ihid. 1992. 31 71. lo' D. K. Jaiswal H. Morimoto P.G. Williams and D. E. Wemmer in ref. 2 p. 7. D. Mo and C. Rongzhen Nucl. Tech. 1991 14 372. lo9 J.-M. Delacotte H. Galons D. Schott and J.-L. Morgat J. Labelled Compd.Radiopharm. 1991,29 1141. K. Manabe T. Tanaka S. Kurozumi and Y. Kato ihid. 1991 29 1107. '11 W. J. Wheeler T. E. Mabry and C. D. Jones ihid. 1991. 29 583. Radiochemistry 46 1 aneboronic acid' l2 tritiated methyl borane is produced. C3H]Methyl borane is a useful reagent which can be used to make tritium-labelled amines. Tritium can be incorporated at a specific site in a molecule by the expedient halogen atom replacement. This approach has been adopted in the preparation of short-chain peptides,' ' [3H]methyl-4-phenyl-1,2,3,6-tetrahydropyridinehydrochloride,' ' and sorbinol.' ' Reduction with tritiated sodium borohydride can also result in tritium being placed at a pre-determined site in a molecule. Clenbutinol derivatives,' l6 musk xylene,"' and spingosine"8 have all been labelled in this way.The use of cobalt(I1) chloride as a catalyst has been recommended' ' to convert an aryl-substituted alkenyl nitrile to the corresponding labelled amine. Exchange reactions involving tritiated water can also produce labelled molecules. The presence of rhodium trichloride has proved remarkably effective' 2o in limiting this exchange to the ortho-position in benzoic acid and its salts. Carbon-1 1.-Rapid growth continues in the development of new techniques for the preparation of' 'C-labelled compounds in the primary steps of incorporating 'C into reactive compounds such as ["Clcarbon dioxide'21 and ["Clhydrogen cyanide,'22 in the devising of new rapid synthetic routes to specific compounds and in the construction of automated procedures.When labelled hydrogen cyanide reacts with either dihalogen alkyl compounds or iodotosylates a range of haloalkano-[ "C]-nitriles can be made' 23 which are useful intermediates in the synthesis of more complex molecules. The reaction of bromine with hydrogen ["Clcyanide leads to ["Clcyanogen bromide,'24 another useful intermediate. In order to make [1-"C]a~rylonitrile'~~ from K"CN and vinyl bromide it was necessary to use both 18-crown-6 ether and the catalyst tet-rakis(tripheny1phosphine)palladium.The same catalyst was effective in facilitating the reaction of "CN-with arenetricarbonylchromium complexes' 26 leading to the production of 'C-labelled aromatic compounds. Labelled hydrogen cyanide can also be used to produce cyanohydrins a route which has proved useful in the preparation of [''Clo~topamine.'~~ When [''Clcyanide reacts with propylene oxide the resulting nitrile can either be hydrolysed to racemic [l-' 'C]-/3-hydroxybutyric acidtz8 or '" A.Burgos. J.-M. Kamenka and B. Rousseau ibid. 1991. 29 1347. 'I3 J. Oehlke. H. Niedrich I. Born K. Neubert and E. Mittag. ihid.. 1991 29 1265. 'I4 Z. Hongliang and Z. Nianbao Nucl. Tech. 1991 14 573. '15 H. R. Howard M. Evans R. Sarges and C.T. Groton J. Labelled Compd. Rudiopharm. 1991. 29 703. I I' G. C. Pegg M.J. Sleeman M. N. Sillence and D. B. Lindsay ihid. 1991. 29 1337. ''' M. Fukuoka S. Nambaru and A. Tanaka ibid. 1991 29 1207. 'I" T. Toyokuni M. Nisar B. Dean and S. Hakomori ibid.. 1991 29 567. 'I9 B.R. Branchini E. W. Adams L.A. Egan and M.H. Murtiashaw ihid. 1992. 31 387. ''O K. Oohashi and Y. Soutome J. Radianu[. Nucl. Chem. Letters 1991. 155 65. 12' (u) R.D. Smith R.H. Mach T. E. Morton. B.S. Dembowski and R. L. Ehrenkaufer Appl. Rudiat. Isot.. 1992.43,466 (b)R. D. Smith. R. H. Mach,T E. Morton B. S.Dembowski. and R. L. Ehrenkaufer. ref. 1. p. 157. 122 G.J. Meyer A. Osterholz and T. Harms ref. 1 p. 154. lZ3 (a)G. Antoni K. Hoernfeldt P. Malmborg and B. Langstroem. ref. 1 p. 143; (b)K. Hoernfeldt. G. Antoni and B. Langstroem Acta Chem. Scand.. 1992 46 87. 124 G.Westerberg P. Malrnborg and B. Langstroem ref. 1 p. 122. (a)G.Antoni P. Malmborg and B. Langstroem ref. 1. p. 145; (b)G.Antoni and B. Langstroem. .4ppl. Radiat. Isot. 1992 43 903. 12' Y.Andersson. P. Malmborg and B. Langstroem ref. 1 p. 141. M. Maeda Y. Koga T. Fukumura. and M. Kojima ref. 1 p. 407. J.-0. Thorell. S.Stone-Elander W. A. Koenig C. Halldin and L. Widen. J. Labelled Compd. Radiophorm. 1991 29. 709. 462 D. S. Urch used'29 to produce "C-labelled busulphan. Labelled cyanide anions have also been used in the preparation of [1-"C]-~-glucose'~~ and ["Clamino acids.13' The use of silica gel as a support for ["C]hydrocyanic acid has been advocated'32 in the preparation of radiopharmaceuticals in general and in the synthesis of 2-[ ''C] cyanoisonicotinic acid' 33 in particular. Another procedure reported' 34 to enhance the efficiency of labelling reactions based on "CN-is to carry out the reaction in a microwave cavity.[''CICarbon dioxide is another widely used primary source of carbon-1 1 for the preparation of labelled complex compounds. Reaction with the appropriate Grignard reagent allows [''C]a~etic'~~ or propenoic acids'36 to be made. The former can then be used in the synthesis of labelled tryptarnine~,'~~ glucosamines,' 38 and al-pra~olam;'~' the latter in the preparation of ally1 and vinylamines. When solid [''Clcarbon dioxide reacts with propyllithium labelled propyl ketene is formed,14' which is a new intermediate for the rapid production of "C-labelled alcohols. However it is mostly ["Clmethyl iodide that is made from labelled carbon di0~ide.I~' This reagent can then be used to introduce both radioactive carbon and a methyl group. A novel method'42 for simplifying procedures and increasing efficiency is to adsorb the labelled methyl iodide onto a column and then add the substrate in a suitable solvent.The labelled product can then be eluted as desired. ["Clmethyl iodide has been used in the preparation of a diverse range of compounds; ampheta- analgesic^,'^^ enzyme inhibitor^,'^^,'^^ 1,4-dihydropyridine~,'~~ mine~,'~~ and N-["Clmethylamine derivative^'^^ such as d0~epin.l~~ [''Clmethyl thymidine can also be made using labelled methyl iodide,'49 but in some cases the methyl side group can cause problems and a new route to [2-"C]thymidine has been reported15' which utilizes ["Clurea. By limiting the reaction of [''Clmethyl iodide with alkyl- a,w-magnesium bromides and then reacting the remaining Grignard group with M.Hassan N. Warne J.-0. Thorell and S. Stone-Elander Appl. Radiat. Isor. 1991 42 1055. 13' S. Stone-Elander C. Halldin G. Blomqvist L. Widen and B. Laangstroem ibid. 1992 43 721. 13' M. M. Goodman J.L. DeVinney C. P.D. Longford M. Ladetsky G. W. Kabalka J. Larsen K. F. Hubner and E. Buonocore ref. 1 p. 189. 13' M. Sajjad C. W. Somawardhana and R. M. Lambrecht ref. I p. 177. 133 C. W. Somawardhana M. Sajjad and R. M. Lambrecht ref. 1 p. 158. J.-0. Thorell S. Stone-Elander and N. Elander J. Labelled Compd. Rudiophurm. 1992 31 207. 135 J. P. Norenberg N. R. Simpson B. B. Dunn and D.O. Kiesewetter Appl. Radial. Isof.,1992 43 943. 136 (a)M. C. Lasne Ph. Cairon and L. Barre ibid. 1992,43,621; (b)M. C. Lasne B. Moreau L. Barre and V.W.Pike ref. 1 p. 125. 13' M.Tada A.Oikawa and R.Iwata J. Labelled Compd. Radiopharm. 1991 29 949. 138 M. Tada A.Oikawa and R.Iwata ibid. 1991 29 485. 139 F. R. Dobbs T. J. Tewson W.A.Banks G. A.Digenis and J.C. Fleishaker ref. 1 p. 237. (a) R. Fujii T. Yagyu H. Horii K. Wakita H. Nakahashi Y. Imahori S.Ueda and T. Ido ref. 1 p. 123; (h) R. Fujii Y. Imahori T. Ido and J. Tatsuo J. Labelled Compd. Radiopharm. 1991 29 497. 141 C. Prenant and C. Crouzel ref. 1 p. 121. 142 R. Iwata C. Pascali M. Yuasa T. Takahashi T. Ido and K. Yanai Appl. Radiat. Isof. 1992 43 1083. 143 A.Gee and B. Laangstroem Acta Chem. Scand. 1991 45 431. 144 (a) A.L. Feliu Appl. Radiat. Isot. 1992 43 1159; (b) R. Gail H. H. Coenen K. Hamacher and G. Stoecklin ibid.1992 43 1129. 145 C. Prenant C. Crouzel D. Comar J. M. Valois and D. W. Robertson ihid. 1992 43 946. L46 S. Bonnot C. Prenant and C. Crouzel ref. 1 p. 414. 14' M. Holschbach W. Roden and W. Hamkens J. Labelled Compd. Radiopharm. 1991 29 431. H.T. Ravert R. F. Dannals A.A.Wilson and H. N. Wagner Jr. ibid. 1992 31 403. P. Goethals J. Sambre M. Coene K. Casteleyn and E. Poupeye Appl. Radiat. Isof.,1992 43 952. 150 D. Labar and T. Van der Borght ref. 1 p. 432. 14' Radiochemistry 463 unlabelled carbon dioxide a rapid route to [o-"C]carboyxlic acids'" has been created. Further conversion of methyl iodide to [''Clnitromethane has been used in the preparation of labelled sugars' 52 and ranitidine.' 53 Larger labelled alkyl iodides have been used in the preparation of 5-[l-' 'Clethyl barbiturates,' 54 ["C-isopropyl] nim~dipine,'~'and various [p-"Clamino acids.' 56 The short half-life of carbon-11 requires that the chemical reactions to produce labelled compounds be carried out as quickly as possible.This has lead to the introduction of many automated procedures.'30*' 57 319135*142*149,1 Carbon-14.-Whilst many new 14C-labelled compounds have been prepared no new synthetic routes or techniques have been involved and so none will be reported here. It may however be of interest to record that many 14C-labelled peptides can be made' '' by allowing barley seeds to germinate in an atmosphere containing 14C0,. Nitrogen-13.-The deuteron bombardment of methane or the proton irradiation of water'59 or acetic acid and ethanol16' all lead to the formation of ['3N]ammonia.From this starting material new rapid routes to ['3N]glutamate,'61 ['3N]-y-aminobutyric acid and ['3N]putrescine' 62 have been reported. Oxygen-15.-Proton irradiation of water can also lead to the formation of ''0. The addition of a small amount of oxygen to the water is reported'63 to augment the yields of [''Oldioxygen and carbon [''O] monoxide. The reaction of labelled oxygen with tributylborane' 64 leads to [''Olbutanol. Automated procedures using inexpensive microcomputers have been reported for both this reaction16' and the production of labelled oxygen gas. '66 Fluorine-18.-Almost all fluorine labelling reactions use the ['*F]fluoride anion as a reagent and microwaves have been reportedI6' to have beneficial effects by shortening reaction times and boosting yields.An urgent need in nuclear medicine is the preparation of compounds in which the 15' T. Kihlberg P. Malmborg and B. Laangstroem ref. I p. 149. 15' K.-0. Schoeps C. Halldin B. Laangstroem and S. Stone-Elander Appl. Radiat. isot. 1991 42 877. 153 C. Le Breton and C. Crouzel ref. I p. 263. 154 (a)A. D. Gee P. Malmborg and B. Laangstroem ref. I p. 127; (b)A. D. Gee and B. Laangstroem Appl. Radiat. Isot. 1991 42 1195. S. Stone-Elander C. Halldin P. Roland L.. Widen and E. Schwenner ibid. 1991 42 871. 156 K. F. Fasth P. Malmborg and B. Laangstroem ref. 1 p. 411. 157 (a)J. D. Fissekis C. M. Nielsen S. Tirelli A. F. Knott and J. R. Dahl Appl. Radior. fsot. 1991.42 1169; (b) A.Zobeley H. Knigge W. J. Obers F. Oberdorfer and W. Maier-Borst ref. 1 p. 161;(c)S. K. Luthra. D. R. Turton K. Dowsett D. M. Bateman M. J. Kensett S.L. Waters and V. W. Pike ref. I p. 264. J. R. Ling P. B. Cooper S. J. Parker and 1. P. Armstead J. Labelled Compd. Radiopharm. 1992,31.417. 15') F. Oberdorfer and W. Maier-Borst ref. 1 p. 195. B. Wieland G. Bida H. Padgett G. Hendry E. Zippi G. Kabalka J.-L. Morelle R. Verbruggen and M. Ghyoot Appl. Radiat. Isot. 1991 42 1095. ''I F. Helus K. Weber S. Zeisler and W. Maier-Borst J. Radioanal. Nucl. Chem. Letters 1991 155 9. 16' G.W. Kabalka Z. Wange J. F. Green and M. M. Goodman Appl. Radiat. fsot. 1992 43 389. J. M. Link K. A. Krohn and J. H. Courter ref. I p. 112. B.Bauer and R. Wagner ref. 1 p. 67. 16' M. M. Goodman J. L. DeVinney,G. W. Kaba1ka.C. P. D. Longford M. Ladetsky and J. F. Green ref. 1 p. 168. 166 D. Le Bars F. Lavenne K. Sasse and P. Landais. ref. 1. p. 110. (a)S. A. Stone-Elander and N. Elander ref. 1 p. 174; (h)S. A. Stone-Elander and N. Elander Appl. Radiat. Isot. 1991 42 885. 464 D. S. Urch fluorine label is bound to an aromatic ring. Such compounds can then be incorporated into dopamine derivatives and dopamine receptors. However fluoride engages in nucleophilic aromatic substitution reactions with some reluctance. Encouragement is needed and this has been found to be by many researchers,'"-' 73 the presence of an aldehyde group. Thus in 2-or 4-nitrobenzaldehyde and 2-methoxy-4-nitrobenzal-dehyde the labelled fluoride anion will replace the nitro-group.Subsequent reactions at the aldehyde site lead to I8F-labelled fluor~phenols,'~~ fluoroanisoles,' 70 fluorocatechols,' 71 4-fluorobenzyl iodide,' 72 and fluorobenzyl bromides.' 73 In 2-and 4-nitrocinnamaldehydes,' 74 nitrophenones '' and N-methyl-4-nitrospiperone' 76 the electron withdrawing carbonyl group exercises a similar activating effect so that fluoride replacement of the nitro group becomes possible. The diazonium group can also activate the aromatic ring'77 to nucleophilic attack by I8F-.The preparation of 6-[ '8F]fluoro-~-dopa by many routes has been reported; by the fluoride displacement of nitro groups'78 as described above by the use of "F labelled fluorine gas in the presence of hydrogen fluoride and boron trifluoride' 79 to initiate direct fluorination of an aromatic ring and by the use of acetyl ["F]hypofl~orite."~ In the latter case a wholly automated procedure has been described.' 8oc,' 8' Labelled hypofluorite has also been used to prepare ['8F]tyrosine derivatives.' 82 There is still interest in the preparation of ''F-labelled sugars.' 83 Fluoride exchange reactions can be used'84 and automated procedures have been described.' 8s These include the development of a laboratory robot' 86 which can be used in the preparation of other labelled compounds such as ["F]estradiols.' "Exchange reactions have also been used to produce labelled chloro-fluoro aryl ethers,' 6-deoxy-6-[' 8F]fluoro- 16' C.Lemaire M. Guillaume A.Plenevaux R. Cantineau P. Damhaut and L. Christiaens. ref. 1 p. 131. 16' P. K. Chakraborty and M. R. Kilbourn. Appl. Rudiat. Isot. 1991 42 1209. 170 A. Plenevaux C. Lemaire A. J. Palmer P. Damhaut and D. Comar Appl. Radiat. Isot. 1992 43 1035. 17' P.K. Chakraborty and M.R. Kilbourn ref.'l p. 130. 17' R.H. Mach J.G. Scripko. R. L. Ehrenkaufer and T. E. Morton ref. I p. 152. 173 (a)C. Lemaire P. Damhaut A. Plenevaux R. Cantineau L. Christiaens and M. Guillaume Appl. Radial. [sot. 1992,43,485; (b)K. Hatano T. Ido K. Ishiwata and R. Iwata ref. 1 p. 134; (c)K. Hatano. T. Ido and R. Iwata J. Labelled Compd. Radiopharm. 1991 29 373. 174 Y.S. Ding J. S. Fowler and A. P. Wolf ref. 1 p. 146. 17' (a)D. R. Hwang C. S. Dence and M. J. Welch ref. I p. 138; (b)D. R.Hwang C. S. Dence J. Gong and M. J. Welch Appl. Radiat. Isot. 1991 42 1043. 176 K. Hamacher B. Nebeling. H. H. Coenen and G. Stoecklin ref. 1 p. 361. 17' (a)A. Knoechel and 0.Zwernemann Appl. Radiat. Isor. 1991,42,1077;(h)0.Zwernemann Ph.D. Thesis University of Hamburg Germany 1991. "' (a)C. Lemaire M. Guillaume R. Cantineau A. Plenevaux. and L. Christiaens ref. 1 p. 274; (h)B. B. Dunn M. A. Channing H. R. Adams D. S. Goldstein. K. L. Kirk and D.O. Kiesewetter ref. 1 p. 298. 179 R. Chirakal G.J. Schrobilgen G. Firnau and E. S. Garnett ref. 1 p. 294. (a)M. Namavari A. Bishop N. Satyamurthy J. R. Barrio and G. Bida Appl. Radiat. lsot.,1992.43,989; (b)0.T. DeJesus D. Murali C. A. Chen J. J. Sunderland M. Weiler and R. J. Nickles. ref. 1 p. 279 (L.) M. J.Adam and S. Jivan J. Labelled Compd. Rudiopharm.. 1992 31 39. T. Ruth M. Adam S. Jivan D. Morris and S. Tyldesley ref. 1 p. 310. 18' D. Murali O.T. Dejesus J. J. Sunderland and R. J. Nickles Appl. Radiut. Isot. 1992 43. 969. M. M. Goodman G. W. Kabalka X. Meng. G. B. Daniel C. P. D. Longford G.T. Smith and M. K. Hunter ref. 1 p. 301. lE4T. Haradahira A. Kato M. Maeda Y. Torii Y.-I. Ichiya and K. Masuda Appl. Radiat. Isof.. 1992.43 627. I*' E. L. Kaemaeraeinen and A. Paajanen ref. I p. 181. J. W. Brodack and M. J. Welch. ref. I. p. 171. M.J. Welch J. W. Brodack C. J. Mathias M.G. Pomper K. E. Carlson and J. A. Katzenellenbogen ref. 1 p. 438. ''* M.R. Kilbourn and R. Subrdmanian ref. I. p. 151. Radiochemistry 465 L-ascorbic acid,' 89 17-['8F]fluoro-3-or 5methylheptadecanoic acid,' 90,1 91 and ['8F]fluoromethane.192 The role of solvent in promoting the efficiency of exchange reactions involving adsorbed fluoride anions has been investigated' 93 and procedures described' 94 for recovering unreacted [18F]fluoride from dry supports for re-use.Elements of Modest Mass.-Methods for the preparation of [32P]-labelled nucleo- tides 195.196 and the synthesis of ["S]- 1,l'-thiobis(2-~hloroethane)'~~ have been described whilst recent work ~ith~~Cu seems to have been confined to the preparation of bis(thiosemicarbazone) derivatives.' 98 Gallium C6'Ga or 68Ga] can be complexed with polydentate ligands such as bisaminoethanethiol' 99 for direct use in nuclear medicine or if the ligand is bifunctional the chelate can be coupled to monoclonal antibodies,200 or other proteins via carbodiimide links.201 New methods for the preparation of ~-[~~Se]selenomethionine~~~ have been reported.A variety of bromine isotopes have been used to label diverse molecules; 6-[82Br]bromomethyl choles- ter01,~'~[5-80mBr]bromodeoxyuridines,204[77Br]monoclonal antibodies,205 [2-76Br]bromoketanserin and [2'-76Br]bromospiperone.206 A method for the incorpor- ation of 89Zr into water-soluble p~rphyrins~'~ has been described. Te~hnetium-~~"Tc.-This element continues to be one of the most widely used radioactive isotopes in nuclear chemistry. It is easily and widely available in kit form and new guide-lines208 for the preparation of such kits have recently been issued by the IAEA.Pertechnate(vI1) ions are washed from a suitable column bringing,209 it is to be hoped negligible 99Mo with them. A range of different complexes can then be prepared with the technetium in a reduced valence state and encapsulated by a suitable ligand. The use of esters and derivatives of dithiocarbazic acid2' leads to complexes in which IR9 F. Yamamoto S. Sasaki and M. Maeda Appl. Radiar. Isot. 1992. 43 633. 19" T. Takahashi T. Ido and R. Iwata Appl. Radiat. Isor. 1991 42 801. 19' T. Takahashi T. Ido and R. Iwata Appi. Radial. Isor.. 1992 43 822. 192 S. J. Gatley R. Franceschini R. Ferrieri I). J. Schyler and A. P. Wolf Appl. Radiat. Isot. 1991.42 1049. 193 D. M. Jewett and G. K. Mulholland ref. 1 p. 193. 194 G. K. Mulholland Appl. Radiat.Isot. 1991 42 1003. 195 S. Deheng and W. Meizhong J. Nucl. Radiochem. 1991. 13 44. 196 J. J. Di Meo 'Synthetic process for preparation of "P-labelled nucleotides' US patent Document 5087 565/A Patent and Trademark Office Box 9 Washington DC USA 1992. 19' J.M. Harrison J. Labelled Compd. Radiopharm. 1991 29 1175. 19' (a)E. John. A. J. Barnhart P. W. Wade and M. A. Green ref. 1 p. 53; (b)A. J. Barnhart and M. A. Green ref. 1. p. 64; (c)T. W. Lee D. W. McPherson A. P. Callahan. D. E. Rice F. F. Knapp. Jr. and G. Ting ref. 1 p. 76. 199 L.C. Francesconi B. L. Liu J. Billings M. P. Kung A. Alavi and H. F. Kung ref. 1. p. 70. 20" Y. Arano H. Matsushima M. Tagawa. M. Koizumi Y. Watanabe K. Endo J. Konishi and A. Yokoyama ref. I p. 318. *01 J. Schuhmacher.G. Klivenyi W. Maier-Horst and S. Matzku. ref. I p. 323. *02 (a)G. Engelskirchen K. Hamacher and G.Stoecklin ref. I. p. 140; (b)J. Roemer P. Maeding and F. Roesch Appl. Radial. Isot. 1992 43 495. '03 Z. Xiaoxiang and L. Boli J. Nucl. Radiochem.. 1991 13 49. '04 R.C. Mease S.J. Gatley and A.M. Friedman J. Labelled Compd. Radiopharm. 1991 29 393. '05 F. Lambert G. Slegers and P. Goethals ibid. 1991 29 729. '06 M. Gysemans and J. Mertens ref. I p. 372. '07 S. A. Ali and E.G. Shankland ref. I p. 334. 'OH 'Preparation of kits for 99mTc radiopharmaceuticals'. IAEA Technical Document No. 649 International Atomic Energy Agency Vienna 1992. '09 K. K. Kothari and M. R.A. Pillai ref. 40 paper AR-19. 'lo (a)M. Borel M. Rapp J. C. Madelmont D. Godeneche A.Veyre. and R. Pasqualini Appl. Radiat. Isot. 1992 43 425; (b)A. Duatti A. Marchi and R. Pasqualini ref. 1 p. 13. 466 D.S. Urch the technetium is bound to nitrogen by a triple bond. Other radiopharmaceuticals can be produced by preparing 1,lo-phenanthroline complexes of technetium(lr).2 l1 Nitrosyl and carbonyl groups are also very effective in forming bonds to techne- tium,2' and new complexes based on dimethoxy- and diethoxyhexanedione diox- ime2' have recently been reported. Phosphorus based ligands have also been widely used to produce technetium complexes that could be used as radiopharmaceuticals; methylene diphosphonic acid,2 l4 1,2-epoxypropylphosphonicacid,2 phenyl-bis-hydrazide-phosphine,2' and also bidentate phosphino-amine ligands" ' in which both nitrogen and phosphorus bond to the technetium.Bonding to nitrogen is clearly important in technetium complexes with porphyrins,2 * amino acids and small peptides. In the latter cases sulfur too will often be involved as in complexes with ethylenedi~ysteine,~ or valine,221 l9 glycine alanine,220*221 An appreciation of the ability of sulfur to form strong bonds with technetium has led to a much more sophisticated approach to the direct labelling of large protein molecules and monoclonal antibodies. Such molecules contain cysteine groups linked by sulfur-sulfur bonds which can be broken by gentle reduction yielding two thiol groups available for complex formation.222 With care this procedure can be carried out without apparently impairing the overall biological activity of the protein.As many of the reducing agents that are used contain sulfur e.g. 2-mercaptoethan01,'~~2-amin~ethanethiol,~~~ complications can arise.225 Another related approach is to synthesize a 'bifunctional' molecule one part of which will form a strong complex with technetium and another part of which will readily conjugate with a Recently many mercaptoamides228 and aminothio12' 7,229 have been studied to assess their suitability as complexing sites in such molecules and derivatives of mercapto-acetyltriglycine technetium complexes230 are already in use in nuclear biology. 211 K. Schwochau K. H. Linse. and A. F. Su Appl. Radiat. /.sot. 1992 43 1079. '12 H. H. Knight Castro C. E. Hissink H. H. Teuben and W. Vaalburg ref.1 p. 73. '13 Z.F. Su K. H. Linse H. J. Steinmetz and K. Schwochau J. Lahelled Compd. Radiopharm. 1992,31 61. '14 F. Budsky J. Prokop V. Sara and B. Angelis Jad. Energ. 1992 38 149. '15 M. Neves. A. Paulo I. Castanheira and L. Patricio Appl. Radiat. Isot. 1992 43 731. 216 K. V. Katti P. R. Singh W.A. Volkert A. R. Ketring and K. K. Katti. ihid. 1992 43 1151. '17 F. Refosco A. Moresco G. Bandoli U. Mazzi M. Nicolini and A. Duatti ref. I p. 16. 21R A. B. Packard ref. 1 p. 14. 219 C. Van Nerom. D. Osiadacz B. Cleynhens M. De Roo and A. Verbruggen ref. 1 p. 36. R. F. Schneider G. Subramanian J. G. McAfee D. Karczewski L. Fantinato G. Gagne and F. D. Thomas ref. I p. 33. 221 E. Havranek A. Bumbalova P. Krenek M. Strasak. M. Belakova. and M. Komova J. Radioanal.Nucl. Chem. Letters 1991 55 253. 222 (a)B. A. Rhodes. Nucl. Med. Biol. 1991,18,667; (h)J. R. Thornback B. Bastin. and E. Joiris 'Procedures for the labelling of proteins or polypeptides with '""'Tc. The use of the labelled conjugates in medical imaging. Details of a preparative kit' French Patent Document 2 650672/A Institut National de la Propriete Industrielle Paris France 1989. 223 J. DeFulvio and M. L. Thakur ref. I p. 225. 224 J.Y. Garron M. Moinereau R. Pasqualini and J. C. Saccavini Nucl. Med. Biol. 1991 18 695. 225 M.V. Pimm R. S. Rajput S.J. Gribben and M. Frier Eur. J. Nucl. Med. 1991 18. 973. 226 P. Angelberger R. Portner 0.Buchheit F. Fally M. Egger and A. Schwarzl in 'Functional Liver Imaging with 99mTc-NGA' ed. I. Virgolini and H.Sinzinger Wien Facultas Universitatsverlag Vienna. Austria 1989 p. 1. 227 M. Eisenhut. M. Missfeldt W. D. Lehmann and M. Karas J. Luhelled Cnmpd. Radiopharm. 1991 29 1283. 228 G. Bormans M. Malfait b. Cleynhens D. Crombez M. De Roo and A. Verbruggen ref. 1. p. 21. 229 (a)K. Shiba H. Mori H. Matsuda S.Tsuji K. Kinuya and K. Hisada. Appl. Radiar. /sot. 1991,42 1159; (b)C. S. John P. Hosain L. Cioloca C. H. Paik R.C. Reba and E.0.Schlemper. ref. I. p. 18. 230 (a)B. Noll H. Spies B. Johannsen,and K. May Appl. Radiat. /sot.. 1992.43.899 (h)M. Subhani H. Van Radioc hemistry 467 Indium.-Much the same philosophy applies to the preparation of indium complexes for nuclear medicine as for technetium complexes. Bifunctional chelate molecules have been ~ynthesized~~ ’ and bifunctional diamide dithiol complexes prepared.232 Quite complicated ligands have been made e.g.trans-1,2-diaminocyclohexane-N,N,N’,N’-tetraacetic involving ~enta-*~~ (triethylenetet-and even hexa-c~ordination~~~ raaminehexaacetic acid) of the indium. Iodine.-For the most part radioactive isotopes of iodine can be incorporated into organic molecules by quite conventional procedures the commonest being radioiodine-iodine exchange which can be assisted by chloramine-T. A more specific method is ‘de~tannylation’~~~ in which an organotin group usually tributyltin is replaced by iodine. Recently this technique has been used to label 4’-iodo~ocaine~~~ with 1231and monoclonal antibodies238 with 13’1 after they had been conjugated with pyridine and furan derivatives.Other reagents that have been proposed for protein labelling are [’251]tyramines,239 N-succinimidyl m-[’ 251]benzoate,240 tetrafluoro- phenyl-m-[’ 251]iodobenzoate and tetrafluorophenyl-5-[’ 251]iodopentenoates;241 it appears that iodine at the meta position is less susceptible to metabolic deiodination than at the ortho or para sites. There has been some interest in the preparation of glucose derivatives labelled with either [1231]242 or [1251]243 and rather more interest in radioiodine compounds244 that are related to dopamine or dopamine D2 antagonists. Many compounds in the latter group are of the type 2,3-disubstituted- 5-iodobenzamides and the preparation of [1231],[’251],245 and [1311]246 labelled examples have all been reported.Some effort has also been directed at the preparation of iodinated estrogen derivatives for nuclear medical (breast cancer) applications. 16a-Iodoestradiol seems to be rather too easily deiodinated and so the 7a-methyl-and 1Ifl-ethoxy-l6a-[ ‘251]iodoestradiols have both been prepared.247 A series of com- Billoen B. Cleynhens G. Bormans C. Van Nerom D. Crornbez M. De Roo and A. Verbruggen ref. 1. p. 80; (c) Y. Dehua Z. Jun and X. Jiaqi hucl. Tech. 1991 14 266. 231 S. W. Schwartz C. J. Mathias W. G. Dilley S.A. Wells Jr. M. J. Welch Y. Sun and A. E. Martell ref. I p. 320. 232 V. K. Sood C. H. Paik C.S. John and R.C. Reba ref. 1 p. 231. 233 R. C. Mease J. F. Gestin G. E. Meinken. and S.C. Srivastava ref. 1 p. 202. 234 Z. Lin L.Boli and M. Kojima J. Nucl. Radiochem. 1991 13 223. 235 K. K. Bhargava Z.Y. Zhang B.S. Chun. and S.A. Acharya ref. 1 p. 222. 236 R.N. Hanson in ref. 9 vol. IB 1991 p. 285. 237 S.A. M. Metwally S.J. Gatley A. P. Wolf and D.-W. Yu J. Labelled Compd. Radiopharm. 1992,31,219. 238 S. Garg P. K. Garg D. D. Bigner and M. R. Zalutsky ref. 1 p. 214. 23y S. E. Kakabakos E. Livaniou S.A. Evangelatos G. P. Evangelatos and D.S. Ithakissios Eur. J. Nucl. Med. 1991 18 952. A. Freud A. Canfi and N. Hirshfeld. ref. I p. 211. X. Shen R.N. Hanson and D. R. Elmaleh ref. 1 p. 229. 242 (a) M. M. Goodman G. W. Kabalka R. N. Waterhouse and G. B. Daniel ref. 1. p. 285 (b)M. M. Goodman G.W. Kabalka X. Meng G.B. Daniel and C. P. D. Longford ref. I p. 287; (c)T. Lutz D.M. Lyster H.Dougan T. Rihela M. Hudon W.R.E. Jamieson and P. Cohen J. Labelled Compd. Radiopharm. 1991 29 535. 243 Y. Magata M. Inagaki Y. Yamada H. Saji A. Yokoyama and Y. Ohmomo ref. I p. 306. 244 (a)M. J. Adam Y. Z. Ponce and J. M. Berry ref. 1 p. 284; (b)M. J. Adam J. Lu Y. Z. Ponce J. M. Berry J. Labelled Compd. Radiopharm. 1992 31 3. 24s J. A. Clanton D. E. Schmidt M. S. Ansari R. G. Manning R. M. Kessler T. de Paulis,and R. M. Baldwin J. Labelled Compd. Radiopharm. 1991,29.745; (b)C. A. Mathis J. M. Gerdes A.T. Shulgin S. Hanrahan B. Faggin and R. Mailman ref. 1 p. 370; (c) M. Ponchant T. Koscielniak M. Hamon and H. Gozlan J. Labelled Compd. Radiopharm. 1991 29 1147. 246 R. Cantineau P. Damhaut A. Plenevaux. C. Lemaire and M. Guillaume ref. I p. 368. 247 H.Ali J. Rousseau and J. E. van Lier ref. I p. 451. 468 D. S. Urch pounds based on .17c(-[' 231 or '251]iodovinylestradiol has also been made.248 Radioactive iodine isotopes can also be incorporated into deoxyuridine~~~~q~~~ and rn-[' 'I]iodobenzylguanidine250 by exchange reactions. Heavy Elements.-Some preliminary results have been published2 ' on the possible pharmaceutical applications of rhenium [186Re or '"Re] labelled liposomes. The use ofcisplatin as an anti-tumour drug has lead to improved,252 automated253 methods for its preparation labelled with 195mPt. Other radioplatinum compounds have been made by Szilard-Chalmers type reactions. Neutron irradiation of ( -)-(R)-2-aminomethyl-pyrrolidine(1,l-cyclobutanedicarboxylato)-2-platinum(r1), which had been made with enriched 194Pt gave good yields of the same complex labelled254 with 195mPt whilst cis-1,l-cyclobutane-dicarboxylato-(2R)-2-methyl-1,4-butanediamine platinum(Ir) en- riched with 192Pt gave the complex but labelled255 with 191Pt 193mPt 195mPt,and 19'Pt.The gold isotope [199A~]has attractive properties for nuclear medicine applications. It can be incorporated into proteins256 by the expedient so successfully used for technetium reduction of a cyst disulfide bond to two thiols which can then chelate to the gold Au'. The bifunctional ligand approach was both to label a monoclonal antibody with '03Pb and proteins258 with 21 'At. 5 Environment The dangers posed by the increasingly widespread use of nuclear power and of radioactive substances have generated much study towards determining the environ- mental fate of radioactive materials how they may be detected and how they may be contained.In the case of nuclear reactors for power generation two aspects have exercised the minds of workers in the field first to contemplate what would happen in the event of a 'severe' a~cident;~~~.~~' second to consider methods for the disposal of waste. These are considered in detail below. Fission Products (excluding iodine).-Much recent research has investigated the efficiency with which various materials can adsorb fission products. Layer silicates 248 (a)J. Quivy M. Zeicher A. Delcorde P. Henrot M. Deblaton R. Pirotte A. Verbist and J. Fruehling ref. 1 p. 454; (b)G. W.Kabalka T. M. Shoup and M. M. Goodman ref. I p. 441. 249 N. Scherberg I. Bloch and P. Gardner Appl. Radiut. Isot. 1992. 43 923. 250 M. Neves A. Paulo and L. Patricio Appl. Radiat. Isot. 1992 43 737. 251 U. Haefeli P. Blaeuenstein L. Tiefenauer. and P.A. Schubiger. ref. I p. 341. 252 H. Jackson A. Perera. C.A. McAuliffe H. L. Sharma and N. J. Tinker. J. Labelled Compd. Radiopharm. 1991 29 1121. 253 D. Anand and W. Wolf Appl. Radiat. Isot. 1992 43 809. 254 K. Kawai Y. Nakano H. Maki M. Akaboshi S. Takada. and W. Ehrlich J. Radioanal. Nucl. Chem. Letters. 1992 164 123. 255 M. Suwa 0.Kogawa Y. Hashimoto H. Nowatari Y. Murase and Y. Homma J. Labelled Cornpd. Radiopharm. 1992 31 349. 256 L. Zhaoqing W. Yonghui and L. Yuanfang J. Nucl. Radiochem. 1991 13 18.251 R. Clem R. M. Lambrecht S. Mirzadeh C.G. Pippin M. W. Brechbiel M. Roselli 0.A. Gansow and D. Colcher ref. 1 p. 335. 258 D.S. Wilbur S.W. Hadley J. J. Hines. and R. W. Atcher. ref. I p. 220. 259 A. L. Nichols 'Fission Product Chemistry in Severe Nuclear Reactor Accidents' Report AEA-TRS-5024. AEA Winfrith UK 1990. 260 A. M. Beard P. J. Bennett C. G.Benson and F. Sabathier. 'Chemistry aspects of the Falcon programme'. Report AEA-TRS-5072. AEA Winfrith UK 1990. Radiochemistry 469 (clays montmorillites) were found2’’ to be particularly effective at removing ’37Csand 90Sr from water whilst trace amounts of 90Sr were extracted262 from lake waters by a titania-silica gel. Radioactive caesium ( 134Csand 137Cs) is adsorbed by copper hexacyanoferrate loaded resins263 and can be separated from solutions containing calcium264 by an inorganic ion-exchanger.The ion-exchange behaviour of fission produced yttrium and ruthenium26s in acid has also been studied; the sorption properties of shales for caesium strontium and technetium266 ions have been investigated. As might be expected crystal defects are important in regulating adsorption reactions.267 Investigations have also been made on bitumen to determine its sorption behaviour towards strontium268 and whilst activated carbon has been shown270 to be an effective adsorbant for pertechnate ions. Once adsorbed however the question then arises for how long?; for 137Csin cement this question has been addressed,271 if not yet answered. Iodine.-The dangers posed by the volatility of many iodine species and the possibility of such volatiles being produced by has made radioiodine the subject of particularly intense research.Experiments to study the behaviour of radioiodine in a wide variety of situations were carried out in the Canadian Radioiodine Test Specific experiments investigated the formation of organic iodides from surfaces274 and epo~y-resins~~’ as well as the behaviour that might be expected under severe reactor accident conditions.276 The feasibility of using the iodine-starch complex to extract iodine from aqueous solutions has been it works well in acid. A new device for the on-line monitoring of air-borne radioiodine has been described278 and its reliability under extreme conditions assessed.Heavy Elements.-Radon is now appreciated to make a major contribution to the radiation dose which we all receive from natural sources. Recent studies have ”’ B. Yu. Kornilovich G. N. Pshinko A. A. Kosorukov A. N. Mas’ko L. N. Spasenova and T.N. Dregval Khim. Tekhnol. Vody. 1991 13 1025. 262 E.G. Belyakova V. V. Kaftajlov V. M. Shamrikov Yu. V. Egorov V. I. Malkiman and S. I. Kon’kov Radiokhirniya 1990 32 111. 263 I. J. Singh and M. Ramaswamy Report HARC-1991/E/OZZ Bhabha Atomic Research Centre Bombay India 1991. 264 R. Stella M.T. Ganzerli Valentini and I,. Maggi ref. 25 p. 49. 265 T. Sato J. Radioanal. Nucl. Chem. Articles 1991 152 219. ”‘ P.C. Ho Radiochim. Acta 1992 56. 159. 26-I. V. Melikhov S. Bachich V. F. Komarov S. Lazich Zh.Vukovich Radiokhimiya 1991 33. 87. 26H L. R. van Loon and 2.Kopajtic Radiochim. Acta 1991 55 83. 269 L.R. van Loon and Z. Kopajtic Radiochim. Acta 1991 55 91. 270 K. Ito and K. Akiba J. Radioanal. Nucl Chem. Articles 1991 152 381. 27’ I. Plecas. A. Peric J. Drljaca and A. Kostadinovic J. Radioanal. Nucl. Chem. Letters 1991 154. 309. 272 (a)N. Ishiwatari in ‘Proceedings of the Third CSNI Workshop on Iodine Chemistry in Reactor Safety’ ed. K. Ishigure M. Saeki K. Soda,and J. Sugimoto Japan Atomic Energy Research Inst.,Tokyo Japan. 1992 p. 81; (b)M. Naritomi H. Nagai S. Okagawa and N. Ishiwatari ibid. p. 97. 273 (a)W. C. H. Kupferschmidt G. J. Evans D. J. Jobe A. J. Melnyk R. Portman A. Palson and G. G. Sanipelli. ibid. p. 249; (b)R. J. Fluke J. H.Edward K.R. Weaver and G. J. Evans ibid. p. 396. 274 A.M. Deane ihid. p. 181. 27s G.J. Evans and A.S. Palson ihid. p. 230. ”’ (u)G. J. Evans and R. E. Jervis ref. 25 p. 20; (h)J. M. Buron. S. Fernandez and A. Alonso ref. 272(a) p. 446. 2’7 V. P. lgnatov and I. V. Kolomejtseva Radiokhimiya. 1990 32 114. B. S. Lee W. A. Jester and J. M. Olynyk. Nucl. Technol. 1992 97 63. 470 D.S. Urch investigated the state of radon in crystalline polymers;279 have shown how to produce a radon-rich solution in water for test purposes;280 and have considered the chemistry of radioactive lead and bismuth281 produced by radon decay. A detailed study has also been made of the fate of the daughter atom l8Po in propene-nitrogen mixtures. Both the radon concentration and humidity were found282 to be important in determining the rates of ion neutralization and of formation of polonium hydroxide.The chemistry of francium and radium is of course quite different; the problem here can often be the removal of their cations from solution. For 223Frthis can be achieved by adsorption on zinc or nickel hexacyanoferrates(r1) whilst 223Ra is held by hydrated antimony pentoxide .283 The Actinides.-The transport of many transuranic elements by ground water and highly saline solutions has been studied. The behaviour of both americium284 and neptunium is affected by their ability to form complex carbonates285 and neptunium(v) is present286 as both [NpO,] + and [Np02C03] -. A detailed investigation of 237Np in intertidal sediments in the Irish Sea has that its ‘environmental chemistry’ is quite different from that of plutonium or americium.In saline solutions (i.e.the sea) the behaviour of Puv1284 is strongly affected by its own alpha radiation.288 The chemistry of transplutonium elements both in aqueous and terrestrial environments has been briefly surveyed.289 Finding a permanent home for the actinide elements out of harms way is proving quite difficult. Two recent studies that might be helpful have been an investigation of the bonding of uranyl cations to m~ntmorillite~~~ and a measurement ofdiffusion coefficient^^'^ for 241Am 239Pu and 237Np in various glasses. The dangers of plutonium metal have been emphasized292 in a reassessment of basic ther- modynamic values which suggests an exothermic reaction with most solvents.6 Miscellaneous Thin Films.-Thin radioactive sources would appear to be in vogue. Descriptions of sources made from thin deposits of lanthanides,293 46Sc and 88Y,and 294 251as well as 2’y I.N. Bekman and I.M. Buntseva J. Radioanal. Nucl. Chem. Lett. 1991 153 345. 280 C. A. Hazin in ‘Proceedings of the First Brazilian Meeting on Nuclear Applications’ Cornissio Nacional de Energia Nuclear RJ Brazil 1991 vol. 1 p. 231. ’*’ A. W. Casteman Jr. Enuiron. Sci. Technol. 1991 25 730. 282 C. R. Phillips Report INFO-0364 Atomic Energy Control Board Ottawa Canada 1988. 283 C. Loos-Neskovic B. Bartos M. Hussonnois. and 0.Constantinescu J. Radioanal. Nucl. Chem. Lett. 1991 155 243. 284 J.I. Kim B. Delakowitz R. Klenze V.Koss G. Meinrath I. Pashalidis and H. Wimmer Report RCM-01390 Bundesrninisterium fur Forschung und Technologie Bonn Germany 1990. 285 G. Meinrath Ph.D. Thesis Tech. Univ. Munich Germany 1991. 286 E. P. Kajmin and L. I. Konstantinova Radiokhimiya 1991 33 210. 287 M. Yamamoto Y. Yamauchi K. Komura K. Ueno and D. J. Asinder J. Rudioanal. Nucl. Chem. Lett. 1991 154 299. I. Pashalidis Ph.D. Thesis Tech. Univ. Munich Germany 1991. 289 F.I. Pavlotskaya Yu. N. Pospelov B. F. Myasoedov Yu. V. Kuznetsov and V. K. Legin Radiokhimiya 1991 33 112. 290 C. Chisholm-Brause D. E. Morris P. G. Eller. T. Buscher and S. D. Conradson in ‘Proceedings of 15th International Symposium on the Scientific Basis for Nuclear Waste Management’ US Govt. Printing Office Dep. 1991 p.19. I. A. Ivanov V. M. Sedov A. N. Gulin V. M. Shatkov and E. A. Shashukov Radiokhimiya 1990,32. 139. 2y3 L. E. I. Lanthanides and A. F. Novgorodov Report R-9-91-56 Joint Inst. for Nuclear Research Dubna USSR 1991. Rad iochemistry 471 thorium and uranium oxides295 have all appeared recently as well as a recipe296 for the deposition of alpha-emitting isotopes on the surface of ferric hydroxide colloid particles. Analytical Methods.-Tritium can be located in organic molecules by NMR spectro-sc~py.~~’ It can also be used to investigate the spatial structure of biological macromolecules. In this technique298 the sample surface is tritiated by ‘hot-atom’ bombardment and structural information deduced from the positions of the tritium atoms.Procedures to ensure the accurate determination of the specific activity of tritium in biosystems have been described.299 This determination is rendered difficult by isotope effects that accompany fractionation in tissue water separation. Somewhat different problems are encountered in monitoring ‘‘’I contaminati~n,~~~ and the stability of counting standards has been critically assessed. y-Decay can sometimes proceed by a cascade mechanism and there is then the possibility of observing some angular correlation between the emitted prays. This is so for “In where chemical effects can perturb the correlation. This in turn provides301 a valuable in situ probe of the chemical environment of the indium. Whilst it might be thought that their intrinsic radioactivity would enable transuranic elements to be detected even at great dilution the new technique of laser-induced photoacoustic spectroscopy302 has proved superior at the nanomole level.Speciation as well as detection is possible for uranium neptunium plutonium and americium ions in aqueous solution. 294 J. J. McGovern and J. M. Olynyk Norwtyian Patent Document 167 343/B Patent Office Oslo Norway 1991. 295 Y. Shiokawa A. Nomura M. Yagi and R. Amano. J. Radioanal. Nucl. Chem. Articles 1991. 152 373. 296 R. W. Atcher and J. J. Hines US Patent Documents 5030441/A Patent and Trademark Office Box 9 Washington DC USA 1990. 297 D. K. Jaiswal H. Morimoto M. Salijoughian and P.G. Williams in ref. 2. p. 6. 298 A.V. Shishkov Khim. Fiz. 1991 10 878. 299 M.A. Kim F. Baumgaertner and C. Schulz Radiochim. Acta 1991 55. 101. 300 M. E. McLain and S.C. Yoon Radiat. Prot. Manage. 1987 4 57. 30’ P.J. Marsden F.A. Smith and S. Mather Appl. Radiat. Isot. 1991 42 815. 302 J.I. Kim R. Stumpe and R. Klenze in ‘Chemical Applications of Nuclear Probes’ ed. K. Yoshihara Springer Berlin Germany 1990 p. 129.
ISSN:0260-1818
DOI:10.1039/IC9928900453
出版商:RSC
年代:1992
数据来源: RSC
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25. |
Chapter 25. Inorganic mechanisms |
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Annual Reports Section "A" (Inorganic Chemistry),
Volume 89,
Issue 1,
1992,
Page 473-493
N. Winterton,
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摘要:
25 Inorganic Mechanisms By N. WINTERTON ICI Chemicals and Polymers Ltd Runcorn Technical Centre The Heath Runcorn Cheshire UK 1 Introduction A chemical transformation cannot be said to be understood fully unless the identity and nature of intermediates formed between reactants and products have been identified and an intimate knowledge of the processes of bond making and breaking and electron transfer established. Inorganic reaction mechanisms concerned with such processes are important both academically and technologically for the light such understanding may throw on key biological biomedical environmental and industrial processes. Space does not permit a comprehensive survey; excluded from the report are mechanisms of heterogeneous reactions homogeneous catalysis of organic reactions fluxional or site exchange processes photochemical and radiochemical processes organic reactions of the p-block elements molecular dynamics and other simulations and topics covered in other sections unless an overriding mechanistic reason justifies their inclusion.The highlight of 1992 was the award of the Nobel Prize for Chemistry to Rudolph A. Marcus for his work which has provided the theoretical foundation for the understanding of electron transfer reactions in chemical systems. Major reviews la.' have appeared on the study of the kinetics of inorganic reactions under high pressure and on solvent and microdomain effects on inorganic reactions.lc Pressure and temperature effects on rates and equilibria are the subject of a monograph.2 2 Redox Reactions A compilation of recent reviews has a~peared.~" Aspects of electron and proton transfer in chemistry and biology have been re~iewed.~" Long-range Electron Transfer.-A current major area of study concerns the develop- ment and experimental testing of through-space and through-bond theories of electron ' (a)R.van Eldik and A. E. Merbach Comments Inory. Chem. 1992 12. 341 ; (b)R. van Eldik Pure Appl. Chem.. 1992. 64 1439; (c)J. Burgess and E. Pelizzetti Proy. Reaction Kinetics. 1992 17 I. ' M. J. Blandamer 'Chemical Equilibria in Solution. Dependence of Rate and Equilibrium Constants on Temperature and Pressure' Ellis Horwood/Prentice Hall Chichester. 1992. (a) M. A. Fox Chem. Rec. 1992,92 365; (b)'Electron and Proton Transfer in Chemistry and Biology'.ed. A. Miiller H. RatajcLak. W. Junge and E. Diemann Studies in Physical and Theoretical Chemistry. Elsevier Amsterdam. 1992. Vol. 78. 473 474 N. Winterton tunnelling focusing particularly on the nature and dynamics of the medium separating and surrounding donor and acceptor. Marcus and others continue to provide the theoretical tools for modelling such proces~es.~~-~ Developments in theory have been of particular significance to an understanding of electron transfer in biological systems. Dutton and co-~orkers~~ have found the slope of a linear relationship between intramolecular electron transfer rate and donor-acceptor separation for a series of biological and chemical systems to lie between values expected for a vacuum and covalently-bonded model systems.They conclude that the intervening medium resembles an organic glass and that the intra-protein electron transfer rate is controlled solely by distance free energy and reorganization energy; this view was challenged by Beratan Gray and others,5b who suggest that the rate ofelectron transfer between two centres will depend on the number and nature of links connecting them. A difference in distance dependence of protein electron-transfer rate at short (< 5 A) and long distances is predicted from studies on specifically ruthenated protein^.^^.^ Through-bond rather than through-space tunnelling is also supported from cyclic voltammetric studies of monolayers of [Ru(NH3)J2 +-functionalized thiols HS(CH,),C-(O)NHCH,py n = 10 11 15.5eDonor-acceptor separation effects on intramolecular Co"-Fe"' electron transfer in a series of specifically cobalt-cage-functionalized cytochrome c proteins have also been studied.5f Most of the activation volume measured for inter- and intramolecular electron transfer between Ru" and Fe"' in two [Ru(NH3)J2 +-modified ferricytochrome c proteins is attributed to solvent electros- triction at the Ru ~entre.~q The outer-sphere oxidants [Cr(phen)J3+ and [CO(NH,),]~ + react with the two forms of [2Fe-2S] ferredoxins isoferredoxin FdI and FdII in the Fe"Fe"' state with 1 1 stoichiometry and saturation kinetics.6a The data are consistent with through- bond electron transfer at a single recognition site which is probably negatively charged.Localized electrostatic interactions between oxidant and charged residues on Anabaena variabilis plastocyanin and azurin and the inorganic complexes [Co(phen),13+ or [Fe(CN)J- have also been suggested.,' Protein-protein orientation effects are thought to control electron transfer" between zinc cytochrome c and plastocyanin with medium viscosity-dependent rate-determining interconversion of two precursor complexes one of binding-(a)K. D. Jordan and M. N. Paddon-Row Chem. Rev. 1992,92,395;(6) P. Siddarth and R. A. Marcus J. Phys. Chem. 1992,96 3213; (c)J. Malinsky and Y. Magarshak J. Phys. Chem. 1992,96,2849;(d)M. J. Weaver Chem. Rev. 1992,92,463;(e)D. K. Phelps and M. J. Weaver J. Phys. Chem. 1992,96,7187;(f) R. A. Marcus J.Phys. Chem. 1992.96 1753; (9)J. N. Gehlen D. Chandler H. J. Kim and J. T. Hynes J. Phys. Chem. 1992 % 1748; (h) A.M. Kuznetsov J. Phys. Chem. 1992 96 3337. (a)C.C. Moser J. M. Keske K. Warncke R. S. Farid and P. L. Dutton Nature (London) 1992,355,796; (6) D. N. Beratan J. N. Onuchic J. R. Winkler and H. B. Gray Science 1992,258 1740; (c)J. R. Winkler and H. B. Gray Chem. Reo. 1992,92,369; (d)D. N. Beratan J. N. Betts and J. N. Onuchic J.Phys. Chem. 1992 96 2852; (e) H.O. Finklea and D. D. Hanshew J. Am. Chem. Soc. 1992 114 3173; (f)D. W. Conrad H. Zhang D. E. Stewart and R. A. Scott J. Am. Chem. Soc. 1992,114,9909;(g)J. F. Wishart R. van Eldik J. Sun C. Su and S. S. Isied Inorg. Chem. 1992 31. 3986. ' (a)E. Lloyd N. P. Tomkinson and A. G. Sykes J. Chem.Soc.. Dalton Trans. 1992 753; (h) D.G. A. Harshani de Silva D. Beoku-Betts P. Kyritsis K. Govindaraju R. Powls N. P. Tornkinson and A. G. Sykes J. Chem. Soc. Dalton Trans. 1992 2145. (a)J. S.Zhou and N. M. KostiC,J. Am. Chem.Soc. 1992,114,3562;(6)A. M. English and E. Cheung Inorg. Chim. Acta 1992,201,243;(c)E. P. Sullivan Jr.. J. T. Hazzard G. Tollin. and J. H. Enemark J. Am. Chem. Soc. 1992,114,9662:(d)M. C. Walker and G. Tollin Biochemistry 1992,31,2798;(e)H.-Y. Zhang K. Y. Faridoon and A. G. Sykes Inorg. Chim. Acta 1992,201.239;(f) B. R. Van Dyke L. Katen J. Hegenauer and P. Saltman Inorg. Chem. 1992 31 4017. Inorganic Mechanisms 475 optimized and the other of reaction-optimized orientation. Ferrocytochrome c peroxidase reduction of ferricytochrome c is thought to be rate limited by a conformation change in the free per~xidase.~~ Anion binding has been shown to control intramolecular electron transfer in sulfite oxida~e.~' Pyruvate can similarly affect electron transfer reactions of flavocytochrome b,.7d The variation in kobsfor the dithionite reduction of the [3Fe4S] (inactive) form of beef-heart a~onitase~~ + favours a mechanism involving SO,'.Differences in the kinetics of reduction of Cu" and Fe"' by tetrameric haemoglobin and its isolated o! sub-units have been st~died.'~ Interest has also centred on the effect of superstructures such as a series of peptide linkages on electron transfer in metalloporphyrins.* Solvent reorganization is found to be the dominant rate-controlling factor.Comparisons of systems with and without the superstructure suggest that such superstructure affects the thermodynamics of electron transfer rather than the kinetics. Long-range intramolecular transfer has been investigated in a series of Ru" diimine donor-acceptor complexe~,~~.~ in which donor and acceptor are linked by bridges containing -(CH,)"- (n = 2-7 12) phenylene or cyclohexene spacers. Rate constants decrease sharply as the number of methylenes separating the donor and acceptor increases (with an oddmen alternation in rate constant being seen). Smaller effects were noted for bridges containing other types of spacers. The results suggest that the bridges may mediate electron transfer. Short-range intervalence transfer has also been ~tudied.~'-j Outer-sphere Electron Transfer.-Lappin and co-workers have examined stereoselectivity effects on electron transfer between chiral and racemic reactants.Oxidation of (labile) [Co(edta)12 -by a series of chiral bis(dipeptide)Ni"' complexes is first order in each reactant with a complex pH dependence. In the pH range 4-10 an acid-catalysed formation of a precursor complex precedes electron transfer with strong hydrogen bonding between a carboxylate residue of the reductant and the N-terminal amine N-H of the coordinated peptide. Such interactions are seen to affect the relative orientation of the reacting ions and may influence stereoselectivity. Both inner-sphere and outer-sphere electron transfer reactions between [Co(ox),13 -and [Co(phen),12+ or [C~(phen),(H,O),]~+ show significant stereoselectivities.' Oh At low [phen] a doubly-bridged oxalato group is transferred in an inner-sphere process.By examining the ion association constants for the diastereomeric ion pairs for the analogues [Rh(ox)J3- and [Ru(phen),]'+ [K(AA)/K(AA) = 1.051 it is argued that chiral discrimination in the outer-sphere electron-transfer pathway occurs in the ' E. Anxolabehere D. Lexa and J.-M. Saveant J. Phys. Chrm. 1992 96,1266. (a)E. H. Yonemoto R. L. Riley Y. I. Kim S. J. Atherton R. H. Schmehl and T. E. Mallouk J. Am. Chem. Soc. 1992 114 8081; (h)C. K. Ryu R.Wang R. H. Schmehl. S. Ferrere M. Ludwikow J. W. Merkert. C. E. L. Headford and C. M. Elliott J. Am. Chem. Soc. 1992,114.430; (c) D. A. V. Kliner. K. Tominaga G.C.Walker and P. F. Barbara J. Am. Chem.Soc. 1992,114,8323; (d)S. K. Doorn P.0.Stoutland R. 9. Dyer and W. H. Woodruff J. Am. Chern.Soc. 1992,114,3133; (e)J. T. Hupp G. A. Neyhart. T.J. Meyer and E. M. Kober J. Phys. Chem. 1992,96,10 820 (f)K. Nozaki T. Ohno and M. Haga J. Phys. Chrm.. 1992 % 10880; (g) C. A. Bignozzi R. Argazzi. C.G. Garcia F. Scandola J. R. Schoonover and T.J. Meyer J. Am. Chrm. Soc. 1992,114,8727. (h)W. E. Jones Jr.. P.Chen and T.J. Meyer J. Am. Chrm.Soc. 1992 114,387; (i) J. M. Zaleski C.K. Chang. G. E. Leroi R. 1. Cukier. and D.G. Nocera. J. Am. Chem. Soc. 1992,114,3564; 0')C. Turro. C. K. Chang G. E. Leroi R.1. Cukier and D. G. Nocera J. Am. Chrm. Soc. 1992 114 4013. lo (a) S. E. Schadler C. Sharp and A.G. Lappin Inorg. Chern. 1992.31. 51; (h) R. M. L. Warren A. G. Lappin and A. Tatehata Inorg. Chem. 1992. 31 1566; (c) R. 9. Rexwinkel S.C.J. Meskers. H. P. J. M. Dekkers and J. P. Riehl. J. Phys. Chem.. 1992 % 5725. 476 N. Winterton intramolecular electron-transfer step within the ion pair. Enantioselective lumines- cence quenching has also been described for [Tb(pd~)~],(pdc = 2,6-pyridinedicar--boxylate).' OC Nord," in a survey of transition metal complex outer-sphere oxidations of I-and SCN- has shown that the rates display a linear free-energy relationship. The rate constants for oxidation of iodide by [1rC1,l2- are subject to marked salt effects" with the special effect of KNO being associated with specific interactions. Pressure effects on the [Co"'(edta)] -/[Co"(Hedta)(H,O)] -reaction are consistent with a non-adiabatic outer-sphere process with ring closure and water loss occurring prior to electron transfer.' The kinetics of the reduction of the bis(p-oxo)Mn"'/Mn'" complexes [Mn,L,0,I3+ (L = phen tmpa) with [C~(bipy),]~+ have also been studied.'" Outer-sphere oxidation of thiosulfate by [Ni(tacn),13' to give the Ni" complex and S,Og-follows the rate law -d[Ni"']/dt = 2k,[Ni"'][S20~-].' Cataly-sis by trace Cu" can be suppressed by addition of oxalate.Similar kinetics are seen when [Fe(bipy),13+ and [IrCl,]'- are used as oxidants. Reactions involving the Ni"' and Fe"' oxidants are activation controlled whereas that involving Ir" is limited by the diffusion apart of the products. Electron transfer between [PW 10,,Ru"1(H,0)]4- and [PW,10,,Ru"(H,0)]5- has been studied by 31P NMR line broadening.16 The oxidation of arsenous acid by the polyoxymetallated cobalt(II1) complex [COW,,O,,]~-follows the rate law 2(k + k,K,[H+]-')[As(OH),] with k and k relating to reactions involving As(OH) and [As(OH),OH] -.The reaction is accelerated by metal ions17 in the order K+ > Na+ > Li'. Self-exchange rates have been estimated for the systems [Fe(CN),13 -I4-(the dominant electron-transfer pathway involving the ion aggregates (K ,[Fe(CN),I3 ) and ((K+),,[Fe(CN),l4- ) suggesting specific cation involvement separate from charge neutralization effects),I8" [Co([ 10]aneS,)2]3+'2' and [C0([9]aneS,),]~+'~+ (measured by 59C0 NMR line broadening),18' [Cu[14]aneS4]' +/+ (with ligand conformational changes rate determining under certain circumstances),' 8c Crlll'lv,'8d sf [Fe(ox),] -',-,'8e ~.~~-[CO(NH,),(H,O),]~+'",' [Co(bipy),13 +I2 ,I0" + [Cu(aq)I2+I+ Cu"''(CI), and Cu"/'(IrnH),,' 8g trans-[R~L(OH)(H,0)]~''~ and + trans-[RuL(H,O),] +12 + (L = 6,7,8,9,10,11,17,18-octahydro-6,10-dimethyl-5H-dibenzo[e,n][ 1,4,8,1 2]dioxadiazacyclopentadecine),'sh parsley plastocyanin and A.tlariabilis plastocyanin.6h Inner-sphere and Atom Transfer Pro~esses.-[Co((p-OH),Co(en)~),]~ has been + shown"".' to react with aqueous acidic Cr(aq),' in discrete steps. The rate of I' G. Nord Comments Inorg. Chem.. 1992 13 221. A. Rodriguez M. Bejarano E. Fernandez-Boy M. del Mar Graciani F. Sanchez and M. L. Moyii J. Chem. Soc. Faraduj Trans. 1992 88 591.l3 W. H. Jolley D. R. Stranks and T. W. Swaddle Inorg. Chem.. 1992 31 507. l4 M. M. Monzyk and R.A. Holwerda. Inorg. Chem. 1992 31. 1969. R. Sarala and D. M. Stanbury. Inorg. Chrm.. 1992 31 2771. l6 C. Rong and M.T. Pope J. Am. Chem. Soc. 1992 114. 2932. " S. Dholiya A. Prakash and R. N. Mehrotra. J. Chem. Soc. Dalton Trans. 1992 819. (a)H. Takagi and T. W. Swaddle Inorg. Chem. 1992,31 4669; (h)S. Chandrasekhar and A. McAuley Inorg. Chem. 1992,31,480; (c)N. E. Meagher K. L. Juntunen C. A. Salhi L. A. Ochrymowycz and D. B. Rorabacher J. Am. Chem. Soc. 1992,114 1041 1; (d)M. C. Ghosh and E. S. Gould J. Chem. Soc. Chem. Commun. 1992 195; (e)B. Biinsch R. van Eldik and P. Martinez. Inory. Chim. Actu 1992,201.75; (1') P. Martinez. J. Zuluaga P.Noheda and R. van Eldik Inorg. Chim. Actri 1992 195.249; (8) M. J. Sisley and R. B. Jordan. Inorg. Chem.. 1992,31. 2880; (h)C.-K. Li C.-M. Che. W.-F. Tong and T.-F.hi J. Chem. Soc. Dolton Trans.. 1992. 813. Inorganic Mechanisms 477 + is less than that for intramolecular electron transfer in [(en)2Cr"'(p-OH)2Cr"(aq)]3 the single-bridge ion [(H20)(en)2Cr"'(p-OH)Cr"(aq)]2While it was not possible + to isolate or detect the corresponding [Cr"'(H,O),A]"+ from the redox reaction of [Co"'(NH,),A]"+ [A = SO:- S,O<- (n = 1); A = C,H,SO; (n = 2)] with Cr" an inner-sphere mechanism was inferred.20 The study also produced a new value for the rate constant for the Cr" reduction of trans-[Co(NH,),(OH,)(SO,)] of + (1.1 f0.1) x lo5M-s-which is consistent with other data and ground-state effects associated with trans bond lengthening.The earlier value (18.6~~~ s-') is now thought to be incorrect. The reactivity of thiyl radicals SH' with a series of simple hexaaqua ions21a and other metal complexes21b has been studied. EtS' reacts with [M(H20)J2' by inner-sphere processes.21a Reaction of the porphyrin complexes (ttp)Criv oxide and (oep)Cr"' chloride proceeds with a second-order rate constant to form an equilibrium mixture of [(ttp)CrCl] and [(OEP)Cr=O] cia an inner-sphere process involving a p-0x0 intermediate formed after C1-dissociation from [(oep)CrCl].2 Miscellaneous.-Disproportionation of Cr" in the presence of anions of branched r-hydroxyacids LH pH 2.5-4.0 is second order in [Cr"] and believed to occur via [Cr'VL,(0)(OH)] which is also implicated in the catalysis of disproportionation by Mn11.23a Cr" reductions by Sn" and Ce"' have also been Mn2+ inhibition of the reduction of CrV' to Cr"' by HCI-IO in aqueous perchloric acid is believed to involve a competition with HCHO for Cr" and points to the intermediacy of Cr" in the uninhibited reaction.24 Two groups have studied the reduction of CrV' by glutathione in attempts to understand further of CrV' toxi~ology,~~" at neutral pH suggesting a one-electron pathway the at pH 1.8-3.5 proposing two parallel pathways.Multiple electron-transfer processes involving dioxo complexes of RuV' and R~V ,~~~,~~~ ,26d oxoaquo complexes of R u ~ ~ and diaquo complexes of Ru"' . 26a~and~ ~ 11 ~~ 18h have been studied.Reactions of Oxygen-containing Oxidants and Reductants.-Homogeneous metal catalysed oxidations involving dioxygen have been reviewed and classified by Drago and Beer2".' into five categories defined by the role of the metal in O2activation and '' (a)R. D. Cannon S. Benjarvongkulchai A. Gair. and M. I. M. Ibrahim. Polyhedron. 1992. 11. 739 (h)S. Benjarvongkulchai and R. D. Cannon. Polyhedron 1992 11 517. ") M. D. Johnson and R. J. Balahura Inory. Chem.. 1992 31. 808. " (a)P. Huston. J. H. Espenson. and A. Bakac. Inorg. Chem. 1992,31 720; (h)P. Huston J. H. Espenson. and A. Bakac J. Am. Chem. Sot. 1992. 114 9510. " L. K. Woo J.G. Goll L. M. Berreau. and R. Weaving. J. Am. Chem. Sor. 1992. 114. 741 1. 23 (a)M.C. Ghosh E. Gelerinter and E.S. Gould Inory. Chem. 199Z31.702; (h)M. C. Ghosh R. N. Bose. E. Gelerinter. and E. S. Gould Inory. CCwm. 1992. 31 1709. 24 J. F. Perez-Benito C. Arias and D. Lamrhari. J. Chem. SOL..,Chrm. Commun. 1992. 472. l5 (u)R. P. Farrell and P.A. Lay Comment7 Inory. Chem.. 1992. 13. 133; (h)P. O'Brien and G. Wang. J. Chem. Soc.. Chem. Commun.. 1992. 690; (c) P. O'Brien G. Wang and P. €3. Wyatt Polyhedron 1992 1 I 321 1; (d)R. N. Bose. S. Moghaddas and E. Gelerinter Inory. Chem. 1992 31. 1987. 26 (u)S. A. Adeyemi A. Dovletoglou. A. R. Guadalupe and T. J. Meyer fnory. Chrm.. 1992. 31 1375 (h) C.-M. Che W.-T.Tang. W.-0. Lee K.-Y. Wong and T.-C. Lau,J. Chem.Soc.. Dalton Truns. 1992. 1551; (c) C.-M. Che C.-K. Li. W.-T. Tang. and W.-Y. Yu,J. Chem. Soc,.,Dulrnn 7rans.1992. 3153; (d)L.M. Jones-Skeens X. L. Zhang. and J.T. Hupp Inory. Chrm. 1992 31. 3879; (e) R.A. Binstead M. E. McGuire. A. Dovletoglou. W. K. Seok L. E. Roecker and T. J. Meyer. J. Am. Chem. Soc. 1992. 114. 173. 27 (a)R. S.Drago and R. H. Beer. Inory. Chim. Acta. 1992 198 200. 359 (h)R.S. Drago Coord. Chem.Re[.. 1992 117. 185. 478 N. Winterton the metal-0, 0x0 peroxo and higher oxidation state metal oxidants formed. The slow reduction of 0 by [Co"(tim)]'+ in the presence of Br- strongly catalysed by [Co"(dmgBF,),] follows a sixth-order rate law,28" first order in [O,] [Co"-(tim)I2'] [Br-1 and [Hf] and second order in [catalyst]. A clean 4e- reduction of 0 to 2H,O. by-passing the formation of H,O, is proposed uia [Co(dmgBF,),O,] from which p-peroxo bridged [Co(dmgBF,),0,Co(tim)]2 + is formed.Reaction with a second mole of [Co(dmgBF,),] is Br- and H+ catalysed to give [Co(dmgBF,)- (O,H)C~(tim)BrCo(dmgBF,)]~+. This reacts with three moles of reductant to give 4[Co"'(tim)l3+ + 2H,O + Br-+ 2 catalyst. The complex [Co(hm~)(H,0),]~+ re-acts with 0 in aqueous solution at pH > 7 to give [Co(hm~)(OH)0,]+.~~* The rate constant for 0 loss from this is 106-fold less than for that of the aquo complex [C0(hmc)(OH,)0,]~+ . Oxygen dissociation from [Co(hmc)(SCN)O,] occurs some + 800 times faster than for the hydroxo complex. Ferrous ion reacts with ozone in aqueous acid by oxygen atom transfer to give Fe02+,29 which reacts with excess Fe2+ to give 2 Fe3+ + H,O. With excess 0,,reactions involving OH' HO, and HO are implicated.HO free radicals oxidize [Ni1'(hmc)12 (pH 3-7) in the presence of anions + X = HCO, SO:- and H,PO, to give the octahedral Ni"' complex [Ni(hmc)X,] via contact ion pairs {[Ni(hm~)]'+,X}.~~ At high [XI AV approaches the values associated with the rate constant for inner-sphere reaction of HO with the ion pair to give [Ni"'(hmc)XHO,] as expected for an associative process. Significant charge neutralization and desolvation in the ion pair is proposed. Hydrogen peroxide oxidation of [Fey(ttha)(H20)2]2 -proceeds with a greater than 1 1 consumption of H,O to yield ca. 80% [Fe','O(ttha)]'-and 20% of a tetranuclear complex [Fey1(O),(ttha),l4- oia ferry1 intermediate^.^' These are believed to react with the second Fe" site in the same molecule (or with another mole of reductant) by inner-sphere processes to give the p-0x0 bridged complex (or the tetranuclear complex) and by an outer-sphere process to give open chain [Fe','(ttha)(H,O),].Further studies directed towards the detection and characterization of intermediates formed in the reactions of H,O with peroxidases have been described both on enzyme and model systems using alkyl and acyl peroxides as probes. Low temperature stopped flow kinetics reveal saturation kinetics for the reaction of horseradish peroxidase and ROOH [R = Et But MeC(0)].32a Rapid scanning spectroscopy was used to characterize intermediates. Balch3,* has studied three such intermediates formed during reaction of peroxides with iron porphyrins.Morishima and ~o-workers~~~'~ have studied the electronic effects of substituents in the porphyrin and the axially bound imidazole on the rates of 0-0 heterolysis in a series of acylperoxidoiron(r1r) substituted porphyrins. Oxoferryl porphyrin cation radical intermediates are directly observed. Vanadium(1v) is oxidized by alkyl hydroperoxides (ROOH R = Bu' Am') to give VO; and alkoxy radicals with the acid dependence of the kinetics pointing to (a)A. Marchaj A. Bakac and J. H. Espenson Inorg. Chem.,1992,31.4860;(h)A. Marchaj A. Bakac and J.H. Espenson Inorg. Chem. 1992. 31. 4164. 29 T. Lagager. J. Holcman. K. Sehested and T. Pedersen. Inorg. Chem. 1992 31. 3523. 3" A. Meshulam H. Cohen R. van Eldik and D. Meyerstein Inorg. Chem. 1992 31 2151. 3' S. Zhang K.S. Snyder and R. E. Shepherd Inorg. Chim. Acta 1992. 201 223. 32 (a)H. K. Baek and H. E. Van Wart J. Am. Chem. Soc. 1992,114,718;(h) A. L. Balch Inorg. Chim. Acta 1992,198-200.297; (c)K. Yamaguchi. Y. Watanabe and 1. Morishima Inorg. Chem. 1992,31,156;(d)K. Yamaguchi Y. Watanabe and I. Morishima J. Chem. Snc. Chem. Commun. 1992. 1709; (e)R. Ma A. Bakac. and J. H. Espenson Inorg. Chem. 1992,31,1925;(f) R. D. Arasasingham S. Jeon and T. C. Bruice J. Am. Chem. Soc.. 1992 114 2536. Inorganic Mechanisms 479 rate determining formation of initial products via the intermediacy of [OVOOR] .32e + Homolytic 0-0 cleavage of alkyl hydroperoxide by the Mn"' porphyrin complex [Mn"'(tdmspp)X,] (X = H20 OH-) is proposed.32f The pH dependence of the products in the presence of imidazole suggests a change from homolytic to heterolytic 0-0 cleavage at high pH associated with proton loss from Mn"'-ImH.The superoxide in binuclear complexes of Co"' may be reduced by thi01s~~" or [CO~'(O,)(CN),,]~ reduction is catalysed dramatically by Cu', a~corbate.~,~ -yielding the corresponding disulfide and [Co,(O,)(CN) ,I6- which decomposes rapidly to [Co(CN),(H20)l2 -and H,02. High [RSH] suppresses the catalytic effect possibly because of the formation of less catalytically active copper(rkthio1 ad duct^.^,' For the copper-catalysed process involving ascorbate an unusually facile inner-sphere pathway for the reaction of Cu' with [CO,(O,)(CN),,]~- is proposed. The reaction between ascorbate and [Co~'(O,)(NH,) ,I5 gives the binuclear peroxo complex and + then Co'l NH, and O, via a 1 1 decaammine :ascorbate monoanion complex within which a one electron transfer takes place.Thiolatoruthenium(Ir1) complexes e.g. [Ru(NH,),(SH)]' and trans-[Ru(NH,),- + (H20)(SH)l2 are oxidized by peroxomonosulfate HOOSO ,in discrete steps first + order in [complex] and [HOOSO,] to give the corresponding sulfenato and sulfinato complexes.34 The decrease in rate of the oxidation of sulfur(1v) oxide and oxoanions by aqueous H,O (pH < 1.5)is associated with H202 protonation. Reaction proceeds via peroxosulfurous acid which goes to Sv' with tt ca. lo3 times less than that for the equivalent N"' to NV reaction of peroxonitrous acid.35 Zhang and Edwards36 have extended to pH 6 the rate law for Co2+-catalysed decomposition of peroxomonosul-fate -d[HOOSO;]/dt = k,,([HOOS0~][Co2+]/[H+]).The rate law for VO; is kv{ [HOOSO;][VO~][H']). CoOHf and V(0)OH2+ are proposed as key inter- mediates. The rate law for the oxidation of a series of Nil' macrocyclic complexes [NiL2'3 (L = cyclam) by perox~disulfate~~ suggests reaction via a pre-equilibrating ion pair followed by metal-ion assisted 0-0 cleavage. Coordinated sulfite in [Fe(edta)(S0,)l3 -is autoxidized in a reaction with a strong [02]dependence to give SO:-and [Fe(edta)12- with the reaction involving Fe"'-edta complexes much slower than that for aquoiron(Ir1) ions.jsa Autocatalysis and synergistic effects of Mn" in reactions of metal ion oxidants with sulfur(iv) oxide and oxyanions have been studied by van Eldik and co-worker~,~~~-~ in relation to their relevance to acid rain formation.Ferrate oxidation of sulfite with stoichiometry 2 FeOi-+ 3 SO:-= 2 Fe"' + 3 SO:-follows the rate law -d[FeV']/dt = k[FeO:-] [SO;-][H'] (rather than the second order dependence on [SO; -1 described earlier by other workers),39 with a pre-equilibrium to give [0,FeOS03H]3- and rate determining dissociation to SO:-and Fe". The rates of the analogous oxidation of 33 (a)S. K. Ghosh S. K. Saha M. C.Ghosh R. N. Bose J. W. Reed and E. S. Gould Inorq. Chem.. 1992,31. 3358; (b) S. K. Saha M. C. Ghosh and E.S. Gould Inorg. Chem. 1992 31 5439. 34 M. D. Johnson and D. Nickerson Inory. Chem. 1992 31 3971. 3s C. Drexler H. Elias B. Fecher and K. J. Wannowius Ber.Bunsenges. Phys. Chem. 1992 96. 481. 36 Z. Zhang and J.O. Edwards Inorq. Chem. 1992 31 3514. R. I. Haines and S. J. Northcott Can. J. Chem. 1992 70 2785. 38 (a) M. Dellert-Ritter and R. van Eldik J. Chem. SOC. Dalton Truns. 1992 1045; (b)R. van Eldik N. Coichev K. Bal Reddy and A Gerhard Ber. Bunsenges. Phys. Chem..1992,96,478;(c.)K. Bal Reddy and R. van Eldik. Atmos. Enuiron. A 1992 26,661; (d) N. Coichev K. Bal Reddy and R. van Eldik Amos. Environ. A 1992,26,2295; (e)M. Dellert-Ritter and R. van Eldik J. Chem. Soc. Dalton Trans. 1992 1037. 39 M. D. Johnson and J. Bernard Inorg. Chem. 1992 31 5140. 3' 480 N. Winterton selenite display both a first and second-order dependence on [SeOi -1 suggesting an additional path involving reaction of [O3FeOSeO3HI3- with a second mole of SeO3 -.0rganometallics.-Outer-sphere oxidation of metal carbonyl anions has been st~died.~~",~ The pressure dependence of the rate of the reaction of [RuCp,]/ [RuCp,X]+ (X = Br I) and [OsCp,]/[OsCp,I]+ in a series of suggests that the dominant effect controlling the activation parameters is the solvation of reactants which is lost on going to the transition state presumed to be halogen atom bridged. The rates of strongly exergonic reactions of [Re(CO),L] radicals with a series of atom and group donors are more sensitive to variations in ligand steric characteristics than to variations in ligand donor-acceptor properties whereas the reverse is the case for endergonic reactions.41b The kinetics of the halide-induced + disproportionation of the 17-electron [M(CO),(PCy3),] (M = Fe Ru 0s) (giving [M(C0)3(PCy3)2] and [MX2(C0)3(PCy3)2] (X = C1 Br)) the rate law k,[NBu4X][complex] with k showing minimal effect of metal period.The pseudo first-order rate constants showed a non-linear dependence on the supporting electrolyte. Equilibration of contact ion pairs followed by reaction within the ion pair was proposed. Mechanistic studies relevant to oxidative addition and related topics have appeared.43a-' Non-metal Reactions.-Han and Bartel~,~~ in an investigation of the reaction of the hydrogen atom with OH -,have challenged the current view that all hydrated-electron reactions proceed via an electron transfer mechanism and conclude that the reaction H + OH-= (e-), + H20,is best described as a proton transfer from the weak acid (H.), to the strong base (OH-),,.Hydrogen atoms are suggested to disproportionate leaving the electron to be hydrated within the hydrogen atom cage. Reactions of (e-)aq with protonated substrates in water may better be interpreted as proton transfers to the weak base the hydrated electron. The kinetics of the reaction 2 NH,OH + I = N20 + 41-+ H20 +4H' pH 3.4-5.5 suggest45 that unprotonated hydroxylamine and molecular iodine are the reactive species with [NH,OI,]- HNO NH,O and 1 as intermediates. The peroxomonosulfate oxidation of hydroxylamine in acetate and the decompo- sition of ozone in aqueous acetic acid47 have been studied. Laser flash photolysis of aqueous dithionite generates both sulfite and the sulfite radical anion.48 The decay of 40 (a)C.K. La] M. S. Corraine and J. D. Atwood Or~unomerallic~s. 1992 11 582 (h)M. S. Corraine C. K. La]. Y. Zhen M. R. Churchill L. A. Buttrey J. W. Ziller and J. D. Atwood Organometallics 1992 11 35. 41 (a)K. A. Anderson K. Kirchner H. W. Dodgen J. P. Hunt and S.Wherland. Inorg. Chem.. 1992,31,2605; (h)M.G. Choi and T. L. Brown lnorg. Chim.Actu. 1992 19S200 823. " L. Song and W. C. Trogler. J. Am. Chem. SOL,.,1992 114 3355. " (a)R. K. Merwin. R. C. Schnabel J. D. Koola. and D. M. Roddick. Orgunomrtullics 1992. 11 2972; (h) M. J. Hostetlerand R. G. l3ergman.J. Am. Chum. Soc.. 1992,114,787;(c) G. J. J. Steyn A. Roodt and J.G. Leipoldt Inorg. Chem. 1992,31 3477; (d)D. C. Woska M. Wilson J. Bartholomew K.Eriks A. Prock and W. P. Giering Orgunomrtullics 1992,ll. 3343; (e)G. Bellachioma. G. Cardaci A. Macchioni and G. Reichenbach Inorq. Chem. 1992 31. 3018; (,f) G. Bellachioma. G. Cardaci. A. Macchioni and G. Reichenbach Inorg. Chem.. 1992 31. 63; (q) M. Bassetti. D. Monti A. Haynes J.M. Pearson 1.A. Stanbridge and P. M. Maitlis Gax. Chim. Ira/.. 1992. 122 391; (h)K. J. Schneider A. Neubrand R. van Eldik and H. Fischer Orgunomi~rullic~s, 1992. 11,267; (i)M. Brookhart. E. Hauptman. and D. M. Lincoln J. Am. Chem. Soc.. 1992. 114. 10394. 44 P. Han and D. M. Bartels. J. Phys. Chem.. 1992. 96 4899. '5 R.T. Wang. G. Ribai. and K. Kustin Inr. J. Chem. Kinet. 1992. 24. 11. 46 M. Sharma D.S. N. Prasad and K.S. Ciupta Inr. J. Chem. Kinet. 1992 24. 665. 4q K.Sehested. H. Corfitzen. J. Holcman. and E. J. Hart. J. Phys. Chem.. 1992 96. 1005. 4x S.J. Waygood and W. J. McElroy .I. <'hem. Soc... Furuday 7rum.. 1992. 88. 1525. Inorganic Mechanisms 481 the latter is a second order process giving either recombination or disproportionation to SO:-and S"'. Oscillating Reactions and Chemical Chaos.-The exotic behaviour such as periodic oscillations travelling waves chemical chaos stirring rate effects and other fascinating dynamic effects displayed by certain redox processes has stimulated the study of many (apparently!) simple experimental systems including the iron(rI1) catalysed decomposi- tion of chlorite ion,49a reaction between chlorite and thiourea," the decomposition of hypochlorous acid pH 5-8,51 thiocyanate reaction with bromine" and bromate,'j the reactions of bromite and i~dide,'~.~' and of chlorine dioxide and iodide.s6 The chlorite-iodide-malonic acid system is of renewed interest because of the observation of Turing patterns (arising from diffusion-induced instability).s7p59 Internally coupled oscillators involving chlorite bromate and iodide have been studied.60 The reactions of iodine and tri-iodide with thiosulfate,61 oxidation of HIO by H,0,,62 and oxidation of Mn" by periodate have also been studied.63 Oscillations in pH are seen in reactions of hydrogen peroxide and thiosulfate hydrogen peroxide and hydrogen sulfide and iodate and hydrogen s~lfite.~~ A model has been developed for the H,02/SZ-~ystern.~' Copper(I1) catalysis is essential for H,O,/S,O -oscillations and Rabai and Epstein have examined the equilibria and kinetics of the Cu"-S,O~- interactions in aqueous solution.66 Non-linear dynamic phenomena in the iodate-As"' system have been studied further.67 Chaos has been observed in the per-oxidase-oxidase reaction.68 Stirring and stirring sense7' effects electric field73 and ill~mination~~ effects have been observed in Belousov-Zhabotinskii (B-Z) reactions.Calculations show that internal thermal fluctuations are highly unlikely to generate a trigger wave in a B-Z oscillatory chemical s~lution.~' A magnetic resonance imaging-based method has been to measure accurately the velocity of chemical waves propagating in a Mn2+-catalysed B-Z reaction in a vertical tube.Both 49 1. Fabian and G. Gordon Inory. Chem. 1992 31 2144. 5" I. R. Epstein K. Kustin and R.H. Simciyi J. Phys. Chem. 1992 96 5852. 51 L.C. Adam I. Fabian K. Suzuki and (3,Gordon Inorg. Chem. 1992 31 3534. '' I. R. Epstein K. Kustin and R. H. Simnyi J. Phys. Chem. 1992 96 6326. 53 Y.-X. Zhang and R. J. Field J. Phys. Chem. 1992 96 1214. 54 R. de Barros Faria I. R. Epstein and K. Kustin. J. Am. Chem. Soc.. 1992. 114. 7164. 55 M. Orban and I.R. Epstein J. Am. Chem. Soc. 1992 114 1252. 56 I. Lengyel J. Li and I. R. Epstein J. Phys. Chem. 1992 96. 7032. 57 Z. Noszticzius Q. Ouyang W. D. McCormick and H. L. Swinney. J. Am. Chem. Soc.. 1992. 114 4290. '' Z. Noszticzius Q. Ouyang W. D. McCorrnick and H. L. Swinney J. Phys. Chem. 1992 96. 6302. '' Q.Ouyang Z. Noszticzius and H. L. Swinney. J. Phjs. Chem. 1992 96 6773. 60 F. Mahootian D.J. Hauri. and J. E. Earley J. Phys. Chem.. 1992 96 1014. " W. M. Scheper and D. W. Margerum Inorg. Chem. 1992. 31 5466. 62 L. Kolar-Anic and G. Schmitz J. Chem. Soc.. Farnday Trans.. 1992 88 2343. 63 G. Sodnorndordi M. MelicharCik and L. Treindl Collect. Czech. Chem. Cornmun. 1992 57. 1210. " G. Rabai and I. R. Epstein J. Am. Chen?. Soc. 1992 114 1529. " G. Rabai M. Orban and I. R. Epstein .I. Phys. Chem. 1992 96 5414. " G. Rabai and I.R. Epstein Inory. Chem 1992. 31 3239. " N. Ganapathisubramanian. J. Phys. Chem. 1992 96. 4446. " T. Geest. C.G. Steinmetz R. Larter and L. F. Olsen. J. Phys. Chem. 1992 96 5678. by J.A. Pojman H. Dedeaux and D. Fortenberry. J. Phys.Chem. 1992 96. 7331. 70 A. K. Dutt and M. Menzinger J. Phys. Chem. 1992. 96,8447. 'I M.J. B. Hauser D. Lebender and F. W. Schneider. J. Phys. Chern.. 1992. 96 9332. 72 L. Gyorgyi and R. J. Field J. Phys. Chrm. 1992 96. 1220. '' K. 1. Agladze and P. De Kepper J. Phys. Chrm. 1992 96 5239. 74 M. Jinguji M. Ishihara. and T. Nakazawa J. Phys. Chem. 1992. 96 4279. Is Y.-X. Zhang P. Foerster and J. Ross J Phys. Chem. 1992 96 8898. 76 M. Menzinger A. Tzalmona R. L. Armstrong A. Cross and C. Lemaire. J. Phys. Chrm.. 1992.96,4725. 482 N. Winterton non-chaotic aperi~dicity~~ and chaos78 are claimed from the same B-Z reaction at high flow rates in a continuously stirred tank reactor. Other studies on B-Z79-88 and other have been reported.3 Substitution Reactions Six-coordination.-Kinetics of dmf exchange with [Ti(dmf)J3 +93a and [V(dmso),13 +,93b and of [V(dmso),(NCS)12 formation and dissociation,93b are + consistent with associative interchange mechanisms I, and confirm for DMF solvates the mechanistic change from I to I seen for other S in [MS,I3' along the first row transition metals. dmso exchange in [TiO(dmso),12+ can be distinguished at axial (fast dissociative D)and equatorial (slow axial-quatorial migration followed by concerted equatorial solvent loss) sites.93' The pressure dependence of the rate of reaction of [Cr(H20),l2+ with a series of carbon free radicals to give [Cr(H2O),RI2 + provides evidence94 for a dissociative interchange I, mechanism for substitution at aquated Cr".The changes in activation energies for a series of substitution and exchange reactions involving [Ni(dmso),12 + in DMSO suggest9 that the three-fold degenerate Ni-0 stretching vibration is involved in the activation process. Kinetic parameters for exchange between [Ni(en),]" and en9 point to a dissociative mechanism involving [Ni(en)J2 as an intermediate with two equivalent monoden- + tate en ligands. The rate is independent of [en] in DMF used as diluent. Complex formation between Clphen and [Niaq12 and [Coaq12+ proceed via dissociative + interchange mechanisms .9 The spontaneous isomerization of [Co(NH,),(SCN)I2 in aqueous Na[S14CN] + leads to the direct incorporation of the label into the reactant and product [CO(NH,),(NCS)]~+~~ and since anation of [Co(NH,),(H20)l3' is relatively slow reaction via an ion-pair {[CO(NH,),(SCN)]~+,SCN-} is proposed; the ratio of S-and N-bound products is similar to those seen from spontaneous aquation of [Co(NH,),XI2+ in the presence of SCN-.The authors conclude that all such 77 R. Blittersdorf A. F. Miinster and F. W. Schneider J. Phys. Chem. 1992 % 5893. " L. Gyorgyi R. J. Field Z. Noszticzius W. D. McCormick and H. L. Swinney J. Phys. Chem. 1992,96 1228. '')S. Keki I. Magyar M.T. Beck and V. Gaspar J. Phys. Chem. 1992 96,1725. 'O H.-D. Forsterling and L. Stuk J. Phys. Chem. 1992 96 3067. " M. MelicherEik M. Mrakavova A. Nagy A. Olexova and L. Treindl J. Phys. Chem. 1992 96 8367. R2 R. P. Rastogi and G. P. Misra J. Phys. Chem. 1992 96 4426. 83 P.Ruoff J. Phys. Chem. 1992 96,9104. 84 J. Liu and S. K. Scott J. Phys. Chem. 1992 % 9870. '5 J. Guslander and R. J. Field J. Phys. Chem. 1992 96 10575. 86 R.R. Aliev and A.B. Rovinsky J. Phys. Chem. 1992 96 732. J. Liu and S. K. Scott J. Chern. SOC.,Faraday Trans. 1992,88 909. '' C. C. D. Giles P. Ibison J. Liu and S.K. Scott J. Chem. Soc. Faraday Trans. 1992 88 917. 89 J.-P. Laplante and T. Erneux J. Phys. Chem. 1992 96.4931. 9" S. K. Scott and K. Showalter J. Phys. Chem. 1992 % 8702. 9' J. Weiner R. Holz F.W. Schneider and K. Bar-Eli J. Phys. Chem. 1992 96,8915. 92 M. Dolnik M. Marek and I. R. Epstein J. Phys. Chem.. 1992 96 3218. 93 (a) I. Dellavia L. Helm and A. E. Merbach Inorg. Chem. 1992,31,2230; (b) I. Dellavia P.-Y. Sauvageat L.Helm Y. Ducommun and A. E. Merbach Inorg. Chem. 1992,31,792;(c)I. Dellavia L. Helm and A. E. Merbach Znorg. Chem. 1992 31 4151. 94 R. van Eldik W. Gaede H. Cohen and D. Meyerstein Znorg. Chem. 1992 31 3695. 95 R. Larsson Inorg. Chim. Acta 1992 191 179. 96 S. Soyama (nee Yokoi) M. Ishii S. Funahashi and M. Tanaka Znorg. Chem. 1992 31 536. '' G. Laurenczy P. Bugnon and A. E. Merbach Inorg. Chim. Acta 1992 198-200 159. 98 D.A. Buckingham C. R. Clark and G. F. Liddell Inorg. Chem. 1992 31 2909. Inorganic Mechanisms 483 spontaneous hydrolyses involve 'tight' regiospecific ion pairs { [CO(NH,),X]~+ ,Y 3 with entry of Y-and H20 being independent of X-. A rein~estigation~~ of the Fe"'(aq)/SCN- system yields values of Am for reactions [Fe(H20),I3+ + SCN- and [Fe(H20),(0H)l2' and SCN- which cast doubt on the conclusions from earlier T-and P-jump studies.The kinetics of spontaneous aquation of geometric isomers of [Cr + (hi~tarnine)(NCS)(H,O),]~to [Cr( histamine)(H 20),]+ Ooa and Of [cr(NCs)6]3-to [Cr(NCS),(H20)l2- loob have been studied. A previously unreported pathway for azide substitution in Fe"'(aq) viz. reaction of [Fe(H20)5(OH)]2+ and N3 has been described,99 with a rate constant 10-100 times larger than for typical [Fe(H,O),(OH)] +/X -reactions. Rate constants and A V values point to pre-association possibly with hydrogen bonding.99 A parallel HN reaction with [Fe(H20),(0H)l2 is preferred to + [Fe(H20),I3++ N;. The [Fe(H20),I3+ + HN reaction is negligible. [Fe(edta)(S0,)l3- is formed from [Fe(edta)] -and SO;-in a limiting dissociative process via the labile [Fe(edta)(H20)]-.38e [Fe(edta)(OH)I2-and [Fe(edta)OFe(edta)]"- are substitution inert.Activation volumes of + 14 to + 18cm3 mol-' for complex formation [Fe(CN),(OH,)I3-+ L"-= [Fe(CN),L](3+")-+ H20,n = 0 1 point to a limiting D mechanism,' la rather than the dissociative interchange or ion-pair dissociative process proposed earlier. Stochel has also reviewed the use of high pressure techniques to study the mechanisms of [Fe(CN),XI2- A direct cis-trans (with respect to coordinated H20) isomerization path has been established for a series of di-p-hydroxo binuclear complexes of the type [Cr(H,O)L(p- OH),CrL(H,0)I4+ [L = tacn ~~C-(NH,),,'~~" pH 2-1 13. Kinetics of equilibration have been studied between [(NH3),1r(p-0H),1r(NH,),]"' and cis,cis-[(H20)(NH3)41r(p-OH)Ir(NH3)4(OH)]4+;102b between c~s-[R~(NH,),(H,O),]~~ cis,cis-[ ( H,0) (N H ,) )]H(0,) )R h (N H H(p-0hR + and C(NH,),Rh(P-OH)2Rh(NH3)4]4+;102c and between [(en)2Cr(p-OH)2Cr(en)2]4+ and [(HO)(en),Cr(p-OH)Cr(en),(OH)]3+ .102d Rate constants for H20 exchange in trans-[Ir(NH,),(OH,)L]"+ (L = H20,n = 3; L = OH C1 n = 2) establishlo2' (with other published data) the kinetic trans-effect order for a fixed set of cis-ligands at an Ir"' centre to be H20 << NH < C1-.Comparisons with Rh"' and Cr"' kinetic trans-effects are discussed in terms of ligand field stabilization energies. Evidence for an I mechanism has been reportedlo3 from a kinetic study of the substitution of axial H20 in aquacobalamin by a series of ligands L chosen to give saturation kinetics at high [L] with the dependence of k,, (and the associated activation parameters) on L indicating that the rate-limiting step is not unimolecular water loss.Acid-independent SCN-substitutions on the clusters [Mo,S,(H,O) ,I4+ [MO,S,(H~O)~~]~+, and [M,S,(H,0),]4+ (M = Mo W) in aqueous [CI0,]-'04",b " M. R. Grace and T. W. Swaddle Inorg. Chem. 1992 31 4674. loo (a)L. Hussain and P. Kita Pol. J. Chem. 1992,66 595 (h)K. Mesbah L. Hussain and P. Kita Pol. J. Chem. 1992 66,427. lo' (a) G. Stochel J. Chatlas P. Martinez and R. van Eldik fnorg. Chem. 1992 31 5480; (6)G. Stochel Coord. Chum. Rev. 1992 114 269. lo' (a) P. Andersen and A. Dsssing Acra Chem.Scand.. 1992 46 354; (h)F. Galsbsl K. Simonsen and J. Springborg Acta Chem. Scund. 1992,46.915; (c)J. Springborg Acta Chem. Scand. 1992,46 956 (d)J. Springborg Acra Chem. Scand. 1992,46 1047;(e) F. Galsbol L. Msnsted and 0.Msnsted Acta Chem. Scand. 1992 46 43. '03 H. M. Marques J.C. Bradley and L. A. Campbell J. Chem. Soc. Dalton Trans. 1992 2019. lo4 (a)Y .-J. Li M. Nasreldin M. Humanes and A. G. Sykes Inorg. Chem. 1992.31,3011; (b)C. A. Routledge and A.G. Sykes J. Chem. Soc. Dalton 7rans. 1992 325. 484 N. Winterton proceed by two consecutive reactions for [Mo,S,(H,O) ,I4+ (the first step establish- ing an equilibrium with four equivalent Mo"' with a slower subsequent isomerization) and two concurrent processes for [Mo,S,(H,O) ,I' + ,corresponding to substitution at Mo"' and a slower process at Mo'".Substitution of H20 in trans-[TcO(CN),- (H20)]-by SCN- and the reverse process have been studied."'" Pyridine exchange on trans-[M(O),(py),]+ (M = Tc Re) follows a first order rate law in [complex] and zero order in [pyridine] (kTc/kRe= 8000) which with derived activation parameters implies a dissociative At pH 3.0 the rate of substitution of H,O in [PW,,O,,RU"(H,O)]~- by dmso is ca. lo3times less than the rate of water exchange in [RU(H,O),]~+.'~ reacts with tyrosine and valine tRNA with [RU(NH~)~(H~O)]~+ second order kinetics." Base Hydrolysis.-Base hydrolysis of (pentaamine)cobalt(m) complexes continues to be a focus of study with particular attention being given to the structure and lifetime of intermediates the site of deprotonation the timing of reprotonation and the effects of ion pairing.Comba Jackson and co-workers have synthesized a series of [Co(dien)(dapo)X]"+ complexes of different stereochemistry configuration and optical form to address particularly the geometry of coordinatively unsaturated intermediates. Base hydrolysis of optically pure mer-exo(H)- and mer-endo(H)- [Co(dien)(dapo)C1I2+ occurs with retention of mer-geometry and complete (99 2 1Yo) racemization. This with H-exchange rate studies at co-ordinated N supports a rate determining loss of C1- in an S,lCB mechanism with the intermediacy of an achiral trigonal bipyramidal species with a deprotonated dien secondary N. Interestingly N-H trans to C1 exchanges more rapidly than cis-N-H establishing for the first time that base hydrolysis can proceed via the less abundant conjugate base.Exchange at this secondary N is still faster than base hydrolysis however. Coordination to CO~~~,~~~"~ ~~111 108d and Rh111 108e of a series of pendant arm macrocycles gives cis-and trans-quinquedentate complexes [MLCl]' + . trans-Cobalt(m) complexes display106' rapid base hydrolysis with second order rate constants apparently not sensitive to ground state effects (as manifested by significantly different Co-Cl separations) in contrast to the analogous cis-Co"' complexes. Similar effects are noted in the analogous Cr"' complexes. Activation volumes for the base hydrolysis of rhodium(m) complexes of pendant arm ligands [RhLCl]* + ,are appreciably lower than for the corresponding Co"' and Cr"' complexes suggesting greater association of the incoming water with Rh during C1- departure or ligand related changes which bring about less solvent re-organization.However A V for [RhLCl12+ are similar to that for [Rh(NH,),- C1I2+,suggesting the process is not spectator-ligand dependent. Base hydrolysis of + + cis-[Ru(en),Cl,] and cis-a-[Ru(trien)CI,] occurs with complete retention of lo5 (a)A. Roodt J. G. Leipoldt. E. A. Deutsch and J. C. Sullivan Inory. Chem. 1992.31,1080;(h)L. Helm K. Deutsch E.A. Deutsch. and A. E. Merbach Heir. Chim. Acru 1992 75. 210. 106 M. A. McNamara and M. J. Clarke Inory. Chim. Actu. 1992. 195 175. lo' (a)P. Cornba. D. A. House W. G.Jackson W. Marty H.Stoeckli-Evans and L. Zipper Hela. Chim.Acta. 1992,75 1130; (h)P.Comba W. G.Jackson W. Marty. and L. Zipper H~LI. Chim.Acta 1992,75,1147;(c) P. Comba W. G. Jackson. W. Marty and L. Zipper. Helc. Chim. Actu 1992 75 1172. (a)G.A. Lawrance M. Martinez. B. W. Skelton and A. H. White,J. Chem.Soc.,Dulton Trans.. 1992,1649; (b)G.A. Lawrance T. M. Manning M. Maeder M. Martinez M. A. O'Leary W. C. Patalinghug B. W. Skelton and A. H. White,J. Chem.Soc. Dalton Trans.,1992.1635; (c*)T.W. Hambley G. A. Lawrance. M. Martinez B. W. Skelton and A. H. White J. Chum. Soc. Dalton Trans. 1992 1643; (d) G. A. Lawrance M. Martinez B.W. Skelton and A. H. White J. Chem. Soc..,Dalton Trans..1992.823; (e)G..4.Lawrance M. Martinez. B.W. Skelton R. van Eldik and A. H. White Aust. J.Chem.. 1992 45 351. 1norganic Mechanisms 485 configuration. A conjugate base mechanism involving a square pyramidal intermediate is proposed.' O9 N; anation of mer-exo(H)- and mer-end~(H)-[Co(dien)(dapo)(OH)]~ + is unex-pectedly rapid. The results are believed to support an internal conjugate base mechani~m'~~' in which an OH-catalysed substitution of [Co(dien)(dapo)(H20)I3+ occurs with deprotonation at the dien secondary N tlia the same penta-coordinated intermediate which arises from the base hydrolysis of the corresponding chloro- complexes. Four-coordination.-The non-linear dependence at low pH of the rate of complexation of [M(NH3)5(H,0)]3+ (M = Co Cr) with [HCrO,]- is accounted for by a new mechanism involving proton-assisted rupture of the labile CrV1-0 bond in a hydrogen-bonded transition state rather than by Cr"'-0 fission.'"JGeier has + + established that the formation of [Cu(biq)(Me,phen)] from [Cu(biq),] and Me,phen in acetone or methanol follows two parallel pathways:' It' a direct reaction via an outer-sphere encounter complex and asolvent-assisted path via an intermediate in which one biq is lost. The kinetic behaviour is different in the two solvents. Substitutions in acetone are catalysed by Lewis bases,' 'Ib involving the formation of [Cu(biq)L]"+ (e.g. L = MeCN n = 1; I- n = 0) intermediates. Rate constants for complex formation between [M(H20),I2+ (M = Pd Pt) and the thioethers Me,$ Et,S S(CH,CH,),S and S(CH,CH,),O in aq. HClO suggest' l2 that substitutions at Pt" are more sensitive to the relative hardness and softness of the entering ligand than are those for Pd".Patient study' 3' has permitted a half-life of 23 years to be estimated for the direct exchange of NH in [Pt(NH,),]" at 25 "C. The observed kinetics follow the relationship kabs= kHio + kNH3[NH3] revealing the direct reaction and a parallel indirect process involving rate determining formation of [Pt(NH3)3(H20)]2',t+ = 56 years. The direct exchange is 107-8-fold slower than for the analogous Pd and Au complexes. Clean second order kinetics first order in [CN-] and without a solvent pathway have been established for CN- exchange in [Pt(CH,)(CN),]-in aqueous solution."3h CN- cis to Me exchanges lop3 and the CN-trans to Me lop7 times the rate of CN- exchange in [Pt(CN),I2-.The displacement ofthe first NH from [Pt(NH3),I2+ by aqueous CN- is rate limiting.' 13' Intermediates in similar displacements from cis-and trans-[Pt(NH,),(CN),] cis-and trans-[Pt(NH,),Cl,] and [Pt(NH,)CI,] can be observed. The similarity of the rate of NH displacement from cis-and trans-[Pt(NH,),(CN),] suggests that the cis-effect of CN- is comparable to its trans-effect. The reaction of cis-[PtR,(dmso),] + bipy to give [PtR,(bipy)] + 2 DMSO (R == Me Ph) in acetonitrile is believed to proceed by a dissociative mechanism and involves [PtR,(dmso)] and cis-[PtR,(dmso)(NCMe)] as kinetically important intermediates.' [Pt(tmeda)(dmso)Cl]Cl reacts in CH,Cl to '"' J.A. Broomhead and N.A. Pasha Transition Met. Chrm. 1992. 17 209.(a)M. R. Grace and P. A. Tregloan Zncwg. Chrm.. 1992 31 4524; (h) N. P. Sadler and T. P. Dasgupta Transition Met. Chern.. 1992 17. 317. 'I' (a)U. M. Frei and G. Geier Znorg. Chem. 1992,31 187; (h)U. M. Frei and G. Geier Znorg. Chum. 1992. 31. 3132. S. Elmroth Z. Bugarcic and L. I. Elding Inorg. Chrm. 1992 31 3551. 'I3 (a)B. Brprnnum H. S.Johansen and L. K. Skibsted Inorg. Chem.,1992.31,3023; (h)A. Y.C. Hung J.C. Woolcock M. F. Rettig and R. M. Wing Znorg. Chem. 1992,31,810; (c)L. Cattalini F. Guidi and M. L. Tobe J. Chem. Soc. Dalton Trans.. 1992 3021. l4 la)S. Lanza G. Alibrandi L. M. Scolaro and S. Sergi Inorg. Chim. Acta 1992,201. 137; (h)G. Alibrandi. R. Romeo L. M. Scolaro and M. L. Tobe Znory. Chum. 1992,31,5061;(c)G.Annibale M. Bonivento L. Cattalini and M.L. Tobe J. Chem. Soc,. Dalton Trans.. 1992 3433. 486 N. Winterton release DMSO and form [Pt(tmeda)Cl,] with a first order rate constant.' '4b Added [AsPh,]X accelerates the reaction but with saturation. Interchange within ion aggregates occurs with the limiting interchange rate constant varying only by a factor of two for C1- Br- and I-. Sterically hindered heterocyclic bases L react with cis-[PtCl,(dmso),] in nitromethane to give cis-[PtCl,(dmso)L] whereas less bulky bases give the trans- isomer which slowly isomerizes to cis.' 14' The anti-tumour properties of inorganic compounds such as cis-[Pt(NH,),Cl,] (cisplatin) have stimulated many mechanistic studies. Recent work involving mono- nucleosides and mononucleotides has been reviewed.' '5a The relevance of hydrogen bonding to the mechanism of action of such compounds has also been surveyed.' '5b The reaction between 5'-guanosine monophosphate (GM P) and "N-labelled cisplatin leads to [Pt(GMP),(NH3),l2+ (probably via [Pt(NH,),(H,O)CI]+) in which hydrogen bonding interactions are seen.''5c The rates of displacement of guanosine from cis-[Pt(NH,),(g~anosine)~]Cl~by sulfur nucleophiles containing structural features of compounds used to control the adverse effects of the use of cisplatin in uivo have been reported.' 15d Complex formation in aqueous solution between [Pd(en)(H,0),I2+ or [Pd(R4en)(H2O),l2+ (R = Me Et) with purine nucleosides' '5e and 5'-nucleoside monophosphates' 5f occurs in two consecutive steps each depend- ent on [Nu] by associative mechanisms.All the nucleotides react significantly faster than the corresponding nucleosides suggesting the involvement of the phosphate residue in the stabilization of the transition state. The steric bulk of R appears to affect the formation of the bis-complex to a greater extent than for that of the mono-complex with formation rate constants decreasing by ca. lo3 fold in the series R = H > Me > Et. The effect of [Cl-] on the kinetics of the reaction of [Pd(tmeda)Cl,] with inosine and 5'-inosine monophosphate suggests that [Pd(tmeda)CI(H,O)] is the active species.' '5g + Alkene exchange on [Cl(C,H,)M(p-CI),M(C,H,)Cl] and [MCl,(C,H,)]-(M = Pd Pt) in THF is first order' l6 in [C,H,] with evidence for the formation of bis(ethy1ene)Pt complexes at low temperatures.Reactions of Coordinated Ligands and Linkage Isomerism.-The rate determining step for the decarboxylation of cis-[Cr(hrc)F(OC(O)OH}]+ (in which CO; -chelation is prevented) is proton transfer from an uncoordinated 0 to the coordinated 0 of the carbonato ligand.' '7a A unified mechanism for the decarboxylation of such complexes and for the carbonic anhydrase enzymes' l7~vc is proposed.' 17a Slow proton transfer associated with the extensive geometric and electronic rearrangement involved in p-0x0 protonation has been studied kinetically' '* in the system [{LMn111(p-0)),]2+ (L = 6-Mebispicen) in aqueous MeCN/HClO,; a second order rate constant for the formation of [LMn11'(p-O)(p-OH)Mn111L]3+ of 5440M-' s-' has been measured.(a) M. Green M. Garner and D. M. Orton Transifion Met. Chem. 1992 17 164; (b) J. Reedijk Inorg. Chim.Acra 1992 198-200 873; (c) S.J. Berners-Price T. A. Frenkiel J. D. Ranford and P.J. Sadler J. Chem. Soc.,Dalton Trans. 1992,2137;(d) J.A. Beaty and M. M. Jones Inorg. Chern. 1992.31.2547;(e)H. Hohmann B. Hellquist and R. van Eldik Inory. Chem. 1992,31,345;(f)H. Hohmann B. Hellquist and R. van Eldik inorg. Chem. 1992,31 1090; (g) M. Shoukry H. Hohmann and R. van Eldik Inorg. Chim. Acfa 1992 19S200 187. A. Olsson and P. Kofod inorg. Chem. 1992 31 183. (a)J. Eriksen L. Msnsted and 0.Msnsted Acta Chem. Scand. 1992,46,521; (b)Y.-J. Zheng and K. M. Merz Jr. J. Am. Chem. Soc. 1992 114 10498; (c) M. Sola A. Lledos M. Duran and J. Bertran J. Am. Chem.Soc. 1992 114 869. J. M. Carroll and J. R. Norton J. Am. Chem. Soc. 1992 114. 8744. Inorganic Mechanisms 487 Hydrogen isotope exchange rates in cis-[Pt(NH,),Cl,] [Pt(en)Cl,] and [Pt(tn)Cl,] are proportional to [OD-]."9a H-D exchange rates for polyamines bound to inert transition metal ions have been reviewed.' 19b The rate of interconversion of q'-bound (via0;favoured by Ru"') and q2-bound (via C-0; favoured by Ru") [Ru(NH,),(acetone)]"+ (n = 2 3) is much greater than the acetone-solvent exchange rate suggesting intramolecular isomerization.' 2o Reduc-tion of amide-N bound [Ru(NH,),{n-NHC(0)py) J3 + (n = 3,4) to Ru" is followed by a rapid intramolecular isomerization to the pyridyl-N-bound form.' ' By contrast complexes of simple amides for which such processes are impossible suffer aquation with a pH dependent rate consistent with reaction of a protonated complex.Intramolecular isomerism of 0-to N-bonded acetamide and formamide complexes [Pt(dien){ OC(R)NH,)I2+ has also been studied,', with the N-bonded isomer existing in the imidol form. Metal Ion Complexation with Macrocycles and Che1ates.-On reduction macrobicyc- lic cage complexes of Co"' (1 ) give Co" complexes that are very inert to substitution and R R racemization (half lives of the order of 4.5d at pH 7.1).' 23 Complex formation between Ni2+ and Cu2+ in DMF with cyclic N-' 24a and C-124b3c methylated tetraamines L is found to be a two-step process with a fast initial second order reaction rate = kl[M2+],[L] a square planar intermediate proceeds to the products with first order kinetics rate = kJML?'f].A linear free energy relationship was established between k and the pK of the diprotonated species LH; indicating that the formation of the second M-N bond is rate determining in the formation of [ML]?":. Rapid rearrangement uia M-N bond inversions in the intermediates [ML]?' leads to a more thermodynamically stable form [MLI2+. It is believed that intermediate formation does not involve rate determining formation of the first M-N bond 119 (a)E. Koubek and D. A. House Inorg. Chim.Acta 1992.19t+200,103; (h)D. A. House Coord. Chem. R~L?. 1992 114 249. I20 D.W. Powell and P.A. Lay Inory. Chem. 1992 31 3542. 121 M. H. Chou B. S. Brunschwig C. Creutz. N. Sutin A.Yeh R. C. Chang and C.-T.Lin Inorg. Chrm..1992. 31 5347. 122 T. C. Woon and D. P. Fairlie Inorg. Chrm. 1992 31 4069. 123 R. J. Gene W. R. Petri A.M. Sargeson and M. R. Snow Aust. J. Chem. 1992 45 1681. 124 (a)J. R. Roper and H. Elias Inory. Chem.,1992,31 1202; (h)J. R. Roper and H. Elias. Inorg. Chem.. 1992 31 1210; (c) R. W. Hay and N. Goran. Transition Met. Chem. 1992 17 119. 488 N. Winterton suggesting instead that conformational changes are dominant. Formation rate constants for complexation of Cu" by branched aminopolythiaether chelates L and LH' [L = N(CH,CH,SMe),N N(CH,CH,SEt), and (EtSCH,CH,),NCH,-CH,N(CH,CH,SEt),] support initial Cu-S bond formation followed by rate determining chelate ring closure.' 25 Copper(I1) (and Mn") incorporation into the porphyrin H,tmpyp is catalysed by cuI,1260 uia Cu'-induced deformation of the porphyrin involving the intermediate [Cu'(tmpyp)Cu"] ; Cu2+ incorporation into the porphyrin core is rate determining.Four atropisomeric forms of 'picket fence' porphyrin derivatives of meso-tetrakis(o- alkylamidopheny1)porphyrinare less reactive to Cu" incorporation than H tpp. Steric interactions between o-substituents and the porphyrin core and transannular side chain interactions affect porphyrin core rigidity and thereby metallation rates. '26b Zn2+ incorporation into H,tpp H,tpc and H,tpibc in pyridine solution is thought to proceed via a Zn-H,L intermediate.' 26c,d Incorporation of Cu" into the non-planar dodecaphenylporphyrin (DMF 30°C) is 6 x lo5 times faster than for planar H,tpp.Saturation kinetics are seen with the non-planar ligand.' 26e Metal Dissociation from Macrocyclic Complexes.- Dissociation of iron from the iron-binding protein transferrin has been studied in the presence of pyrophosphate' and organic chelating agents.'27h The variation of the observed pseudo first order rate constant (for C-terminal monoferric transferrin) with P,07 as a function of added monoanions favours' parallel Fe removal from anion- and pyrophosphate-bound protein. Removal of Fe in the presence of the poly(phosphonic acid) H,dtpp pH 7.4 follows complex kinetics suggesting two parallel pathways,' 27h one first order in [dtpp] and the other displaying saturation kinetics. Simple first order kinetics are seen for iron removal from N-terminal monoferric transferrin in the presence of dtpp.Dissociations of Cu" from the macrocyclic tetrathioether complexes [CuL] + L = [12]aneS4 [13]aneS, and [14]aneS4 studied',*" in aqueous Hg2+ as afunction of added [ClO,] and other 'non-coordinating'128h anions such as BF CF,SO; NO, proceeds by parallel spontaneous and Hg2 +-induced ligand loss. The rates of both processes are depressed in the presence of ClO, BF, and CF,SOJ but not NO;. The effective anions are believed to interact directly with CU" to decrease the rate of Cu-S bond rupture. Host-Guest Chemistry.-The kinetics of formation of Li + and Cd2 + complexes with interlocked macrocycles (catenands) in mixed solvent (MeCN/CH,Cl,/H,O) reveal two steps the first a bimolecular complexation and the second independent of [metal] The temperature dependence of the latter suggests the existence of a pre-equilibrium between the first intermediate and a second transient with the latter suffering a first I25 T.H. Cooper M. J. Mayer K.-H. Leung. L. A. Ochryrnowycz and D. B. Rorabacher Inory. Chem.. 1992 31 3796. (a)M. Tabata and M. Babasaki Inorg. Chrm.,1992,31,5268; (h)D. C. Barber D. S. Lawrence and D. G. Whitten J. Phys. Chem. 1992,96. 1204; (c)T. P. G.Sutter and P. Hambright Inorg.Chem.,1992.31,5089; (d) Y. Shimizu K. Taniguchi Y. Inada S. Funahashi Y. Tsuda Y. Ito M. Inarno and M. Tanaka Bull. Chem. SOC.Jpn.. 1992 65. 771; (e)J. Takeda T. Ohya and M. Sato Inorg. Chrm. 1992. 31 2877. 127 (a) T. J. Egan. D. C. Ross L.R. Purves. and P. A. Adams Inorg. Chem. 1992.31 1994; (h)W. R. Harris P. K. Bali and M. M. Crowley. Inorg. Chern. 1992 31. 2700. 128 (a)L. L. Diaddario Jr. L. A. Ochrymowycz and D. B. Rorabacher Inorg. Chrm. 1992.31. 2347; (b)M. Bochrnann Angew. Chem. Inr. Ed. Eng.. 1992 31 1181. Inorganic Mechanisms 489 order rearrangement.' 29a The effect of cyclodextrin encapsulation on the electron transfer reaction of [R~(NH~)~(4,4'-bipy)]~ + and [Co(edta)] -129b has also been studied. The inclusion of the bridging ligand l,l'-(cc,o-alkanediyl)bis(4,4'-bipyridin-+ ium) dication [4,4'-bipy(CH2),4,4'-bipyl2 (n = 8-12) by r-cyclodextrin (a-CD) enhances the kinetic stability of the N-Fe bond in the 'rotoxane' complex [(NC)5Fe{bipy(CH,),bipy.a-CD}Fe(CN),14-'29c [in which a cyclic molecular bead (cr-CD) is threaded by a linear chain bearing bulky end groups].Mechanistic developments in complex formation of macrocycles with neutral molecules have been reviewed.129d The equilibria for complex formation and kinetics of the exchange of monovalent metal ions such as Li' Na' Kf ,Rb+ and Cs+ in their complexes with C22C8 have been measured in MeCN py MeOH and DMF.' 29e Similar studies' 291*g have been undertaken for the complex [ML]' (M = Na Li; L = benzo-15-crown-5 15-crown-5) in nitromethane for which an associative metal interchange mechanism is proposed (with ligand conformational changes being important) and in MeCN for which a dissociative mechanism is proposed (with solvation of the complexed cation being important).Complexation kinetics of Li + by triethylene glycol and tetraethy- lene glycol in acetonitrile have been studied by ultrasonic relaxation.' 29h Five- Seven- and Higher Coordination.-In a study relevant to the use of Re and Tc therapeutic and diagnostic pharmaceuticals an associative mechanism has been pr~posed'~' for the exchange of 0 between [M(O)(N,S,)]-(M = Re Tc; N,S = dbds2- and similar ligands) and water. The value of k,,/k, of 0.1 compares with that of ca. lo3 expected for the dissociative mechanism of analogous six- coordinate complexes. The first study of the kinetics of substitution on seven-coordinate [ML7I2+ (M = Mo W; L = Bu'NC) using X = C1- Br- and I-in acetonitrile (and of X loss from [ML,X]') concludes that substitution is dissocia-tive involving both ion-paired and non-ion-paired complexes.' lo The sequential replacement of I- by C1- in [MoI,(PMe,),Cp] in CH,Cl is each the sum of two second order processes involving solvated and ion-paired C1- as nucleophiles.' '' The corresponding Cp* complexes react lo5 times faster than the Cp complexes. The substitutions are catalysed by one-electron oxidants.' '' [Ln(en),13+/en exchange kinetics,13 first order in [en] for Ln = Pr Nd and Eu have been discussed in terms of a nine-coordinate intermediate. For smaller ions (Ln = Er Yb) a more complex [en] dependence is seen with parallel I and D mechanisms proposed. Main Group Reactions.-The variation of rate constant with [H'] for the reaction of HNO with [NH30H] + has been interpreted in terms of reversible 0-nitrosation 12' (a) A.-M.Albrecht-Gary C. Dietrich-Buchecker Z. Saad. and J.-P. Sauvage J. Chem. Soc.. Chem. Commun. 1992,280; (h)M. D. Johnson V. C. Reinsborough and S.Ward Inorg. Chem. 1992,31 1085; (c) R.S. Wylie and D. H. Macartney J. Am. Chem. Soc. 1992,114,3136; (d)R. M. Izatt J.S. Bradshaw. K. Pawlak R. L. Bruening and 9.J. Tarbet Chem. Rev. 1992 92 1261; (e) S. F. Lincoln and A. K. W. Stephens Inorg. Chem. 1992,31,5067;(1)K. M. Briere and C. Detellier Can.J. Chem. 1992,70,2536;(y) K. M. Briere and C. Detellier. J. Phys. Chem.. 1992,% 2185; (h)D. P. Cobranchi. B. A. Garland M.C. Masiker E. M. Eyring P. Firman. and S. Petrucci J. Phys. Chem. 1992 96 5856. 13" B. Chen M. J. Heeg and E. Deutsch Inory. Chem. 1992 31 4683.13' (a)A. F. Lindmark Inorg. Chem. 1992,31,3507; (h)R. Poli. B. E. Owens and R. G. Linck Inorg. Chem. 1992 31 662; (c) R. Poli B.E. Owens and R.G. Linck J. Am. Chrm. SOL... 1992 114 1302. 132 J. H. F0rsberg.T. J. Dolter A. M. Carter D. Singh S. A. Aubuchon. A. T. Timperman,and A. Ziaee Inorg. Chem.. 1992 31 5555. 490 N. Winterton followed by 0 to N migration of the NO group in the conjugate base intermediate NH,0N0.'33a ''N tracer studies of the reaction of nitrous acid and hydrazine do not support an earlier suggestion of a cyclic azide intermediate. The data instead support three separate pathways one uia formation of HN, one via the dinitrosated species ONNHNHNO and a third possibly involving HN = NN(NO)OH.'33bA stopped flow ESR kinetic study of the reaction of HNO and HSO at pH < 5.8 supports the involvement of the nitrene HON as a reactive intermediate.' 33c Halide exchange between S,Cl and Se,Br has been studied by 77Se NMR.'33d Solvent and Other Medium Effects.-Burgess and Pelizzetti" have produced a timely extensive and authoritative review of solvent and microdomain effects on inorganic and substitution and redox reactions highlighting the paucity of data on such medium effects for intramolecular transfers and homogeneous catalysis.Salt effects have also been re~iewed.'~~" Salt effects on the substitution of 4-pyCN by CN- in [Fe(CN),(4- NCpy)13- confirm a D mechanism and permit an estimate to be made of AV which however is in only fair agreement with that measured from pressure dependent kinetic studies.' 34b Abbott has investigated correlations between solvent polarity scales and electron transfer kinetics.'34c NMR imaging has been used to visualize iron redox reactions in a polyacrylamide gel.' 34d The [Ru(bipy),12 photosensitized reduction of + a Co"' tetraazamacrocycle complex in a gelatin hydrogel and hydrosol'34' has also been studied.Reference has been made in other sections to specific ion effects of alkali metal 2,170.18a.138j and anions.128a Additional work has been reported on micellar effects on inorganic reactions. u-Bonded Organotransition Metal Compounds.-Rate and activation parameters for the acetate-catalysed heterolysis of [Cr(H,0),Rl2' trans-[Cr([lS]aneN,)(H,O)-RI2+ and cis-[Cr(nta)(H,O)R]- (R = CH,OH CMe,OH) are consistent the trans-labilization of R by coordinated acetate and attack of H,O on Cr-C in a dissociatively activated heterolysis.The chemistry of organochromium(m) complexes has been reviewed.' 35b The kinetics for the formation and dissociation of PhCH,Cu" complexes in aqueous solution and of Cu" and Cu' transient o-bonded alkyls with 'CH,CMe(NHl)CO, have been reported.' 35c,d p-Hydrogen abstraction to give ethylene is observed in the reaction of alkanethiyl radicals with the ethyl-metal compounds [ML(H,O)R]" (M = Co L = [14]aneN4; M = Cr L = [lS]-aneN,).' 36 Methylcobalamin homolyses in the presence of a spin-trap to give Co"B 2r and the 133 (a)G.C. M. Bourke and G. Stedman J. Chem. Soc. Perkin Trans. 2 1992 161 ; (6) R.J. Gowland. K. R. Howes and G. Stedman J. Chem. SOC.,Ddton Trans. 1992 797; (c)S. N. Mendiara E. Ghibaudi L. J. Perissinotti and A. J. Colussi J. Phys. Chem. 1992,% 8089; (d)J. Milne and A. J. Williams Inorg. Chem.. 1992 31 4534. 134 (a)A. Loupy B. Tchoubar and D. Astruc Chem.Rev. 1992,92,1141; (6) A. Barrios. M. del M. Graciani R. Jimenez E. Muiioz F. Sanchez M. L. Moya S.Alshetiri. and J. Burgess Transition Met.Chem. 1992. 17,231; (c)A. P. Abbott J. Electroanal. Chem. 1392,327,31; (d)B. J. Balcom T. A. Carpenter and L. D. Hall J. Chem. Soc.,Chem. Commun.. 1992.312; (e)M. Yagi K.Okajima and Y. Kurimura J. Chem. Soc. Faraday Trans. 1992 88 1411. 135 (a)H. Cohen W. Gaede. A. Gerhard D. Meyerstein and R. van Eldik Inorg. Chem. 1992.31 3805 (h) J. H. Espenson Ace.Chem. Re.?. 1992,25,222; (c)A. Mayouf H. Lemmetyinen 1. Sychttchikova and J. Koskikallio Int. J. Chem. Kiner. 1992,24,579:(d)S.Goldstein G. Czapski H. Cohcn and D. Meyerstein Inorg. Chem.. 1992 31 2439. 136 P. Huston J. H. Espenson. and A. Bakac Organometallics. 1992 11 3165. lnorganic Mechanisms 49 1 trapped methyl radical.' 37Q*bThe rate (extrapolated to -30 "C) is 10'' k4less than that for methylcobamide radical anion the acceleration for the latter is related to the electron in the a*-LUMO of the Co-C bond. The lability of such reduced species has also been noted in of models of the nickel-containing factor F-430 which participates in methane biogenesis. Reaction of [Ni(oeibc)] -with alkyl halides gives the products of reduction coupling.and dehydrohalogenation with reactivity orders MeX > primary C-X secondary GX > tertiary C-X and RI > RBr > RCI being established' 37c9d for an S,2 process. Rate constants suggest that [Ni(oeibc)] -is the fastest transition metal nucleophile yet recorded. Different mechanistic proposals were made. Stolzenberg and co-workers.' 37d conclude that free radical processes can be ruled out proposing reaction at the Ni of the transient [RNi(oeibc)]. Helvenston and Ca~tro'~~~ propose two R-Ni transients [RNi(oeibc)] and a reduced form R-Ni" produced from R-Ni"' and Ni'. A novel three-electron process was also discussed with RX giving R' and X-directly without R-Ni"' formation. Increasing steric demand at RX leads to a shift in mechanism of reaction with porphyrinatocobalt(1) from a two-electron to a one-electron process.' 37f The intercon- version of Y-and b-methylcobinamide is catalysed by non-alkylated cobinamides by direct Co to Co methyl transfer.Such isomerizations are not seen with other alkylcobinamides.' 379-h Mechanisms of alkyl transfer between alkyl metal carbonyls and [Fe(CO),Cp] -have also been studied.'37' A reinvestigation' 37j of the intermolecular benzyl migration of the co-enzyme B model (2) to (3) (Equation 1) has demonstrated the operation of the principle of internal suppression of fast reactions propounded earlier by H. Fischer. Dissociation of either (2) or (3) gives caged radical pairs which can equilibrate with free PhCH; and [Co" (macrocycle)] with the former either dimerizing or being spin trapped.Careful analysis for the previously undetected dibenzyl allowed an estimate of a lo5:I selectivity between the intermolecular reaction of the two radicals giving (2) and (3)and that giving dibenzyl. Cage recombination efficiencies have also been assessed for the b-elimination process in ado-cobinamide (axial base off) Co-C thermolysis' 37k and 13' (a)B.D. Martin and K. G. Finke J. Am. C'hem.Soc. 1992 114 585; (h)A. Vlceck Jr. Chemrracts Inory. Chem.. 1992,4 107; (c) M.C. Helvenston and C.E. Castro. J. Am. Chem. Scrc.,1992.114.8490 (d)G.K. Lahiri L. J. Schussel and A. M. Stolzenberg Inorq. Chem. 1992,31 4991; (e)T. Arai H. Kondo and S. Sakaki J. Chem.Soc.. Dalton Trans. 1992.2753; (f) D. L. Zhou P. Walder R. Scheffold and L.Walder Helc. Chim. Acta 1992,75,995;(Q) K. L. Brown and X. Zou. Inorg. Chem. 1992.31.2541 (h)X. Zou K. L. Brown and C. Vaughn. Inory. Chem.. 1992. 31 1552; (i) P. Wang and J. D. Atwood J. Am. Chem. Soc.. 1992 114,6424; (i) B.E. Daikh and R.G. Finke. J. Am. Chem. Soc.. 1992 114,2938; (k)C. D. Garr and R.G. Finke. J. Am. Chem. So(..,1992. 114. 10440; (I) L. E. H. Gerards M. W. G. de Bolster. and S. Balt. Inorq. Chim. Actu 1992 192.287. 492 N. Winterton from AV measurements' 71 (corrected for pressure effects on the axial base on-off equilibrium) for alkylcobalamin Co-C thermolyses in mixed solvents. Ligand Displacement Reactions of Metal Carbonyl Compounds. -Solvent-dependent competitive solvent displacement processes are seen for ligand substitution of S in [C r (CO ),S] ' a 3 and for chelate ring closure in cis-[W(CO),SL] [L = Ph,P(CH,),CH=CH, n = lWl].'38'q6 Ligand C-H agostically bound inter- mediates are propo~ed.'~~' [W(CO),Xe] reacts with CO in liquid xenon by a dissociative process.'38e The rapid exchange of [1rClH2(H2)(PPr3),] with molecular hydrogen,'38f and other observations,' 38g suggest that H is molecularly bound q2. Intramolecular exchange between dihydrogen and the hydride ligands is also observed.'38s Increased steric hindrance in L changes chelate ring closure in [Mo(CO),L] from an associative interchange I, for L = bipy 4,4'-Me,bipy to a dissociative interchange I, for L = 4,4'-Ph2bipy.' 38h The previously reported acceleration by alkali metal cations of CO exchange with [Co(CO),]-is now ascribed13*' to redox processes initiated by traces of oxygen.Substitution of CO by PR in the radicals [Cr(CO),Cp] to give [Cr(CO),(PR,)Cp] proceeds via an associative interchange.' 38j Associative CO replacement by Bu'NC in the 17-electron [Cr(CO)(3-C,H9)Cp*] + can be compared with the dissociative CO exchange in the 18-electron half-open chromocene carbonyls.' 38k A common inter- mediate link~',~' [Re(CO),L,(q'-C,H,)] and [Re(CO),L(q5-C,H7)] formed from [Re(CO),(q'-C,H,)] and L = PR or P(OR),. Steric and electronic factors on the rate of CO displacement from substituted indenyl-Rh complexes [Rh(CO),(qs-C,R,H,-,)] (all believed to have the same coordination at Rh) tentatively support a new q5-q3-exo-q5ring slippage mechani~m.'~~" A linear correlation is noted between lo3Rh chemical shifts and the log kobsfor CO displacement by PPh in [Rh(CO),(q5- C,H,X)] .'38" Two groups have re-examined substitution processes in [{Fe(CO),- Cp),I.' Turner Poliakoff and co-~orkers'~~' have shown that by better controlling the processes of CO ejection and Fe-Fe homolysis reaction with phosphites can be seen to involve rapid substitution of CO in [Fe(CO),Cp] to give [(Fe(CO)LCp),] [L = P(OMe),] followed by dimerization to give [(Fe(CO)LCpj ,I. Brown and co-workers have proposed three new intermediates,' 39b3c viz. [CpFe(p-CO),(p-q' :q2-CO)FeCp] [(q3-C,H,)(CO),Fe(p-q' :q2-CO)Fe(CO)Cp] and [(q3-C,H,)(CO),FeFe(CO),Cp] from similar studies. The mechanisms of the reaction of the intermediate [Fe,(p-CO),Cp,] with a range of ligands have also been studied.13' (u)S. Zhang and G. R. Dobson Orgunomerullics 1992 11,2447; (h)S. Zhang H. C. Bajaj. V. Zang Ci. R. Dobson and R. van Eldik Orgcrnometallics 1992 11 3901; (c) V. Zang S. Zhang C. B. Dobson G.R. Dobson and R. van Eldik Orgunometullics 1992 11 1154; (d)S. Zhang I.-H. Wang P. H. Wermer C.9. Dobson and G.R. Dobson Inorg. Chem. 1992 31 3482; (e) B.H. Weiller J. Am. Chem. Soc.. 1992. 114,10910; (f) M. Mediati G. N. Tachibana and C.M. Jensen. Inorg. Chem.. 1992. 31 1827; (g) M.A. Esteruelas J. Herrero A. M. Lopez L. A. Oro M. Schulz and H. Werner Inorg.Chem..1992.31.4013; (h) K. B. Reddy. R. Hoffmann G. Konya R. van Eldik. and E. M.Eyring Orgunomefullics 1992 11.2319 (i) G. Fachinetti and T. Funaioli Angew.Chem.,In[.Ed. Engl. 1992,31 1596; (j)W. C. Watkins K. Hensel S. Fortier D. H. Macartney M.C. Baird and S. J. McLain Orgunometullics 1992 11 2418; (k) J. K. Shen J. W. Freeman N. C. Hallinan A. L. Rheingold A.M. Arif R. D. Ernst and F. Basolo Orgunometullics 1992 11 3215; (i) H. Bang T. J. Lynch and F. Basolo 0rgunomefullic.s. 1992 11.40; (m)A. K. Kakkar N. J. Taylor. T. 9. Marder J. K. Shen N. Hallinan and F. Basolo Inorg. Chim. Actu 1992 198-200,219; (n) M.Koller and W. von Philipsborn Orgunomefullicx 1992. 11 461. (u) A. J. Dixon. M. W. George C. Hughes M.Poliakoff. and J. J. Turner J. Am. Chem. Soc... 1992. 114. 1719; (h)S. Zhang and T. L. Brown J. Am. Chem. Soc. 1992 114 2723 (c) S. Zhang and T. L. Brown Oryunomerallics 1992. 1 I.4166. Inorganic Mechanisms Cage recombination efficiencies' 40 in the photochemically generated radical cage pairs from [(M(CO),Cp'),] (M = Mo W) are significant even in common solvents. In contrast to other ligands (e.g. RNCI4'") CO reacts with five-coordinate hemes and heme proteins at rates which are significantly less than diffusion controlled. Photolysis of BHmCO (e.g.,B = methanol 1-methylimidazole Hm = heme protein) displays no observable CO return on a picosecond timescale in non-viscous solution and part return in highly viscous media such as glycerol.'41b Studies of the pressure dependence of the reaction of CO with protohaemin 3-(1-methylimidazoyl)propylamidestearyl ester chloride suggest that the rate limiting process changes from bond formation to diffusion as the pressure 140 K.J. Covert E. F. Askew J. Grunkerneier,T. Koenig,and D. R. Tyler J. Am. Chrm. Soc.. 1992,114.10446. 141 (a)T. G. Traylor D. Magde J. Luo K. N. Walda. D. Bandyopadhyay G -Z. Wu and V. S. Sharma J. Am. Chrm. Soc. 1992 114 9011; (h) T.G. Traylor D. Magde D.J. Taube K.A. Jongeward D. Bandyopadhyay. J. Luo,and K. N. Walda. .I. Am. Chem.Soc.. 1992,114,417 (c) T. G.Traylor J. Luo,J. A. Simon and P. C. Ford J. Am. Chem. Soc 1992 114 4340.
ISSN:0260-1818
DOI:10.1039/IC9928900473
出版商:RSC
年代:1992
数据来源: RSC
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Chapter 26. Bioinorganic chemistry |
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Annual Reports Section "A" (Inorganic Chemistry),
Volume 89,
Issue 1,
1992,
Page 495-513
J. D. Crane,
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摘要:
26 Bioinorganic Chemistry By J. D. CRANE School of Chemistry and Molecular Sciences University of Sussex Falmer Brighton East Sussex BN1 9QJ UK 1 Introduction As bioinorganic chemistry has not been covered before as a separate topic in Annual Reports this review of the highlights of the field for 1992 will also refer to a few important books and articles published in 1990 and 1991. Interest in bioinorganic chemistry has increased greatly over recent years testifying to the importance of understanding the many essential functions that transition metal ions perform in biology. 1-3 Recent developments towards elucidating transition metal biosite structure and function,4p6 and investigations into the fundamental electron transfer reactions of metal lop rote in^,'^^ have been reviewed.For a wide variety of transition metal biosites the metal oxidation state(s) have been deduced from EXAFS data by bond valence sum (BVS) analysis; the empirical quantity BVS correlates with oxidation state for a range of relevant model compounds." Details of the structure and function of particular transition metal biosites in metalloproteins along with relevant model compounds are discussed in the following sections. 2 Vanadium The distribution and chemistry of vanadium sites in biology have been reviewed." Vanadium haloperoxidases are found in marine algae and terrestrial lichen and catalyse the halogenation of organic compounds (Equation 1). EXAFS studies of vanadium bromoperoxidase indicate a Vv centre with one 0x0 group and five or six N/O-donor ligands at least one of which is a histidine residue.Several Vv and V'" potential model compounds with imidazole coordination have been structurally characterized and the ESR parameters of the V" complexes compared with those of the R. J. P. Williams J. Chem. Soc. Dulton Truns. 1991 539. * J.J.R.F. Da Silva and R.J.P. Williams. 'The Biological Chemistry of the Elements the Inorganic Chemistry of Life' Clarendon Press Oxford 199I. ' I. Bertini L. Messori and M. S. Viezzoli Coord. Chem. Re[>. 1992 120. 163. Proy. Inorg. Chem. 1990 38. ' Ah. Inorg. Chem. 1991 36. ' Ah. Protein Chem. 1991 42. ' J.R. Winkler and H. B. Gray Chem. Rec. 1992 92. 369. ' S. S. Isied. M. Y. Ogawa and J. F. Wishart Chem. Reu. 1992 92 381. ' G. McLendon and R.Hake Chem. Rec.. 1992 92 481. H.H. Thorp Inorg. Chem.. 1992 31 1585. 'I R. Wcver and K. Kustin Adr. Inorg. Chem. 1990. 35 81. 495 496 J. D. Crane inactive reduced VIV form of the en~yme.'~.'~ The dioxovanadium ion [V"(O),] has + also been shown to display bromoperoxidase activity albeit at a much lower pH than the enzyme.' RH + [HI' + [XI-+ H,02 [''I-RX + 2H20 (1 1 (X=Cl,Br,I) Vanadates are potent inhibitors for ATPases phosphatases and nucleases and are believed to coordinate to these enzymes as trigonal bipyramidal Vv complexes with 0 donor sets. This metal environment is found in the structurally characterized complex [(l)]" which is reported to be a model of particular relevance to vanadium substituted ribonuclease and transferrin.' Other V'" complexes with predominantly phenolate and imidazole ligation have been structurally characterized and are relevant as general models for tyrosine and histidine coordination in vanadium metalloen- zyme~.'~'~~ 3 Manganese Manganese is found in a wide range of metalloproteins of different function including manganese superoxide dismutase (Mn-SOD) manganese peroxidase manganese pseudocatalase manganese ribonucleotide reductase (Mn-RR) and the 0,-evolving complex of photosystem I1 (PS 11) of which the last three are known to contain two or more manganese atoms at the active site.4" '-,' The Mn-SODS are mononuclear Mn"' with N/O-donor sets and potential model compounds for these biosites have been structurally characterized.'., These models also have some relevance to the [4Mn] site of PS IT which may exist as a trinuclear/mononuclear (3 + 1 ) arrangement of manganese sites.The manganese pseudocatalase from Lactobacillus plantarum contains a dinuclear manganese site and can exist in four oxidation states Mn"/Mn" to Mn"'/Mn'" inclusive. EXAFS studies of these two extremes indicate coordination with N/O-donor 12 C. R. Cornman J. Kampf and V. L. Pecoraro Inory. Chem.. 1992. 31. 1981. I3 C. R. Cornman J. Kampf M. S. Lah and V. L. Pecoraro. Inorg. Cheni. 1992. 31. 2035. 14 R. I. de la Rosa M. J. Clague and A. Butler J. Am. Chrm. So(,.. 1992 114 760. 1s T. W. Hambley R. J. Judd. and P. A. Lay. Inorg. Chem. 1992 31 343. 16 A. Neves A. S. Ceccato. I. Vencato Y.P. Mascarenhas and C. Erasmus-Buhr. J. Chetn. SO,.. Chrm. Commun. 1992 652. 17 L. J. Calviou. J. M. Arber. D. Collison. C. D. Garner. and W. Clegg. J. Chtm.So(,..Chem. Commun.. 1992. 654. I8 G.C. Dismukes NATO AS1 Srr. Ser. C. 1991 343 137. 19 G. W. Brudvig H. H. Thorp and R.H. Crabtree. Aw. Chrm. Rrs. 1991 24 31 I. 20 'Manganese Redox Enzymes' ed. V. L. Pecoraro VCH New York. 1992. 21 S. K. Chandra and A. Chakravorty. Inorgl. Chem.. 1992 31. 760. 22 A. Neves S. M. D. Erthal I. Vencato. A.S Ceccato. Y. P. Mascarenhas 0.R. Nascimento. M. Horner and A. A. Batista Inorg. Chem.. 1992. 31. 4749. Bioinorganic Chemistry 497 ligands and are consistent with a [Mn(p-O),Mn13+ core in the oxidized form (Mn-Mn = 2.67 A) and apparent loss of this bridging structure in the reduced form.23 Binuclear manganese complexes with oxidation states ranging from Mn"/Mn" to Mn"/Mn" have been prepared and are proposed as potential models for the manganese pseudocatalase and Mn-RR bio~ites.,~~~~ The Mn"' complex of [L 'I3 is tetranuclear in the solid state but has been shown to adopt a dinuclear structure with high catalase-like activity in DMF.2 The binuclear complex [L2Mn'V(p-O),Mn'VL'] also displays catalase-like activity.which is suppressed by protonation of one of the 0x0 bridges.28 H,L* The 0,-evolving complex of PS I1 is known to contain a [4Mn] site probably arranged as a tetranuclear structure. Although a (3 + 1)arrangement is still considered to be a possibility ESR studies have shown that the ground spin state of the S resting state of PS I1 is diamagnetic thus strongly favouring the tetranuclear f~rmulation.~~ Nevertheless several trinuclear manganese complexes have been reported as potential structural model^.^'-^^ The S state of PS 11 is characterized by the g = 4.1 and g = 2 ('multiline') ESR signals which are believed to arise from a combination of Mn"' and Mn" in the tetranuclear cluster.An asymmetric binuclear Mn"'/MntV complex gives similar signals at g -5 and g -2 and the temperature dependence of the low field component suggests that it may arise through thermal population of the S = 3/2 first excited state.34 Many tetranuclear model complexes for PS I1 with different arrangements of the manganese ions have been reported including chain-like (2),3 dimer of dimers (3),j6and cubane structures (4).37-39 23 G.S.Waldo S. Yu and J.E. Penner-Hahn. J. Am. Chem. Soc. 1992. 114 5869. 24 S.-B. Yu S.J. Lippard I. Shweky and A. Bino Inory. Chem. 1992 31 3502. 25 Y. Gultneh A. Farooq S. Liu K. D. Karlin and J. Zubieta. Inory. Chem.. 1992. 31 3607. 26 E. Larson M. S. Lah. X. Li. J.A. Bonadies and V. L. Pecoraro. Inory. Chem.. 1992 31 373. 27 K. Shindo. Y. Mori K. Motoda H. Sakiyarna N. Matsurnoto and H. Okawa Inorg. Chem.. 1992 31 4987. zn E. J. Larson P.J. Riggs J. E. Penner-Hahn and V. L. Pecoraro. J. Chem. Soc.. Chem. Commun. 1992 102. 29 D. Koulougliotis D. J. Hirsch. and G. W. Brudvig. J. Am. Chem. Soc.. 1992 114 8322. 30 S. Pal. M. K. Chan and W. H.Armstrong J. Am. Chem. Soc.. 1992. 114. 6398. 31 S. Pal and W. H. Armstrong Inory. Chem.. 1992. 31. 5417. 32 D. P. Kessissoglou M. L. Kirk M.S. Lah X. Li C. Raptopoulou W. E. Hatfield. and V. L. Pecoraro Inory. Chem.. 1992. 31. 5424. 33 M. Mikuriya K. Majirna and Y. Yarnalo Chem. Lett.. 1992 1929. 3 4 E. Larson A. Haddy. M. L. Kirk R. H. Sands W. E. Hatfield. and V. L. Pecoraro J. Am. Chem. Soc. 1992. 114 6263. 3 4 C. Philouze G. Blondin S. Minage N. Auger. J.-J. Girerd. D. Vigner. M. Lance. and M. Nierlich Anyew. Chem. Int. Ed. Enyl. 1992 31 1629. 3h M. Mikuriya Y. Yamato and T. Tokii Bull. Chem. Soc. Jpn. 1992 65.2624. 3' D. N. Hendrickson G. Christou E. A. Schmitt E. Libby J. S. Bashkin S. Wang H.-L. Tsai J. B. Vincent P. D.W. Boyd. J.C. Huffrnan K. Folting Q. Li. and W. E. Streib J. Am. Chem. Soc. 1992. 114 2455. 3X E. A. Schrnitt L. Noodlernan E. J. Baerends and D. N. Hendrickson J. Am. Chem. Soc.. 1992,114,6109. 39 S. Wang. H.-L. Tsai W. E. Streib. G. Christou and D. N. Hendrickson. J. Chem. So(,.,Chem. Commun.. 1992 1427. 498 J. D. Crane (31 (4) (X= C1 Br) 4 Iron Haem Biosites The I3C NMR resonances for the proximal histidine in horse deoxymyoglobin have been identified and found to be sensitive probes for both the iron-histidine interaction and protein-histidine hydrogen bonding.40 The effect of subtle protein-ligand interactions in azidomet- and cyanomet-myoglobins have been studied by vibrational circular dichroism and low temperature near-IR spectro~copy,~ ',42 and the perturba- tion of Fe-CN groups in sterically hindered cyanomet-haem model compounds has been probed by I5N NMR.43 Several synthetic sterically-hindered porphyrin compounds have also been prepared as models for the reversible 0 binding of myoglobin and haem~globin,~~~~~ and for the possible transient binding of a water molecule after the breaking of the iron-histidine bond at low pH.47 The haem resonances in the 'H NMR spectrum of oxidized cytochrome c3 from Desulfovibrio vulgaris have been assigned.48 Spectroscopic model compounds for the cytochromes b have been studied by 57Fe Mossbauer ESR and 'H NMR spectros- co~ies,~~.~~ and an Fe" cytochrome c model has been synthesized and characterized by 'H NMR.'* A model for haem d of bacterial nitrite reductase has also been structurally and spectroscopically ~haracterized.~ The binding of [N3]-to cytochrome c oxidase in a range of oxidation states has been studied by IR and electronic absorption spectro~copy.~~ The observed independence of Cu and haem a3indicates the presence of an [Fe(~,)"'00H]~+ structure rather than a bridged [Fe(a3)''1(p-0,)Cu~]3 structure as the intermediate in the reduction of 0,; + other studies of this reaction suggest that the 0 molecule transiently binds to Cu 40 Y.Yamamoto and R. Chiijj8 J. Chem. Soc. Chem. Commun. 1992 87. 41 R. W. Bormett S. A. Asher P.J. Larkin W. G.Gustafson N. Ragunathan T. B. Freedman L. A. Nafie S. Balasubramanian S.G. Boxer N.-T. Yu K. Gersonde R. W. Noble B. A.Springer and S.G. Sligar J. Am. Chem. Soc. 1992 114 6864. 42 M. Leone A. Cupane E. Vitrano and L. Cordone Biophys. Chem.. 1992 42 111. 43 G. Aviles and C. K. Chang J. Chem. Soc. Chem. Commun. 1992 31. 44 I. P. Gerothanassis B. Loock and M. Momenteau J. Chem. Soc. Chem. Commun. 1992 598. 45 C. Cartier M. Momenteau. E. Dartyge A. Fontaine G. Tourillon. A. Michalowicz and M. Verdaguer J. Chem. Soc. Dalton Truns. 1992 609. 46 H. Imai S. Nakagawa and E. Kyuno Inorg. Chim. Actu 1992 193 105. 47 L. Leondiadis M. Momenteau. and A. Desbois Inory. Chem. 1992 31. 4691. 48 M. Sola and J. A. Cowan. Inorg. Chim. Actu 1992. 202 241. 49 M. K. Safo G. P. Gupta C.T. Watson U. Simonis F. A. Walker and W. R. Scheidt J. Am. Chem. Soc. 1992 114 7066.50 Q. Lin U. Simonis A. R. Tipton C. J. Norvell and F. A. Walker Inorg. Chem. 1992. 31. 4216. 51 B. Boitrel A. Lecas-Nawrocka and E. Rose Tetrahedron Lett.. 1992 33 227. 52 K. M. Barkigia C.K. Chang J. Fajer. and M. W. Renner J. Am. Chem. Soc.. 1992 114 1701. 53 S. Yoshikawa and W. S. Caughey. J. Biol. Chem.. 1992 267. 9757. Bioinorganic Chemistry before transferring to haem u3.54 An ESR signal at g' = 2.95 for a slow form of cytochrome c oxidase has been shown to display the same reductive decay rate and temperature dependence as the characteristic g' = 12 signal for the Cu,/haem a3 centre and is consistent with a CuL/ferryl-haem a3f~rmulation.~~ The Fe" haem site in reduced yeast cytochrome c peroxidase undergoes a transition from five-coordinate high-spin to six-coordinate low-spin over the pH range 7.0 to 9.7 associated with the binding of histidine at the vacant coordination site.56 Dinuclear iron/copper model compounds for cytochrome c oxidase with [02J2-and an S-donor bridging ligand [(5)] have also been prepared and their spectroscopic properties and reactivities reported.7+58 Ph The biochemistry of the cytochrome P-450monoo~ygenases~~ and the mechanism of the alkene epoxidation reactivity displayed by cytochrome P-450model compounds used as organic reagents6' have been reviewed. Synthetic cytochrome P-450 model compounds have also been shown to insert oxygen into non-activated C-H bonds (hydroxylation),61*62 and asymmetrically to oxidize aryl sulfides to chiral sulfoxides with 18 to 71% enantiomeric excess.63 Model compounds for the P-460 centre of the hydroxylamine oxidoreductase from Nitrosomonns europene have been studied by ESR and 57Fe Mossbauer spectros~opies.~"~~~ The Fe''=O stretching vibration (vFeO = 790 cm- [I 60], 756 cm ["01) has been identified by resonance Raman spectroscopy for the transient species formed in the reaction of H,02 with the thiolate-ligated haem of chloroperoxidase from 54 M.Oliveberg and B.G. Malmstrorn Biochemistry 1992 31. 3560. 55 C. E. Cooper and J.C. Salerno. J. Riol. Chem. 1992 267 280. 56 J. Wang N. J. Boldt and M. R. Ondrias. Biochemistry 1992 31 867. 57 A. Nanthakumar M. S. Nasir K. D. Karlin N. Ravi and B. H. Huynh.J. Am. Chem. Soc.. 1992,114.6564. B.R. Serr C.E. L. Headford 0. P. Anderson. C. M. Elliott K. Spartalian V. E. Fainzilberg W. E. Hatfield €3. R. Rohrs S. S. Eaton and Ci. R. Eaton Inory. Chem. 1992 31 5450. '' FASEB J. 1992,6 661-810. 6o D. Ostovic and T.C. Bruice Acc. Chem. Res.. 1992 25. 314. 61 T. G.Traylor K. W. Hill W.-P. Fann S. Tsuchiya and B. E. Dunlap. J. Am. Chem. Soc.. 1992. 114 1308. 62 H. Patzelt and W. D. Woggon Helr. Chim. Acta 1992 75. 523. 63 L.C. Chiang K. Konishi T. Aida and S. Inoue. J. Chem. Soc.. Chrm. Commun.. 1992 254. 64 E. L. Bominaar X.-Q. Ding A. Gisrnelseed E. Bill H. Winkler A.X. Trautwein. H. Nasri J. Fischer. and R. Weiss Inory. Chem.. 1992 31 1845. " E. Bill E. L. Bominaar. X.-Q. Ding J. Fischer. A. Gismelseed H. Nasri A. X. Trautwein R. Weiss. and H. Winkler Hyperfine Intivwt.1992 71. 1295. 500 J. D.Crane Caldariomyces fumago and demonstrates the formation of an oxoferryl porphyrin n-cation radical.66 A number of oxoferryl porphyrin n-cation radical model com- pounds have been prepared and studied by ESR 57Fe Mossbauer and resonance Raman spectros~opies.~~~~~ The 'push effect' of substituted imidazole proximal ligands on the heterolytic cleavage of the 0-0 bond in acylperoxo-Fe"' porphyrin model complexes to yield oxoferryl derivatives has been studied by electronic absorption spectroscopy and ESR.71*72 5 Iron Non-haem Biosites The electronic structures of mononuclear and dinuclear non-haem iron biosites with N/O-donor ligands have been reviewed.73 Thirteen new desferrioxamine siderophores have been obtained by the directed fermentation of Streptomyces oliuaceus and the stability constants of the corresponding mononuclear Fe"' complexes determined.74 The nitrosyl derivative of the iron site of soybean lipoxygenase has been investigated by magnetic circular dichroism resonance Raman and X-ray absorption edge spectros- copies; these indicate a (Fe"'/[NO]-) formulation for the observed S = 3/2 ground Theoretical studies are consistent with the experimental data and suggest that the S = 3/2 state arises from the antiferromagnetic coupling of [NO]- (S = 1) and high spin Fe"' (S = 5/2).EXAFS studies of the Fe" active site of isopenicillin N synthase from Cephalosporiurn acrernonium indicate four or five N/O-donor ligands at 2.15A of which two or three are likely to be his ti dine^.^^." In the substrate bound complex there is evidence for an Fe-S interaction at 2.34 A which has been shown not to arise from endogenous cysteine coordination.The reaction of 0 with the Fe" complex [(6)] + has been studied as a model for the r-keto acid dependent Fe" active sites of some hydro~ylases.~~ The bound 2-keto acid ligand appears to be oxidatively decarboxylated with the production of an oxidizing equivalent which can be efficiently trapped (75%) in the presence of a suitable substrate. The mononuclear Fe" and Fe"' complexes of a tetradentate (imidazole) ligand have been studied both in the solid state and in solution and are proposed as models for the iron site of soybean lipoxygenase.'" The reactivity of mononuclear Fe"' biosites which display dioxygenase 66 T.Egawa. H. Miki T. Ogura R. Makino Y. Ishirnura. and T. Kitagawa. FERS Leir. 1992 305. 206. 67 H. Fujii and K. Ichikawa Inory. Chrm.. 1992. 31. 11 10. K. R. Rodgers R. A. Reed Y.O. Su and T.G. Spiro. Inory. Chrm.. 1992 31. 2688. 69 S. O~awa,Y. Watanabe and 1. Morishirna Inory. Chrm.. 1992 31 4042. '"D. Mandon R. Weiss K. Jayaraj A. Gold. J. Terner E. Bill and A. X. Trautwein. Imwy. Chem.. 1992.31 4404. 71 K. Yamaguchi Y. Watanabe. and I. Morishima. Inorq. Chrm. 1992. 31. 156. i2 K. Yamaguchi Y. Watanabe and I. Morishirna J. Chem. Soc. Chrm. Commun.. 1992 1709. E. I. Solomon and Y. Zhang. AN. Chem. Res.. 1992 25 343. i4 S. Konetschny-Rapp G. Jung K. IS.Raymond J. Meiwes and H. Zihner.J. Am. Chem. Soc.. 1992 114 2224. " Y. Zhang M.A. Pavlosky C. A. Brown T. E. Westre B. Hedrnan K.O. Hodgson. and E. I. Solomon J. Am. Chrm. Soc. 1992 114. 9189. 76 R. A. Scott. S. Wang. M. K. Eidsness A. Kriauciunas C. A. Frolik and V.J. Chen Biochemisrry 1992,31 4596. '' A.M. Orville. V.J. Chen A. Kriauciunas. M. R. Harpel B.G. Fox E. Munck. and J. D. Lipscomb Biochemistry 1992 31 4602. 78 Y.-M. Chiou and L. Que. Jr.. J. Am. Chem. Soc.. 1992. 114 7567. " E. Mulliez G. Guillot-Edelheit. P. Leduc J. C. Chottard C. Bois. A. Bousseksou. and W. Nitschke New J. Chem. 1992 16. 435. '3 Bioinorganic Chemistry 501 activity has been investigated by the study of model Co"' complexes enabling the isolation and characterization of possible intermediates." The superoxide dismutase activity of an Fe" complex with an N donor set has also been investigated." The general properties of the dinuclear iron metalloproteins haemerythrin (Hr) ribonucleotide reductase (RR) purple acid phosphatases (PAPS) and methane monooxygenase (MMO) 4*82,83 and the chemical insights into these biological systems provided by the many characterized dinuclear iron model complexes,84 have been reviewed.In their oxidized forms all these proteins contain the [Fe"'(p-O)Fe"']4 + core and ab initio calculations hake been used to probe the structural dependence of the magnetic coupling between the two Fe'" centres.8s The magnetic susceptibility "Fe Mossbauer and ESR properties of a range of mixed valence Fe"/Fe"' model compounds and an Fe"/Fe" complex have also been The redox behaviour of RR from Escherichia colt has been reviewed," and the structure and reactivity of a model compound for the reduced Fe"/Fe" form of the biosite has been rep~rted.'~ Replacement of Fe" with Co" in the PAP uteroferrin yields the catalytically active Fe"'Co" form 'H NMR studies of which confirm the presence of imidazole and phenolate ligands and provide definitive evidence for carboxylate coordinati~n.~~ A model complex for the oxidized form of PAP with phenolate coordination of a dinuclear Fe"' core has also been reported." HO S.Nakashima. H. Ohya-Nishiguchi. N. Hirota S.Tsuboyama. and T. Chijimatsu. Bull. Chem. Sot,. Jpn. 1992 65,1225. ni L. luliano. J. Z. Pedersen A.Ghiselli D. Pratico G. Rotilio. and F. Violi Arch. Biochem. Biophj.s. 1997 293. 153. n2 J. B. Vincent G. L. Olivier-Lilley and H.A. Averill. Chem. Rev. 1990 90 1447. 83 R.G. Wilkins Chem. Soc. Rev. 1992 21. 171. nJ D.M. Kurtz Jr. Chem. Rut.. 1990 90.585. 85 J. R. Hart A. K. Rappe S.M. Gorun and T. H. Upton. Inory. Chetn. 1992 31 5254. nh M. S. Mashuta R. J. Webb. J. K. McCusker. E.A. Schmitt. K.J. Oberhausen. J. F. Richardson R. M. Ruchanan and D. N. Hendrickson J. Am. Chem. Sue. 1992 114 3815. 87 K.S. Hagen and R. Lachicotte J. Am. Chrm. Soc. 1992 114 8741. xx M. Fontecave. P. Nordlund H. Eklund and P. Reichard. Ah. Enzymol. Rular. Areas Mol. Biol..1992,65. 147. nv S. Menage. Y. Zang. M. P. Hendrich. and L. Que Jr. J. Am. C11rrn.Sue.1992 114 7786. YO R.C. Hob L. Que Jr. and L.-J. Ming. J. Am. Chem. Soc. 1992 114. 4434. 41 A. Neves. S.M. D. Erthal V. Drago. K Griesar and W. Haase. lnory. Chim. kta 1992. 197. 121. 502 J. D. Crane The structure of the hydroxylase component of MMO from Methylosinus trichos- poriurn is unknown. However chemical modification of the protein indicates that two histidines are coordinated to the dinuclear iron centre and suggests that a cysteine residue may also be close to the active site.92 ENDOR studies of the Fe"/Fe"' form indicate the coordination of at least one histidine to each iron site and addition of the inhibitor Me,SO appears to result in the loss of the Fe"-histidine intera~tion.~~ MMO is known to catalyse the oxidation of benzene to phenol; and resonance Raman studies of the coordination of phenol to the Fe"'/Fe"' form provide evidence for an exogenous phenolate ligand at the active site as well as indicating that the biosite may be similar in structure to the PAP ~teroferrin.~~ Dinuclear iron MMO model complexes which oxidize alkanes in the presence of 0 have been ~repared.~',~~ Ethene is a plant growth regulator and is known to be produced from 1-aminocyclopropanecarboxylic acid (ACC).However the mechanism of this reaction is unknown. Interestingly dinuclear Fe"' complexes react with H,O to yield a species which promotes the production of ethene from ACC.97 The catalase activity of a dinuclear iron model complex has also been reported.98 The oxidation of Fe" by apoferritin for subsequent incorporation into the Fe"' core has been followed spectroscopically and the initial product appears to be an [Fe"'(p-O)Fe"1]4+ complex similar in structure to the oxidized form of RR.5399 Model compounds for Fe"'/O aggregation of relevance for understanding iron biomineraliz- ation and ferritin core formation have also been reported."' The structure reactivity and spectroscopy of the different types of iron/sulfur centre found in metalloproteins have been re~iewed.~.' The structure of the rubredoxin from Desulfouibrio uulgaris has been refined to a resolution of 1.O 8 and most of the protein atoms have been resolved as discrete peaks in the electron density maps.' O2 'H NMR studies of the '3Cd substituted rubredoxin from Pyrococcus furiosus provide strong evidence for NH .. . S hydrogen bonding at the Fe" site,lo3 and hydrogen bonding has also been identified in a model compound with relevant peptide ligand~.''~The synthesis and properties of a range of oxidized rubredoxin model compounds of general formula [Fe"'(SR),]-(R = Me Et Pr' Bu' CH,Ph CHMePh Ph) have been rep~rted.''~ The Fe"/Fe" Fe"/Fe"' and Fe"'/Fe"' oxidation states of the [2Fe-2S] clusters in the aldehyde oxido-reductase from Desulfouibrio gigas have been probed by 'Fe 92 D.D. S. Smith and H. Dalton Eur. J. Biochem. 1992 210,629. 93 M.P. Hendrich B. G. Fox,K.K. Anderson P.G. Debrunner and J. D. Lipscomb J. Biol. Chem. 1992 267 261. 94 K. K. Anderson T. E. Elgren L. Que Jr. and J. D. Lipscomb J. Am. Chem. Soc. 1992 114 871 1.95 V. S.Belova A. M.Khenkin V.N. Postnov V. E. Prusakov A. E. Shilov and M. L. Stepanova Mendeleec Commun. 1992 7. 96 A. M. Khenkin and M.L. Stepanova Mendeleev Commun. 1992 57. 97 Y. Nishida T. Akamatsu T. Ishii and Y. Oda J. Chem. Soc. Chem. Commun. 1992 496. 98 Y. Nishida M. Nasu and T. Akarnatsu 2.Naturforsch.. Teil B 1992. 47 115. 99 A. Treffry J. Hirzrnann S.J. Yewdall and P. M. Harrison FEES Lett. 1992 302 108. loo K.S. Hagen. Angew. Chem. Int. Ed. Engl. 1992 31 1010. Adv. Inorg. Chem. 1992 38. Z. Dauter L.C. Sieker and K. S. Wilson Acta Cry~tallogr. Sect. B 1992 48 42. '03 P.R. Blake J.B. Park M.W.W. Adarns and M.F.Summers J. Am. Chrm. Soc. 1992 114 4931. lo4 N. Ueyarna W.-Y. Sun and A. Nakamura Inorg. Chem. 1992 31. 4053. 105 L.E. Maelia M. Millar and S. A. Koch Inory. Chem. 1992. 31 4594. Bioinorganic Chemistry 503 Mossbauer spectroscopy. '06 The fully oxidized enzyme exhibits a single quadrupole doublet (AE = 0.62 mm s-' 6 == 0.27 mm s-') typical of Fe"' whereas the fully reduced form gives two signals (AE = 3.42 2.93 mm s-') indicating the presence of two different types of [2Fe-2S] cluster in the enzyme. Resonance Raman and magnetic circular dichroism studies of three [2Fe-2S] clusters have been used to identify diagnostic spectroscopic fingerprints for the identification of these structures. 'O7 The Fe-S stretching modes could be assigned and D,O substitution revealed little if any hydrogen bonding to the iron-coordinating cysteine ligands. The redox chemistry of the [2Fe-2S] isoferredoxins Fd I and Fd I1 has been reported,"* as have the spectroscopic properties of a series of [2Fe-2S] model compounds coordinated with N/S N/N or N/O-donor bidentate ligands.' O9 The reaction kinetics for the reduction of the inactive [3Fe4S] form of beef-heart aconitase with [S,04]2- to yield the active [4Fe4S] form have been reported 'lo and the reverse (oxidative) process has been characterized for the model compound [Fe4S4(SR)4]2-(R = 2,4,6-Pr',C6H,).' ' ' Electrodes coated with films containing electroactive [4Fe-4S] clusters have been prepared by the electropolymerization of cysteine-substituted pyrroles.''' The putative [6Fe-6S] cluster from Desulfovihrio vulgaris has been studied by ESR and 57Fe Mossbauer spectroscopy in its four accessible oxidation states and the proposed structure is an electron delocalized [4Fe] core flanked at opposite sites by two 'ionic' iron centres with some N-donor coordination.' ' A [6Fe] cluster has also been characterized in a protein extraction from Desulfovihrio desulfuricans and contains one high-spin Fe" site with some N/O-donor coordination and five Fe"' sites; three of the last show parameters characteristic of the tetrahedral S coordination found in the smaller clusters.' l4 6 Cobalt The photochemical reactions of derivatives of vitamin B, and cobalamin B, coenzymes have been reviewed.' l5 In addition many new models for cobalamins have been reported including the Costa-type chloro-complex [(7)] and the analogous + + lariat methyl complex [(S)] which has a Co-Me distance of 2.05(2) A.' 16,' l7 Similar compounds with the sterically more demanding adamantyl ligand have longer Co-C(adamanty1) distances of 2.129(3) and 2.217(7) 8 for the trans-ligands H,O and B.A. S. Barata J. Liang I. Moura J. LeGall J. J. G. Moura. and B. H. Huynh Eur. J. Biochem. 1992,204. 773. 107 W. Fu P. M. Drozdzewski. M. D. Dacies S.G. Sligar and M. K. Johnson J. Bid. Chem.. 1992. 267 15 502. E. Lloyd N. P. Tomkinson and A.G. Sykes J. Chem. Soc. Dalton Trans. 1992 753. lo9 P. Beardwood and J. F. Gibson J. Chum Soc. Dalton Trans. 1992 2457. 'lo H.-Y. Zhang K.Y. Faridoon. and A.G. Sykes. Inorg. Chim. Actu 1992 201. 239. E. K. H. Roth and J. Jordanov. Inorg. Chem. 1992 31 240. 112 C. J.Pickett K.S. Ryder and J.-C. Moutet J. Chem. Soc.. Chem. Commun. 1992. 694. A. J. Pierik W. R. Hagen W. R. Dunham and R. H. Sands Eur. J. Biochem. 1992 206 705. 'I4 1. Moura. P.Tavares J. J.G. Moura N. Ravi. B. H. Huynh. M. Y.Liu and J. LeGal1,J. Biol. Chem. 1992 267 4489. 'Is B. Kraeutler Coord. Chem. Rec.. 1992 ill. 215. 'Ih A. Gerli and L. G. Marzilli Inorg. Chem. 1992. 31 1152. A. Gerli M. Sabat and L.G. Marzilli J. Am. Chem. Soc. 1992. 114 671 1. 504 J D. Crane PPh,Et respectively. ' The structurally characterized pendant alkyl Co"' complex [(9)]' is generated by the addition of strained alkenes (e.g. norbornene) to the Co" compound (10) in the presence of 0 at 0°C.119At higher temperatures dich- loromethane solutions of [(9)] + readily eliminate norbornene with the production of the Co"' complex [(lo)] + .The site specific and almost quantitative oxidative cleavage of a C-N bond of spermine bound to Co"' has been reported and the proposed mechanism may be of relevance for understanding the roles of metal centres in amine oxidase enzymes. 12* c1 Me H :-0 H "0 7 Nickel The ESR and redox properties of the hydrogenase from Desulfouihrio vulgaris suggest the presence of a [Ni-3Fe] biosite very similar in structureI2 * to the hydrogenase from Desulfuoihriu gigas. 57Fe Mossbauer and ESR studies show that the nickel centre in the [NiFeSe] hydrogenase from Desulfotjihrio baculatus is diamagnetic Ni" (low spin S = 0) and in combination with EXAFS data indicate that the nickel is five- coordinate.'22 EXAFS studies of the [NiFeS] biosite of the carbon monoxide 118 S.Geremia L. Randaccio. E. Zangrando and L. Antolini J. Orgunornet. Chcm. 1992. 425 131. P. Kofod P. Moore N. W. Alcock. and H. J. Clase J. Chrrn. Soc. Chern. Cornrnun. 1992 1261. 120 M. Yashiro. T. Mori M. Sekiguchi. S. Yoshikawa and S. Shiraishi. J. Chern. Soc. Chern. Cornrnun.. 1992. 1167. 121 M. Asso B. Guigliarelli. T. Yagi and P. Bertrand. Biochirn. Biophps. Acru 1992. 1122. 50. lZ2 c.-P. Wang. R.Franco J. J. G. Moura 1. Moura and E. P. Day J. Biol. Chern. 1992. 267. 7378. Bioinorgaizic Chemistry dehydrogenase from Rhodospirillum rubrum show that the nickel is coordinated by two S-donor ligands at 2.23 A and two or three N/O-donor ligands at 1.87A.123Neither these values nor the second-shell data are consistent with a [Ni-3Fe4S] cubane cluster and the proposed structure is an isolated nickel centre with N/O-donor coordination linked to one or two [4Fe4S] clusters through cysteine or S2-bridges.The nickel carbon monoxide dehydrogenase from Clostridium therrnoaceticum catalyses the reversible oxidation of CO to CO, as well as acetyl coenzyme A (Ac-CoA) synthesis and the CO/Ac-CoA exchange reaction. Extraction of the labile nickel with phen results in loss of only the synthase and exchange activities suggesting that it is the substrate binding site for the Ac-CoA reactions.124 The Ni" complex (11) can be readily reduced or oxidized to the Ni' or Ni"' analogues and the ESR properties and reactivities of these systems indicate that they are useful models for nickel hydrogenase biosites.l2 The nickel thiolate complexes [(RS)Ni"(p- ~ + SR),Ni"(SR)] (R = 2,4,5-Pr\C6H,) and [(l 2)12 have been structurally character- 126.1 2 7 Together with other potential model compounds with N/S-donor ligands they indicate the variety of structures that may be present at these as yet poorly understood biosites.128 130 Me The Nil octaethylbacteriochlorin anion [( 13)] is a good model for factor F-430 a ~~ nickel corphin from methanogenic bacteria which is believed to play a key role in the hydrogenolysis of Me-S and Me-halogen bonds. G. 0.Tan S.A. Ensign. S.Ciurli. M. J. Scott. B. Hedrnan R. H. Holm. P. W. Ludden Z. R. Korszun P. J. Stephens.and K.O. Hodgson Proc.. Nutl. Ad. Sci. USA. 1992. 89 4427. W. Shin and P. A. Lindahl J. Am. Chern. Soc. 1992 114 9718. N. Baidya M. M. Olrnstead and P. K. Mascharak J. Am. Chem. Soc.. 1992. 114. 9666. IZh A. Silver and M. Millar J. Chrm. Soc.. Chem. Commun. 1992 948. G. J. Colpas R. 0. Day and M. J. Maroney Inorg. Chem.. 1992 31 5053. D. Sellrnann H. Schillinger F. Knoch. and M. Moll Inory. Chim. Acta. 1992 19S200 351. I29 M. Mikuriya M. Handa,S. Shigernatsu S. Funaki. F.Adachi,and H. Okawa Bull. Chem. Soc. Jpn.. 1992 65. 512. '"' T. Yarnamura and H. Arai Bull. Chem. Soc. Jpn. 1992 65. 1799. 13' M. C. Helvenston and C. E. Castro J. Am. Chem. Soc. 1992. 114. 8490. 506 J. D. Crane 8 Copper The molecular and electronic structure the reactivities of mono- and dinuclear copper sites in metal lop rote in^,^.'^^.'^^ and the relevance of the wide variety of model compounds that have been synthesized' 34 have been reviewed.Spectroscopic studies of the stoichiometry of Cut binding to mammalian metal- lothionein indicate that six copper ions bind to each of the 2-and fi-domains and that nine and eleven cysteines respectively are involved in metal c~ordination.'~~ The pH dependence of the Cu"/Cu' reduction potentials for a range of plastocyanins and azurins have been determined.'36*'37 Although the absolute values vary the azurins all display a similar pH dependence; e.g.,over the pH range 5.0-8.0 the potential for the azurin from Pseudomonas aeruginosa shifts from +349mV to +292mV (us SHE).Theoretical calculations have been used to characterize the bonding between the Cu" centre and the axial methionine ligand found in structurally characterized plas- tocyanins and a~urins.'~~ Despite the long Cu-S(methionine) distance of 2.90 8 found in poplar plastocyanin this interaction is calculated to have a bond strength -30% of a 'normal' copper-ligand bond. Several Cu" complexes have been synthesized as potential plastocyanin/azurin model compounds.' 39.140 In particular the complexes with N,S imidazole/thioether donor sets display Cu"/Cu' potentials in the range +250 to +360 mV (us SHE).14' The structurally characterized complex [Cu"(SC,F,)L] (L = [HB{3,5-Pr\pz),]-) has been proposed as a structural and spectroscopic model for the Cu"/thiolate interaction found in the oxidized forms of these biosites.'42 ESR studies of reduced copper amine oxidases indicate that the substrate binds to the 6-hydroxydopamine radical cofactor and that the role of the copper site is to '" E.I.Solomon M. J. Baldwin and M. D. Lowery Chem. Rec.. 1992 92 521. "' E.T. Adman. Curr. Opin. Struct. Bid. 1992 1 895. L34 N. Kitajima Adv. Inorg. Chem. 1992 39 1. Y.-J. Li and U. Weser Inorg. Chem. 1992 31 5526. 136 F. N. Biichi A. M. Bond R. Codd L. N. Huq and H. C. Freeman Inory. Chem. 1992 31 5007. 137 C. Strong St. Clair W. R. Ellis Jr.. and H. B. Gray Inorg. Chim. Acta 1992. 191 149. ''' M. D. Lowery and E. I. Solomon Inorg. Chim. Acta. 1992 19g200 233. 13' H. Masuda T. Sugimori T. Kohzuma A.Odani and 0.Yamauchi BulL. Chem. Soc. Jpn. 1992,65,786. I4O R. P.F. Kanters R. Yu and A.W. Addison. Inory. Chim. Acta 1992 196 97. 141 M. F. Cabral J. de 0.Cabral E. Rouwman W. L. Driessen J. Reedijk U. Turpeinen and R. Hamalainen Inorg. Chim. Acta 1992 196 137. 14' N. Kitajima K. Fujisawa M. Tanaka and Y. Moro-oka J. Am. Chem. Soc. 1992. 114 9232. Bioinorganic Chemistry mediate the regeneration of this radi~al.'~~.'~~ A model compound for this site [( 14)] +,in which a 6-hydroxydopamine molecule is directly coordinated to a Cu" ion has been prepared and shown to catalyse the aerobic oxidation of PhCH,NH to PhCHO.145 The Cu" site of phenylalanine hydroyxlase from Chromohacteritrm OH violuceum has been shown by EXAFS studies to be coordinated by two histidines and two other N/O-donor ligands (probably H,O and/or [HOl-) similar to the copper sites in amine 0~idases.l~~ However EXAFS of the reduced Cu' form are consistent with two histidines at 1.90A and a single S-donor or C1- ligand at 2.20 A.The Cu" nitrosyl complex [Cu"(NO)L] (L =. [HB(3-Butpz),] -) reversibly binds NO and has been proposed as a potential model for the putative NO generating mononuclear copper site in the nitrite reductase from Achromobacter cycloclastes. 47 The crystal structure of yeast copper/zinc superoxide dismutase (SOD) has been refined to 2.5 8 resolution and the coordination of the metal centres is conserved with respect to bovine SOD; the Cu" site is distorted square-based pyramidal with a histidine bridge to the distorted tetrahedral Zn" site.14* The structure of Co" substituted semisynthetic bovine erythrocyte copper/cobalt SOD has also been determined to 2.0 resol~tion.'~"The temperature dependence of the Cu"/Cu' reduction potential of bovine SOD reveals a large negative enthalpy change upon reduction as a result of reorganization of the copper site to stabilize Cu'.' 50 Together with the inaccessibility of the active site this is proposed to explain the high specificity of the site for the superoxide ion 0;.The electrochemistry of several SODS and relevant mutants has been reported.15' Human SOD is found to have a slightly higher potential (+ 360 mV us SHE at pH 7.4) than bovine SOD (+ 320 mV) and the Co" substituted bovine enzyme displays very similar properties to the Zn" form.Signifi- 143 J. McCracken J. Peisach C. E. Cote M. A. McGuirl and D. M. Dooley. J. Am. Chem. So(,.,1992 114. 3715. I44 J. Z. Pedersen S. El-Sherbini A. Finazzi-Agrb and G. Rotilio Biochemistry. 1992 31 8. 14' N. Nakamura T. Kohzuma. H. Kuma and S. Suzuki J. Am. Chem. Soc. 1992 114. 6550. 146 N. J. Blackburn R. W. Strange R. T. Carr. and S. J. Benkovic Biochemistry. 1992 31. 5298. 14' S. M. Carrier C. E. Ruggiero. W. B. Tolnian and G. B. Jameson. J. Am. Chem. Sot,. 1992 114. 4407. 14H K. Djinovic G. Gatti A. Coda L. Antolini. G. Pelosi A. Desideri M. Falconi F. Marm0cchi.G. Rotilio. and M. Bolognesi J. Mol. Biol.. 1992 225 791. 149 K.Djinovic. A. Coda L. Antolini G. Pelosi A. Desideri M. Falconi. G. Rotilio and M.Bolognesi J. Mol. Biol. 1992 226 227. 150 C. Strong St. Clair H. B. Gray. and J. S. Valentine Inorq. Chem. 1992. 31. 925. 15' H. A. Azab L. Banci M. Borsari C. Luchinat. M. Sola and M. S. Viezzoli Inorq. Chem. 1992.31,4649. 508 J. D.Crane cantly more negative potentials are observed for the N; (-220mV at pH 7.3) and CN-(-590 mV at pH 10.2) inhibited enzymes consistent with the ability of these ions to coordinate and stabilize the Cu" centre. The binding of CN to bovine copper/zinc ~ SOD has been followed by IR and Raman spectroscopy and the Cu" site is observed to ~ bind a single end-on CN ligand (vCN = 2 137 cm -').'52 Two-dimensional 'H NMR has been used to identify almost all of the imidazole protons of the coordinated histidine residues in Ni" substituted bovine SOD.*53 Systematic replacement of the coordinating histidine residues of SOD with cysteine results in the formation of stable all-copper SOD mutants one of which has a similar electronic absorption spectrum (i,,, = 458 and 597 nm) to the mononuclear copper centre in nitrite reductase.' 54 An imidazole-bridged model compound for copper/zinc SOD has also been reported.Is' There are two good structural candidates for the binding of 0,at the active site of the dinuclear Cu' oxygen transport protein haemocyanin; p-q2 :v2-[0J2 (15) or ~ p-1,2-[O,l2-(16) where the second bridging ligand X is probably OH-. With both Cu' sites substituted with Co" the haemocyanin from Lirnulus polyphernus has been shown to bind 0 to form structure (16),although the relevance of this observation to copper haemocyanin chemistry is limited.15' The reaction of [Cu'L] (L = [HB(3,5-Pripz)3] -) with 0 yields the dinuclear oxyhaemocyanin model compound [LCu"(p- 0,)Cu"LI which has structure (15) and has been shown to liberate 0 in the presence of CO yielding [Cu'(CO)L].' 57 HlS His The reaction of copper complexes with 0 in the presence of suitable substrates has been investigated as a potential functional model for the many oxidative processes mediated by copper proteins; e.g.the dinuclear copper enzyme tyrosinase (mono- oxygenase activity).' 58 A series of electrochemically generated Cu' model complexes of dinucleating ligands has been shown generally to exhibit much greater reactivity towards 0 than the corresponding mononuclear systems.' 59 Dinuclear Cu' model complexes which undergo intramolecular aromatic hydroxylation in the presence of 02,160.161 and thermally stable dinuclear Cu" complexes with 02-and OOH- bridging ligands have been prepared.'62 Other systems that hydroxylate aliphatic 152 J. Han N. J. Blackburn. and T. M. Loehr. Znorq. Chem.. 1992. 31 3223. 153 I. Rertini C. Luchinat L.-J. Ming. M. Piccioli. M. Sola. and J. S.Valentine Inorq. Chern. 1992 31,4433. 154 Y. Lu. E. B. Gralla J.A. Roe and J.S. Valentine J. Am. Chem. Soc.. 1992 114. 3560. 15q Z. Mao D. Chen. W. Tang K. Yu and L. Liu Polyhedron. 1992. 11 191. I56 J. A. Larrabee T. F. Baumann S. J. Chisdes and T.J. Lyons Inorg. Chem.. 1992. 31. 3630. 157 N.Kitajima K. Fujisawa C. Fujimoto. Y. Moro-oka S. Hashimoto T. Kitagawa K. Toriumi K. Tatsumi. and A. Nakamura J. Am. Chem. SOL... 1992. 114. 1277. 158 J. Balla T. Kiss and R. F. Jameson Znorq. Chem. 1992. 31. 58. I50 Y. Nishida. I. Watanabe. and K. Unoura. 2. Noturfhrsch.. Teil R. 1992 47 109. 160 M.S. Nasir B.I. Cohen and K. D. Karlin J. Am. Chem. Soc. 1992. 114 2482. Ihl J. Ling A. Farooq K. D. Karlin. T. M. Loehr and J. Sanders- Loehr. Inorg. Chrrn. 1992 31 2552. 162 M. Mahroof-Tahir. N.N.Murthy. K. D. Karlin N. J. Blackburn. S.N. Shaikh. and J. Zubieta Inorg. Chem.. 1992 31. 3001. Bioinorganic Chemistry C-H bonds,'63 and catalyse the oxidation of phenol and hydroquinone substrates have also been reported.' 64 The structure of the blue oxidase protein ascorbate oxidase has been refined at 1.908 resolution and found to contain a mononuclear copper centre very similar in structure to plastocyanin as well as a trinuclear copper cluster which is the putative 0 binding site.' 65 This cluster is coordinated by eight histidine residues from the protein and has the triangular structure shown in Figure 1.A similar structure is believed to be present in laccase which has been studied by ESR and magnetic circular dichroism.' 66 '68 CUI-CU~ = 3.68 A Cu1-Cu3 = 3.78 A CUZ-CU~= 3.66 A Figure 1 Structure of the trinuclear copper(ii) .site of o.uitiized uscorhate osidasr 9 Zinc The biochemistry of zinc enzymes and storage proteins'"" and the role of zinc biosites as Lewis acid catalysts' 70 have been reviewed.Theoretical calculations have been used to rationalize the effect of metal substitution (Zn" Co" Mn" Cd") on the metal coordination environment and the proton affinity of metal bound OH- at the active site of the zinc enzyme carbonic anhydrase."' Only substitution with Co" yields an enzyme with activity comparable to the native zinc form and multinuclear NMR has been used to investigate the binding of anions at the metal centre of both the Zn" and Co" form^."^ The binding of amide inhibitors to Ni" substituted carbonic anhydrase has also been studied by 'H NMR and UV/vis ~pectroscopy."~ The carbonic anhydrase model complex [Zn"(OH)L] (L = [HB(3-But-5-Mepz),] -) reacts revers- ibly with CO to yield [Zn"(OCO,H)L] which has been isolated as the C0:- bridged complex [LZn'l(p-CO,)Zn"L].' 74 The complex [Zn"(NCS),L] (L = [12]aneN,) has 163 E.Amadei. E. H. Alilou F. Eydoux. M. Pierrot. M. Reglier. and B. Waegell. J. Chem. So(,..Chem. Cornmuti. 1992. 1782. I64 D. A. Rockclife and A. E. Martell J. Chem. Soc. Chew. Commun.. 1992. 1758. 165 A. Messerschmidt R. Ladenstein R. Huber M. Bolognesi. L. Avigliano. R. Petruzzelli A. Rossi and A. Finazzi-Agro. J. Mol. Bid. 1992. 224. 17Y. 1 hb J.-B. Li D. R. McMillin. and W. E. Antholine. J. iim. Chern. Soc,. 1992. 114. 725. I67 P. A. Clark and E. I. Solomon J. Am. Chtrm. Soc. 1992 114. 1108. I6H J. Lu C.J. Bender. J. McCracken. J. Peisach J. C. Severns. and D. R. McMillin Riochernisrry 1992. 31 6265. I hY J. E.Coleman Annu. Rep. Biochem. 1992. 61. 897. 170 J. Suh Acc. Chem. Res.. 1992 25. 273. 1'1 D. R. Garmer and M. Krauss. J. Am. Chem. Soc,.. 1992. 114 6487. 172 I. Bertini C. Luchinat. R. Pierattelli and A. J. Vila. Inory. Clirrn.. 1992 31. 3975. 173 J. M. Moratal M. J. Martinez-Ferrer. H. R. Jimenez. A. Donaire. J. Castells. and J. Salgado. J. Inory. Biochem. 1992. 45. 231. 172 A. Looney. G. Parkin. R. Alsfasser. M. Ruf. and H. Vahrenkamp. .4nqen. Chem.. Inti. Ed. Enql.. 1992.31. 92. 510 J. D. Crane been structurally characterized and proposed as a potential model for the four/five- coordinate geometry conversion at the zinc centre in carbonic anhydrase.' 75 The metal environments of native Zn" and Co" substituted carboxypeptidase A in their solution and crystalline forms have been studied by EXAFS and shown to be structurally very similar; four-coordinate with two histidines one glutamate and one water molecule as well as a fifth long interaction of -2.35 8 to the second oxygen of the glutamate ligand.'76 EXAFS has also been used to study the zinc sites in the alkaline phosphatase from Escherichia coli,and indicates that site A has two imidazole ligands and four other 0-donors at an average distance of 2.04 A.' 77 Site B lies -3.9 8 away and metal binding at this second site does not appear to affect the metal environment at site A.The complex [Zn"(OH)L] (L = [HB{3,5-Pr\pz},]-) has been shown to display alkaline phosphatase activity hydrolyzing OP(OC,H,NO,) to yield a mixture of the complexes (17) and (18).' 78 Mononuclear and dinuclear zinc complexes have also been structurally characterized and proposed as potential model compounds for the dinuclear zinc biosites in phospholipase C and leucine aminopep- tida~e.'~~ (L)Zn"-EXAFS studies of the two zinc sites in the RNA polymerase from E.coli have shown that the tightly bound zinc has four S-donor ligands at 2.368 and two N/O-donor ligands at 2.23 A and the weakly bound zinc has five S-donor ligands at 2.38 8 and a histidine at 2.148,..l8' The binding of Ag' ions to rabbit liver zinc metallothionine in which the zinc is tetrahedrally coordinated by thiolate residues has been followed by circular dichroism spectroscopy.'81 The structures of zinc finger proteins in which the zinc centres are tetrahedrally coordinated by two histidine and two cysteine residues have been structurally investigated by high resolution 'H NMR.'82,'83 '15 E.Kimura T. Koike M. Shionoya and M. Shiro Chem. Lett. 1992. 787. 176 K. Zhang B. Chance D. S. Auld K.S. Larsen and B. L. Vallee Biochemistry 1992 31 1159. 177 S. Mangani P. Carloni M. S. Viezzoli and J. E. Coleman Inorg. Chim. Acta 1992 191 161. 17* S. Hikichi M. Tanaka Y. Moro-oka. and N. Kitajima J. Chem. SOC.,Chem. Commun. 1992. 814. 179 P. Chaudhuri C. Stockheim K. Wieghardt W. Deck R. Gregorzik. H. Vahrenkamp. B. Nuber and J. Weiss Inorg. Chem. 1992. 31 1451. F. Y.-H. Wu W.-J. Huang R. B. Sinclair and L. Powers J. Bid. Chem. 1992 267,25 560. 18' A. J. Zelazowski and M.J. Stillman Inorg. Chem.1992 31 3363. J.G. Omichinski G.M. Clore M. Robien K. Sakaguchi E. Appella and A.M. Gronenborn Biochemistry 1992 31 3907. R. J. Mortishire-Smith M. S. Lee L. Bolinger and P. E. Wright FEBS Left.. 1992 296 1 I. Bioinoryanic Chemistry 511 10 Molybdenum and Tungsten Biosites and the Nitrogenases The structure and biochemistry of pterin molybdenum cofactors in molybdenum enzymes has been reviewed.' 84 The oxotransferase systems catalyse two-electron transfer reactions involving exchange of an oxygen between water and the substrate (Scheme I) and this reactivity has been demonstrated for the model complex [MO~'(O),(SP~)T~'].'~~ Transfer of an oxygen atom to PPh yields [Mo"(O)-(SPh)Tp'] which can reform the starting material either through oxygen extraction from Me,SO or through two one-electron transfer reactions.With the same ligand the complex [Mov'(0)(S)(q '-SP(S)Pr;)Tp'] (19) has been structurally characterized and proposed as a model for the putative [MO"'(O)(S)]~' site in xanthine oxidase.'86 0 Other potential model compounds for both this enzyme and sulfite oxidase with mononuclear [Mo"'(O),]~' or [Mo'"(0)l2 + centres coordinated with S and S2N2 donor sets have been re~0rted.l~~ -'89 The preferred mode of coordination of the substrate xanthine molecule to the molybdenum centre in xanthine oxidase has been inferred to be through N9 and not N7 by the study of structurally characterized Cu" and Zn" model compounds (Scheme 1).l9' EXAFS studies of the tungsten centre in aldehyde-ferredoxin oxidoreductase from Pyrococcusfuriosus indicate a chemical environment consisting of two 0x0 groups at 1.74& three S-donor ligands at 2.31 A and possibly a sixth N/O-donor ligand at 2.1 These observations suggest an octahedral [WV'(O),l2' site rather than a [WFeS] cluster.The structure and function of the molybdenum vanadium and all-iron nitro- gena~es,~, '92-1 94 the wide range of potentially relevant model and the reactivity of the coordinated N molecule in model compounds' 96 have been reviewed. 184 K. V. Rajagopalan and J. L. Johnson J. Biol. Chem.. 1992 267 10 199. I85 Z. Xiao C.G. Young J. H. Enemark and A.G. Wedd J. Am. Chem. Soc. 1992 114. 9194. 186 A. A. Eagle L.J. Laughlin C. J. Young and E. R.T. Tiekink. J. Am. Chem. Soc.1992. 114 9195. I87 D. Sellmann. F. Grasser F. Knoch. and M. Moll Z. Naturforsch.. Teil B 1992 47 61. I8H S. Sarkar and S. K. Das Proc. Indian Acid. Sci. Chem. Sci. 1992. 104 437. I89 P. R. Traill A. G. Wedd and E. R.T. Tiekink Ausf. J. Chem. 1992 45 1933. 190 E. Dubler G. Hanggi and H. Schmalle Inorg. Chem. 1992 31 3728. 191 G. N. George R.C. Prince S. Mukund and M. W. W. Adams J. Am. Chem. Soc. 1992 114. 3521. 192 B.K. Burgess Chem. Rev. 1990 90,1377. 193 B. E. Smith and R. R. Eady Eur. J. Biochem. 1992 205 1. 194 'Biological Nitrogen Fixation' ed. G. S. Stacey R. H. Burris and H. J. Evans Chapman and Hall New York 1992. 195 D. Coucouvanis Acc. Chem. Res. 1991 24 1. 1 Yh G. J. Leigh Ace. Chem. Res. 1992 25 177. 512 J.D.Crane 0 0 [MO~(O)(OH)]~' Scheme I Catalytic cyclejiw the reactirity of'molyhdenum osotrun~f&ruses with sunt hinr shown as a representatice substrate This field has recently been revolutionalized by the determination of the structure of the molydenum nitrogenase from Azotohacter ziinelandii at 2.7 A resolution.' 97.1 98 Based on this X-ray study combined with data from other techniques the proposed structure for the Mo/Fe cluster is a [4Fe-3S] cluster linked to a [Mo-3Fe-3S] cluster by two cysteine residues and a third bridge X with lower electron density probably an N/O-donor ligand (Figure 2). The remarkable features of this structure include the lack of an obvious N binding site at molybdenum and the presence of six trigonal planar S or S,X coordinated iron centres and only one 'normal's coordinated iron centre.The structure of the unusual P clusters is equally interesting with two closely bridged [4Fe4S] clusters (Figure 3). The oxidized form of the P clusters from several molydenum nitrogenase enzymes have also been studied by ESR and 57Fe Mossbauer spectroscopy. 199 (X= NO-donor ligand) Figure 2 Proposed structure ,fkw the uctiw site of the FeMo-cofhctor of' rzitrogrnusr lY' M. M. Georgiadis. H. Komiya. P. Chakrabarti. D. Woo. J. J. Kornuc. and D. C. Rees Science. 1992,257 1653. J. Kim and D.C. Rees. S~%wce.1992. 257. 1677. lYy K. K. Surerus. M. P. Hendrich. P. D. Christie. D. Rottgardt W. H.Orme-Johnson and E. Miinck J. Am. Chem. Soc. 1992. 114 8579. Bioinorganic Chemistry Figure 3 Proposed structure jiv the utirrsuul P-clusters oj nitrogenuse Upon reaction with dry HBr one atom of the two coordinated N molecules in the vanadium nitrogenase model compound [Na(thf)][trans-V(N,),(dmpe),] was con- verted to NH and a trace ofNH,NH, but no H was detected.200 The S,O:-reduced form of the all-iron nitrogenase from Rhodohacter capsulatus has been studied by ESR spectroscopy,201 and a series of iron complexes (20)of a pentadentate NS ligand have been prepared and proposed as potential models for an iron N binding site in these ni trogenases.202 (20) X =CO,NO NH3 NH2NH2 D.Rehder C. Woitha W. Priebsch. and H. Gailus J. Ckrrn. Soc,.,Chrm. Cornmun. 1992. 364. 2"1 A. Muller. K. Schneider K. Kniirtel and W.R. Hagen. FEBS Left.. 1992. 303. 36. D. Sellmann W. Soglowek F. Knoch G. Ritter. and J. Dengler. lnory. Chrni.. 1992. 31. 371 1.
ISSN:0260-1818
DOI:10.1039/IC9928900495
出版商:RSC
年代:1992
数据来源: RSC
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Author index |
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Annual Reports Section "A" (Inorganic Chemistry),
Volume 89,
Issue 1,
1992,
Page 515-567
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摘要:
Author Index Aakeroy. C.B. 170 Aakesson R. 200 Abaouz A,. 423 Abarzhi S.I.. 433 Abbas. S. 75. 160 Abbas T. 443 Abbott A.P. 490 Abboud K.A.. 354 366 367 Abdalian. A.T. 438 Abdi. S.H.R. 285 Abdul-Sada A.K. 38 Abe K.. 437 Abe. T. 438 444 Abe Y. 172 289 Abed Ali Miah M.. 301 Abel E.W.. 222 274 Abel. G.. 2,32 Abeln D. 197 Aboukais. A,. 199 Aboukhassib. A,. 5 Abraham. M.M. 446 447 Abrahams. B.F. 148 Abrahamson. H.B.. 378 Abramkin. E.V.. 88 Abrams. D.N. 460 Abril. A.A. 379 Abruna H.D. 276 Abuhijleh A.L.. 202 Abu-Raqabah A,. 197 Achar. S.. 105 Acharya. S.A.. 467 Achiba. Y.. 34 36. 246 404 449 Achiwa. K. 21 1 Ackerman. J.F.. 424 Ackermann L. 385 Adachi F.194 294 505 Adachi. G.,244. 255. 256 333 Adachi H.. 394 Adachi S. 395 398 399 400 Adachi. 1..33 I. 332 Adachi Y. 441 Adam K.R. 183 339 Adam L.C.. 481 Adam. M.. 258 Adam M.J. 464 467 Adams C.J. 384 Adams E.W..461 Adams G.B..41 Adams. H. 344 354 Adams. H.R.. 464 Adams. M.R. 372 Akashi H. 133 Adams. M.W.W. 502. 51 I Akermark. B.. 366 Adams. P.A.. 488 Akiba. K.. 72. 469 Adams. R.D.. 219 237 382 386 Akimitsu J.. 402 39 1 Akio. Y.. 436 Adcock J.L. 39 86 Akita. M. 361 373 Addison A.W. 275 297 506 Akrivos. P. 195 196 Adelmann P.. 406 41 I Akselrud. L.G.,250. 412 Adelt S.,381 Akulov G.P. 460 Adeyemi S.A. 417 .Akutagawa S. 270 Adhikary. B.. 309 AI-Ahmad S.A. 123. 191 Adloff. J.P. 459 Alam.I.. 32 Adman E.T.. 506 Alario-Franco. M.A. 414 Adolfsson H.. 273 Alavi. A,. 465 Adroja D.T.. 425 Alba. M.. 442. 447 Aeberscild M.. 449 Albano V.G.. 57 205. 234 303. Aeppli. G. 425 440 374. 385 Afarinkia K.. 221 Alberti. G.. 114 ARleck. I.. 431. 436 Albertin. G.. 218 Afonas'sva T.V. 263 Alberto K.. 31 I 456 Aggarwal A.K.. 71 Albertsen J. 49 Aggarwal. R.P. 372 Albertsson J. 178 Agladze K.I.. 481 Albinati. A. 177 Agosta. C.C. 451 Albrecht-Gary A.-M.. 349. 489 Agostinzlli E. 442 Alcala. M. 114 346 Agrawal. J.P. 232 Alcock. N.W.. 8 27. 54. 74 110. Aguiari. A. 330 113 234. 245. 268 312. 313 Aguilar- Parrilla. F.. 142 331. 332. 342. 504 Aguilo. M.. 201 Aldenhoven H.. 47 Aguinaga. S.. 55 Al-Dulaymmi M.F.M. 305 Ahamdme.H.. I13 Alekel T.. 41 5 Aharony A.. 432 Aleksandrov K.S.. 401 Aherne C. 83 Alemany. P.. 57 Ahlrichs R. 20. 55. 195 Aleonard S. 247 423 Ahmed K.J.. 23. 137 Alexoff. D.L.,454 Ahmed. L.. 21 Alford. M.J.. 36 246 261 Ahmed. S.N. 34 Alford N.M. 241 Ahrland. S. 244 Alfredsson V.. 178 Ahsen. V.. 294 Ali H.. 467 Aida. T. 499 Ali. S.A.. 465 Aime S 250. 319 Alibrandi. G.. 485 Ainscough. E.W.. 280 Aliev. R.R.. 482 Aissi C.F. 199 Alilou. E.H.. 509 Aitchison. A.A. 136 Al-Juaid. S.S.. 48 Ajayan. P.M.. 41 Allcock. H.R. 93. 95 96 97 Ajiro Y ,435. 436.439 Allemand. P.-M. 39 449 Ajo. D.. 224. 295 Allen K.D.. 119 Akabori S. 333 Allison J.. 191 Akaboshi. M. 468 Almador. U.. 414 Akamatsu T.. 170 306 502 Almanjano. M.P.. 78.314 515 516 Almarsson O. 38 Almond M.J. 169 Al-Nasr A.K.A. 48 Alonso A. 469 Alonso J. 440 Alonso P.J. 365 Alpoim M.C.. 250 Alsfasser. R. 509 Alshetiri. S.. 490 Alsina T. 91 Al-Taweel S.M.. 61 Althoff U. 62 Alul R. 301 Alvarez M.M.. 34. 36 38 246 Alvarez R. 142 Alvarez S. 57 204 380. 448 Alyea E.C. 148 Amadei E. 509 Amandelli R.. 109 Amano. R. 471 Amatore C.. 165 227 Amaya K. 436 Ambe S. 456 Amberger H.-D.. 254. 258 Amerikova E.V. 442 Amilaprasadh Norbert. W.D.J.. 267 Aminov. T.G. 442 Amoretti. G.. 447 Amorim M.T.S. 333 Amoros P. 433 Amouyal. E. 274 Amputch M.S.A. 181 Anand. D.. 468 Anbang D. 305 Andersen. A.F. 199 Andersen P.483 Andersen R.A.. 112 120 Anderson. A. 77 Anderson B.A. 13 Anderson. D.M.. 256 Anderson G.K. 391 Anderson J.E.. 212 292 Anderson K.A.. 480 Anderson M.T. 41 1 Anderson O.P.. 79. 207. 21 7 240. 499 Anderson R.A. 214 Anderson. S.L. 38 Anderson. G.. 94 Andersson. K.K. 502 Andersson. L.A. 180 Anderson M. 397 Anderson Y. 461 Andjelkovic K. I74 Ando. I. 95 342 Ando K.. 442 Ando. W. 48. 49. 81 Ando. Y .. 36. 245 Andre. J.-J.. 204. 448 Andrei O. 220 Andreoni. W. 36 Andrews L.. 38. 58 81 Anelli P.L. 250 Ang H.G. 71 219 Angadi. M.A. 241 Angaroni M.. 205 Angel. R.J. 30 Angelberger. P. 466 Angelici R.J.. 62. 147. 216. 359 Angelis B. 466 Angelov. S. 436 Anianiec B.C.234 Anjiki A,. 295 Ankers D.L. 185 289 Anma M. 397 Annan. T.A. 25 Annibale G.. 485 Anren. K. 457 Ansari M.A. 79. 80. 84 133 197 241 Ansari M.S. 467 Anselme G.. 44 Anson C.E.. 171 449 Antholine W.E. 279. 509 Antipin. M.Yu. 63 259 Antolini. L.. 504. 507 Antolovich. M. 183 339 Antoni. G.. 461 Antoniutti. S.. 218 Antropiusova H.. 115 Antui-Nsaih. F.. 376 Anwander. R.. 257 253 270 Anuolabehere E. 475 Anrai H. 451 Aoki. H.. 451 Aoki. K.. 31 Aota. H.. 451 Aoyama. T. 174 200 Aoyama Y.. 428 Apblett A.W.. 48 Apeloig Y.. 43 Apostolidis C. 258. 263. 264 Appella. E.. 510 Appelquist. (3..459 Appleton. T.G. 233. 236 Ara I.. I67 Arafa. E.A.. 337 Aragb.J.. 344 Aragon R. 443 Arai. H.. 179 505 Arai M.. 428 435 Arai. S.. 253 Arai T. 253 327 491 Araki. K.. 267 Arana. C. 276 Aranda. M.A.G. 434 Arano Y. 465 Arapkoske. S.K.. 171. 449 Ararsingham. R.D. 478 Aratono. Y. 458 Arher. J.M.. 118. 496 Arbosgast. J.W. 38 Archer. C.M. 68. 163 164 272. 294 Archer. R.D.. 289 Archer. R.G. 11 1 Alehibald R.S.. 43 Author Index Ardizzoia. G.A. 197. 205 Argazzi R.. 475 Arias C.. 477 Arienti. M.T. 248 Arif. A.M.. 237 356. 358 492 Arion. V.B.. 285 Aristov. Yu.1.. 230 Arko A.J. 397 Armaroli N.. 274 Armatage. A,. 167 Armstead. I.P.. 463 Armstrong. A.R.. 29. 401. 412 Armstrong D.R. 45 Armstrong R.L.. 481 Armstrong.W.H. 118 161 162 206 276 296 299 306 448 497 Arnaiz F.J.. 27 Arnason. I.. 44 Arndsten B.A.. 69 Arney D.S.J. 264 Arnold. F.P.. 57 Arnold. J.. 50 1 11. I 13. 332 Arpac E.. 113 Arriortua. M.I.. 202. 276. 277 Arshinova. R.P.. 65 Artelt H.M.. 247 Arts A.F.M.. 442 Arulsamy N. 207 301 448 Asai. K. 306 Asano H.. 398 400. 402 Asano K. 323 Asano T. 133 Ashe. A.J.. 111. 14. 61 Asher S.A. 498 Ashmawy F.M. 185 Askew E.F.. 369 493 Aslanidis. P.. 195 Aslanov L.A.. 128 248 Aspinall H.C. 254 Assinder. D.J. 470 Assink. R.A. 38 Asso. M. 504 Astruc. D.. 35 1. 490 Asuke T. 98 Atagi L.M. 355 Atcher. R.W. 468. 471 Ates M. 61 Athas G.J. 451 Atherton. S.J.. 475 Atkins.A.J.. 176 Atkinson. I.M.. 174 Atkinson N. 207. 342 Atnip. E.V.. 195 Attanasio. D. 77. 224 Attfield. J.P.. 434. 444 Attlield. M.P.. 414 Attini. M. 20 Attwood J.L.. 269 Atwood D.A.. 25. 66. 70 71 Atuood J.D. 480 491 Atwood. J.L.. 75. 45. 142 159 202 Atwood. V.O.,25 Author Index Atyovmyan L.O.. 108 Aubang D.. 204 Auhry A.. 195 Aubuchon S.A. 489 Audebert P. 289 Audeef. A, 292 Auerman L.N.. 256 Auger N. 162 497 Auld D.S.. 510 Auner. N.. 144 Aurang7eb. N.. 161 289 Austin E.J.W.. 233 Austin. R.N. 182 Avent A.G.. 39 43 Averbuch-Pouchot. M.T.. 417 Averill. B.A.. 80 501 Avrgliano I<..509 Aviles G. 498 Auaga. K.. 451 Awate S.V. 29 Awere.E.G.. 58 83 Ayache. C.. 396 Ayad. M.M.. 202 Ayala. J.D. 245 Azab H.A.. 507 ALirni S.. 28 Arnar. R.. 34 Amma. M.. 399 Amma. N.. 62 Baaciocchi. E. 109 Baha. K.. 332 Baha. Y. 210 Babasaki. M.. 207. 488 Babecki. R. 248 Babel D.. 200. 423. 434. 439 Bahich J.W.. 455 Bahin. P.. 48 Babu T.G.N.. 401 Bacher. A.-D.. 54 Bachich. S.. 469 Bachrnan R.E.. 174 Bachrnann. B.. 354 Badding. M.E. 421 Bader. A,. 127 Baek H.K. 478 Baensch B.. 476 Biir. E.. 142 Baerends. E.J 162 432. 449. 497 Biiuerle D.. 397 Bag. N. 269 Baghdadi. J. 221. 365 Bagyinka C. 191 Bahar. I.. 95 Bahr S.R. 48 Bai. J.. 16 Baichtock Yu.K. 209 Baidya. N.. 79. 192. 505 Bailey. A.J..233 Bailey N.A. 221 340. 344 354 365 Bailey. P.J.. 382. 385 Baines. K.M. 42 Baird. M.C. 362 371. 492 Ba-l~sa,A.A. 202 Bajaj. H.C. 492 Bajul. L.J.. 397 Bakae. A,. 317 322. 328. 477 478. 490 Bakalbassis E. 202. 207. 291. 308 448 Bakei- A.D. 283 Baker. C.L.. 197 Bakei- J.M.. 446 Baker. L.J. 239 Baker P.K. 8. 140. 331 Baker. R.T.. 13 Bakir. M. 166 Bakkaloglu O.F.. 444 Bakker. K. 425 Bakker. W.I.I.. 455 Balahan A.T.. 3 Balagopalakrishna C.. 202 Balahura. R.J.. 477 Balakrishna. M.S.. 70 Balasubramanian. K. 57 455 Balasubramanian S. 498 Balcar. E.. 432 Balch. A.L.. 40. 180 223. 387 478 Balcom B.J. 490 Baldas J.. 164 Balduin. D.S.. 183. 339 Balduin. M.J..204. 506 Balduin. R.M.. 467 Balegroune. F.. 366 Bali P.K.. 488 Ball. I1.W.. 195 Ball. G.E. 40. 217. 362 Ball P. 33 Balla J.. 508 Ballester. L.. 449 Bal Reddy. K.. 479 Balseiro. C. 429 Balt S. 491 Balzani V. 274. 28 I 283 Bambcr. M.. 391 Bampos. N.. 176 Banci. L. 507 Banda S.F.. 160 Bandirii. A.L.. 271 Banditelli. G. 271 Bando. Y . 399 Bandoli. G.. 163. 186. 291 318 466 Bandy. J.A. 134 Bandyopadhyay. A.K.. 6 388 Bandyopadhyay. D. 454. 493 Banerjee. T.. 269 Bang. E. 143 Bang. H.. 492 Banister. A.J.. 58. 83 Banks. R.E.. 85 Banks W.A.. 462 Bansenier R.L.. 197 Banyunes. S.A.. 356 Bar. M.R.. 195 Baraff G.A.. 404 Baran E.J.. 87 Baran P.. 201 289 Barata B.A.S..503 Barbara B.. 440 Barbara. P.F.. 475 Barber. D.C.. 488 Barbey. L.. 407 41 1 Bard A.J. 37 Bar-Eli K.. 482 Barichivich. B.A.. 181 Barigelletti. F.. 283 Barkigia K.M.. 180. 182. 498 Barnes. C.L.. 166 Barnes D.L.. 113 Barney G.S.. 454 Barnham. K.J.. 233 Barnhart. A.J.. 465 Barnhart T.M. 361 Barni E.. 213 Barra. A,-L.. 125. 126. 449 Barre. L.. 462 Barrera. J. 218 Barreto. R.D.. 12 Barrett S.E.. 405 Barrie P.J.. 233 Barrio. J.R.. 464 Barrios. A.. 490 Barron. A.R.. 24. 26. 48 Bartels. D.M.. 480 Barth. H.. 457 Barth. S.. 63 Barthelemy P.P. 250 Bartholomew. J.. 480 Bartlett. N. 215 423 Bartlett. R.A.. 19. 20 Bartlett. R.J.. 68 Barton D.H.R.90 171 Barton. J.K. 213 269 270 Barton L.. 5 198 Barton R.J.. 148 Bartos. B.. 470 Bartsch R.. 66. 67 Barude. V.. 43 Barzoukas M.. 269 Bashall A.P. 74. 128. 183. 339 Bashkin J.S.. 162 497 Baskey J.H. 445 Basolo. F.. 356 492 Basset J.M.. 116 215 222 223 413 Bassetti. M.. 480 Basson. S.S.. 166 Bassoul. P.. 269 Bastian H.. 65 Bastida. R.. 110. 294 Bastin B. 466 Basto. M.. 202 Bastos. M.A.V.. 455 Basu. P. 159. 271 Basu. S. 456 Batail. P.. 178 207. 308. 448 Batchelor. R.J.. 178. 387 Bateman. D.M.. 463 518 Batista A.A. 301 496 Batlle X. 439 440 444 Batlogg B.. 395 Batrd. G. 279 Battaglia L.P.. 54. 200 291 448 Battioni P. 182 Battle. P.D. 413.414 444 445 Baturin N.A.,264 Baudler M.. 46 47 59 60 146 Baudry D.,264 265 Bauer B. 463 Bauhofer W.. 244 247 Baum R.M.. 33 Baumann T.F.. 508 Baumegger A, 44 Baumeister. U. 372 Baumgartner F. 3 1 1 471 Baur W.H. 413 Bausch J.W.,4 Bauschlicher C.W..246 Bautista. M.T.,370 Bayon J.C.,291. 448 Bazan G.C.,246 Bazhan. A.N. 433 Beachley O.T.. 24 Beagley. B. 75. 160 Beales T.P. 399 Beard A.M. 468 Beardwood. P. 79. 190 271 503 Beaty. J.A.,486 Beauchamp. A.L.,239 Becalska. A, 178 Beccalli E.M. 197. 205 Becher J.. 342 Beck H.P. 246 Beck M.T.. 482 Beck W. 358 Becker. B. 196 Becker G. 50. 71 Becker J.A.. 450 Becker M. 34 Beckett M.A. 3 8 140 Beckhaus H.-D..35 Beckrnan H.L..377 378 Bedworth P.V.,34 Beer P.D..239.283. 342. 348 Beer R.H..477 Beeth R.J. 124 Beger J. 163 Begley M.J.,54 71 Beguin A,. 215 Begun G.M. 261 Behrn. J. 30 68 Behrendt. A, 67 Behrens U.. 53 54 61 121 Beille J. 440 Bejarano M. 476 Beklroglu O. 294 Bekman I.N.. 470 Belaiche M. 436 Belakova M. 466 Belanger. D.P.,432 Belkhira M.S.. 199. 416 Bell A.T..29 Bell. M.N.. 314 Bell P.. 377 Bell T.W.. 88 340. 365 Bellachioma G. 480 Bellitto. C.. 433 438 Bellouard C.. 443 Belluco U. 210 Belohradsky. M. 334 Belomestnova N.V.,454 Belov. K.P. 442 Belova. V.S.. 502 Belsky. V.K. 7 183 200 204 259 336 348 Belton. P.S.. 84. 236 Beltriii A..200. 205 303 Beltrin. D.. 151. 200. 205. 303 Beltranporter. A,. 433 Beltranporter D. 433 Belyakova E.G.. 469 Benard. M. 41. 107 115. 167 Bencini. A, 160 191. 339 344 347 Bender B.R. 217 Bender. C.J..509 Bendrup U.. 422 Benelli C. 448 Benetollo F.. 248. 295 Benlield R.E.,97 Benhamada L. 417 Benjarvongkulchai S. 477 Benkovic. S.J.,507 Benmoussa A, 41 7 Bennani. A, 199 Benncini A, 80 Bennetau. B.. 48 Bennett D.W.. 201 Bennett F.R. 24 Bennett. M.A.. 362 Bennett. P.J..468 Benning P.J. 405 Renninghoven A.. 179 Bensch. W.. 32 109 Bensebaa F. 204 448 Bensimon C.. 112. 327 336 343 369 Benson C.G. 468 Bentley G.W. 354 Benvenuto. M.A. 18 Beoku-Betts. D.474 Beratan. D.N..474 Berback K.A. 339 Bercaw J.E.. 68. 246 352 Berces J. 460 Berdonosov S.S. 108 Berg B.A.. 433 Bergens. S.H.,220 Bergerat. P.. 202. 207 308. 434. 448 Berglund. K.A. 223 Bergman R.G.,210. 214 224 225. 35 I. 364. 480 Bergstrasser U. 63 Bergstrorn P.-A.. 248 Author index Beringhelli T. 384 387 Berke. H. 140 200. 358 Berlinsky. A.J.. 430 Berrnejo M.R.. 27 161 174 289 Bernal I. 43 174. 200 Bernard. J.. 479 Bernardinelli. G.. 195. 196. 275. 284. 299 Bernardo M.M.. 78 Berneo. S.. 79 Berners-Price. S.J.. 196. 23 1. 486 Bernes. S.. 127 197 Bernhard P.. 348 Bernhardt P.V. 204 273 285. 305 321. 322 Bernier P.. 34 Bernstein S.N.. 167 Bernu. B. 430 Berreau.L.M.. 477 Berridge. M.S.,459 Berry A,. 54 139 Berry. F.J.. 199 442 444 Berry. J.M..467 Bertagnoli. H.. 147. 3S0 Bertani R. 210 Berthet. J.-C.,264 Berthon. R.A. 278 Bertini I. 109 192. 318. 495 508 509 Bertolasi. V.. 164 292 Bertriii J. 176 Bertrand. P. 504 Bertsch-Frank. B.. 75 Beruda H. 44. 374 Berzolla. P.G. 291 Bessel C.A.. 275 Besser. S. 87 Bessonov. A.A. 263 264 Bestari K. 83 Beswick. M.A. 385 Betchaku A.. 332 Bethune. D.S. 36 245 Bettonville S. 265 Betts J.N. 474 Beurskens. G. 78 370 Beurskens. P.T.. 78 370. 389 Beuter G.. 389 Beviere S.D. 171 Beydoun N. 113 Bhadbhade. M.. 74. 213 Bhagat S.M.,442 Bharadwaj? P.K.. 174 176 203. 304. 347 Bhardwaj C..213 Bhardwaj R.C.,213 Bhargava. K.K.. 467 Bharpava S. 110 Bhatia. P.K..203 Bhatt S. 285 Bhattacharjee. M. 120 Bhattacharjee. S. 281 Bhattacharya S.,81 172. 448 Bhattacharyya D.K..456 Bhattacharyya N.K.. 55. 380 Author 1izdes Bhattacharyya. R.. 81. 153. 281 Bhuniya. D.. 276 Bhyrappa. P.. 34 Biagini-Cingi. M.. 202 Bianchi. A,. 344. 347 Bianchi. M. 380 Bianchini C. 27. 177 178. 214. 359. 365 Bianconi P.A.. 118. 253 Bickelhaupt. F.. 67 Bida G. 196 463. 464 Bidell. W.. 200 Bieganowski. R.. 182 Bierbach U.. 191 Bigler P.. 218 Bigner. D.D.. 467 Bignozzi. C.A.. 318. 475 Bigoli F.. 207 Bilinski. H 28 Bill E.. 180 186. 189. 289 315. 448,499.500 Bill. J. 19 Billinghurst. M.W. 460 Billings. J.. 465 Billups W.E.. 35 Binder. H. 20 Binger. P.. 63 Bino. A.. 152. 162. 171 189. 497 bin Shawkataly O. 389 Binstead. R.A.. 213 477 Birca. M.S.. 285 Birgeneau. R.J.. 440 Birkel. M.. 63 Birkett P.R.. 39 Bischoff. C.J.. 147 Bishop. A,. 454 464 Bisi Castellani. C.. 250 Bissinger P.. 31 44. 241 Biswas. R.K.. I14 Bitterer. F. 381 Bizhong. L. 456 Bizot. D.. 423 441 Bjarnson. A,. 44 Bjelica. L.J. 285 Bjoergvinsson M. 58. 73 82 443 Bkouchc-Waksrnan. I.. 196 Blachnik R.. 58. 83 Blackburn. D.W.. 115 353 Blackburn. N.J.. 204. 306 507 508 Blackman A.G. 162 Blaeuenstein. P. 456. 468 Blaise. A,. 447 Blake A.J.31 78 176 183. 207. 314 331. 338 342 Blake. J.. 240 Blake P.R. 502 Blake R.E.. 216 Blanc. E. 35 Blandarner M.J. 173. 473 Blanski R.L. 48 Blasse. G.. 198 271 Bleaney B.. 446. 447 Bleeke. J.R.. 364 Blessing G..455 Bligh. S.W.A.. 74. 128. 255. 339 Blittersdorf. R. 482 Bloch. I.. 468 Block. E. 153 Blorn. H.P.. 13 Blornberg. M.R.A.. 21 1 Blornquist. J.. 182 Blomqvist. G..462 Blondin G.. 162. 432. 448 497 Blonk. H.L. 78. 370 Blosch L.L.. 354 Blum. P. 417 Blumt. T. 89 Boag. N.M.. 367 Boas. J.F.. 164 Bocarsley. A.B.. 238 Bochkarev. M.N.. 257 258 Bochmann. M.. 3. 79. 116. 488 Bocian D.F.. 326 Bocquet. B.. 196. 275. 284 Bodak. 0.1..250 Bodensieck. U.. 216 Bodner.A.. 110 312 Bbgge. H.. 167 Boeknian F. 227 Boersma. J.. 227 Boese. R. 10. 16. 64. 65 Biittcher. A,. 186 289 Bottcher H.-C.. 215. 372 Bogdanovic S. 68 Bogge H.. 65. 66 Bohanna C.. 359 Bohrn. C. 459 Bohm. T. 56 Bohrn;in O. 227 Bohrnt:. D.K. 36. 38 Bohra. R.. 16 110 113. 196. 236 Boireau. A, 199. 416 423. 434. 439 Bois. C.. 145. 183. 204. 236 285. 303 379 500 Boisson C.. 265 Boitrel B.. 498 Boldt N.J. 499 Boli. L.. 465 Bolinger L. 510 Bolle U.,57 68. 345 Bollen. S.K.,414 444. 445 Bolognesi. M.. 507. 509 Bolos. C. 202 Bolt. R.J. 114 Bolvin. H. 192 Bolzati C.. 163. 318 Bombi G.G., 27. 28 Bombieri. G..248 295 Bornbik. A,. 442 Borninaar E.L. 180. 499 Bonadies A.497 Bonadies. J.A.. 161 278 Bonarnico. M.. 77 269 Bonanm. J.B. 147 Bonardi. M.. 454 Bonasia. P.J.. 50. 333 Boncella. J.M.. 354. 366 Bonchev. P.R. 183 Bond. A.H.. 55. 262 263. 332 Bond. A.M. 506 Bond M.R.. 109. 200. 437 Bond S.P. 194 Bondarova. O.S.. 247 Bone. S.P.. 54 Bonino. C.. 169 Bonivento M.. 485 Bonrnann S. 75 Bonneau. P.R.. 81 Bonnemann. H.. 115 Bonnetot €3.. 5 Bonnot S.. 460. 462 Bonornartini Corradi. A.. 200 437 Bonrath. W.. 366 Bontchev. N.. 415 Bontcheb. P.R.. 233 Bonvoisin. J.. 448 Boorrnan. P.M.. 156 230 Boothe. T.E.. 455 Boothman J . 379 Bordet. P.. 395. 401 Bordignon. E.. 2 1 8 Bordoni. S.. 374 Borel. B.. 417 Borel.M.M.. 416 417. 465 Boricha. A.B. 289 Bormans. G.. 466 Bormett R.W.. 498 Born. I. 461 Boroni. E.. 217 Borras-Almenar. J.J.. 434. 435 449 Borrmann. H.. 63. 69. 215. 423 Borsari. M. 507 Borshch S.. 432 Bortolini. 0..318 Bortz. M. 72 Borzunov. V.U.,I20 Bosch. H.W.. 358. 363 Bose. R.N.. 477. 479 Bosio. L.. 204. 448 Boske. J.. 70 Bosman W.P. 389 Bosnich. B.. 116. 214 220. 288 Bossek. U. 137 448 Bott S.G.. 25. 43. 45. 119. 159. 202 269 Botta M.. 250. 250 319 Bottcher. A.. 186 Bottornley. F.. 389 Bouayad. A.. 207 Boubekeur. K.. 207 308. 448 Boucher J.P. 436 Boucherle. J.X. 451 Boudjouk. P.. 48 Bougault C. 116 Bougon. R. 87 Bouillet. M.N.. 447 Bould. J.. 8 520 Bour.J.J. 389 Bourdarot F.. 447 Bourges. P.. 441 Bourke. G.C.M.. 490 Bousseksou A. 183 192 285. 500 Boutry. 0..364 Bouwman. E. 159. 287. 292. 506 Bovey. F.A..98 Bovia B. 271 Bovill. A.J..202 Bowmaker. G.A.. 195 197. 239 262 Bowser. J.R.. 3 41 Boxer S.G.. 498 Boyd. D.A. 212 Boyd D.L. 180 Boyd P.D.W.,21 162. 242 497 Boyko J.A.,203 Boyle. T.J.,45 113. 259 Braaten 0..199 Brabers V.A.M.,445 Bradley D.C. 120 245 Bradley G.W. 89 Bradley. J.C.,483 Bradshaw J.S.,489 Brady. L.A..373 Brady Moreira F.G.. 433 Braga D. 229. 371. 374 380 382 383 385 Branchini B.R.. 461 Brand H. 11 I Brands L.. 24 56 Brandt P.F.. 103 Brard L. 257 Braterman P.S..173 233 Bratsberg H. 446 Braun. J. 56 147 Braun R. 66 Braunstein P. 386. 387 Bravic. G. 200 Bravo-Zhivotovskii D. 43 Brechbiel M.W.,468 Breckenridge S.M.,381 Breen T.L. 108 Brefort. J.L.. 101 Bregadze V.I. 3 Bregaint. P. 363 Bregola M. 109 Breit B. 63 64 Brel V.K. 88 Breliere C.. 51 Brendler E. 29 Brendsdal. E. 35 Brennan T.D.,419 420,421 Bretran J. 486 Breunig H.J. 54 61 Brewing. R.L..489 Brewer. C.T. 289 297 Brewer G.A.. 182 200 289. 297 Brewer. J.H.,436 Brewer K.J. 281 Briat B. 438 Briceno G.. 404 Bricklenank. N.. 53 Bridson. J.N.,329 341 345 Briere. K.M. 336. 489 Brigaud O. 182 Brigden. L.G.,183 339 Bright. T.A.. 147. 380 Brihaye C.. 455 Brill T.M..436 Bringewski F.. 56 Bringley J.F. 80 Brinkman. G.A.. 458 Brisdon A.K. 21 I Brisdon. B.J. 16 Brisdon. J.N.. 284 Brito. F.. 204 Brito. H.F.,244 Britt. J.. 80 Brittain. H.G.,250 Britten J.F.,45 Britton D.. 115. 353 Brnicevic N. 124 Brockmann H. 182 Brodack J.W.,454. 455. 464 Brodbeck A.. 389 Brodbelt J.. 335 Brodie. A.M.,280 Broemme A.D.D..445 Brommer. P.E.. 425 Brannum. B.. 485 Brook. A.G.. 44 Brookhart. M.. 141. 354 362. 363 480 Brooks J.S.,451 Brooks M.S.S.. 425 Broomhead J.A..234 485 Brorson M. 150 Broschag M. 82. 238 Brotzeller. C. 444 Brouca-Cabarrecq. C. 207 Brough. A.R.. 251 Brown C.A.. 500 Brown. D.A. I13 Brown. D.W. 88 Brown.I.D..420 Brown. J.A.. 292 Brown J.M. 223 234 Brown K.L. 491 Brown P.J.,428 440 Brown P.W.,200 Brown S.J.,295 Brown. S.N. 166 Brown S.R. 443 Brown. T.L..370 371 480. 492 Brown T.M.. 123 Brownlee R.T.C.,195 Bruce A.E. 142 Bruce M.I.. 384. 389 Bruce. M.R.M. 142 Bruchertseifer H. 265 Bruck E. 425 Bruck M.A.. 353 Bruckel. T.,435 Brudvig G.W. 160 192 329. 496.497 Author Index Brucher E.. 308. 312 Bruechle W.. 457 Bruggeller. P 2x8 Bruice T.C. 478. 499 Brunel L.-C. 125. 436 Brunner. H.. 20. 123. 379 Bruno. G.. 204 Brunschwig. H.S..487 Brunvoll J.. 35 Bruque. S. 434 Bruynseraede Y.. 396 Bryan J.C..68. 137. 358 Hu X.. 268. 319 Bucci. C.. 428 Buchanan.B.E.. 269 Buchanan. D.N.E..37. 406 Buchanan. G.W..336 341 343 Buchanan. R.M. 189. 306. 448. 50 1 Buchardt. 0..261 Bucher. E.. 425 Buchgeister. M.. 395 Buchhett O. 466 Buchinskaya. 1.1.. 247 Buchkremer-Hermanns. H.. 247 Buchler J.W.. 11 1. 254 Buchwald. S.L.. 62 Buckingham. D.A..482 Budantseva N.A.,264 Budsky F. 466 Budzelaar. P.H.M.. 229 Budzichowski T.A.. 16 48 Buchi. F.N. 506 Buhl. M.. 4. 10 Bunzli. J.-C..275 Burger H.M. 158. 314 Biirgi H.-B.. 35. 218. 272 Bug. A.L.R. 36 Bugarcic Z.. 485 Bugnon P.. 482 Ruhro W.E.. 136. 253 Bukowskastrzyzewska M.. 448 Bulatov. A.V..242 Bulbulian. S. 456 Bull. D.J. 348 Bullita. E. 330 Bulter W.M.,390 Buluggiu E.207 Bulychev B.M. 7 183 200 204. 259 336 Bumbalova. A.. 466 Buner. B.. 448 Bunte E.-A.. 44 Buntseva I.M.. 470 Bunz U. 40. 21 7 Bunzli J.-C.G.,248 Buonocore E.. 462 Burdett J.K.. 195. 395 Burford. N.. 58 84 Burgess. R.K.. 51 1 Burgess. J.. 173. 473 490 Burgess K. 13. 220 Burgess L.F.. 114 Burgos. A. 461 Author Index Burini. A. 139 Burkart. M.D.. 72 Burke. N.. 275 Burkhardt. B.. 69 Burlet P.. 441. 447 Burns. C.J..262. 263. 264. 389 Burns. I.D. 8 Burns R.C. 159 Buron. J.M.. 469 Burrell. A.K.. 68 358 Burriel. R.. 170 Burrow T.E. 139 Burrows A.D.. 229 Burrow's C.J.. 317 Bursten B.E.. 378 Burwell. D.A.. 114 Burzlaff. H. 124 Buscaglioni L..108 Buscher. T. 470 Buschmann H.-J.,341 Buschmann J.. 88 Buseck. P.R. 33 Busetto. L. 374 Buslaev. Y.A.. 27 Bussereau. I.. 199. 416 Bustilln J.M.. 27 Bustos C. 145 Butcher R.J.. 175 Butenschon. H. 364 Butler A.. 179. 301. 496 Butler H.. 87. 88 Butler I.R. 248 275 281 Butler. IS. 5 Button T.W. 241 Buttrey L.A. 339. 480 Butts. M.D. 225 Butzlaff C. 137 315 448 Buvetskii B.V. 108 Buyers. W.J.L..425. 437 Buzek. P. 89 Buzza. S.. 41 107 Byeon. S.H. 414 Rykov M.A. 199 Byriel K.A. 196 236 311. 337 Byszewski P. 404 Caballero C.R..200 Cabell. M. 460 Cabral. J.de O. 203 292. 506 Cabral M.F.. 203 292. 506 Cacace. F. 20 Cacciapaglia. R.. 314 Caciuffo R. 447 Cadieu.F.J.,426 Cadogan J.I.G.. 221 Caignaert V. 398 407 411 412 Caille A. 431 Cairon Ph.. 462 Calabrese J.C. 13. 33. 39. 114. 176. 21 I. 235 269. 272. 273. 292. 351 Caldarelli J.L. 356 Calderazzo. F. 3 353. 354 Calhorda M.J.. 263 521 Callahan A.P.. 465 Carra P.. 447 Callahan J.H. 36 246 Carrano C.J.,301 Calquhoun. H.M.. 210 Carrasco-Flores B.. 391 Calviou. L.J. 118. 496 Carre. F.. 51 Cambet. A,. 283 Carreiio E.P. 379 Camblor. M.A.. 29 1 15 Carreno. R.. 379 Cameron. J.H. 183 185. 288 Carretas. J.M. 252 325 326 Carrier S.M. 195. 273 507 Camercn. S. 38 Carrillo D.. 73 145 146 Cameron. T.S.. 83 Carroll J.M.. 161. 486 Caminade. A.-M.. 117. 127 Carroll P.. 164. 292 Cammack R.. 190 Carroll P.J.. 10 11.289 421 Camp D. 197 239 Carrondo M.A.A.F.de C.T.. 333 Campagna S. 281. 283 Cartensen T.. 14 Campana L.S. 436 Carter A, 11I 489 Campbell. A.M. 428 Cartier C.. 182 498 Campbell D.K. 429 Carty. A.J.. 213. 379 381. 382 Campbell G.C.. 97 Carugo O. 238. 250 Campbell. G.C.. Jr.. 39 Carvalho A. 263 Campbell. I.A. 432 Carvalho J.F..250 Campbrll. L.A.. 483 Carvalho L.R.F.,248 Campion. B.K. 378 Casabo J. 205. 283. 442 Candy. J.P. 223 Casabo J.F. 78. 314 Caneschi. A,. 448 Casarin. M. 328 Canfi A,. 467 Casciola M. 114 Cannon. R.D.. 171 449.477 Casellato. U.. 84. 166. 330 340 Canny. J. 129 Casey. C.P.. 358 378 Cano. hf.. 273 Cassidy E.H.. 459 Cantinedu R. 455 460 464 Cassidy J.M.. 371 467 Cassidy. S.M.. 241 Canty. A.J.269. 274 Castanheira. 1.. 466 Cao. B.. 247 Casteel W. 212. 215 423 Cao. D.S. 61 Casteleyn. K. 462 Cao G.. 114. 446 Castell. E. 203 Cao R.. 133. 180. 203 Castellano. E.E.. 197 Cao X.W. 395. 446 Castellari. C.. 205 234. 303 Cao. Y.. 457 Castells. J. 509 Capdevielle P. 289 Castillo. B.V.. 181 Capdevila M.. 237 Castillo. J. 21 Caplin. 4.D..241 Castleman. A.W. Jr. 41 107 Caramico D'Auria A,. 436 470 Carassiti V.. 109 Castro. C.E.. 491. 505 Caravalho J.F.,335 Castro I. 201. 204 206. 302 Caravatti P. 156 303 448 Cardaci. G.. 480 Castro R.. 197 Cardin C.. 202 Caswell. L.R.. 32 Carducci. M.D.. 119 Catalano V.J..40 223 Cardwell T.J..343 Catrall. R.W.. 343 Cargill Thompson. A.M.W.. Cattalini. L.. 485 267 274. 300. 305 Caubet A,.205 Carlin. R.L. 170. 200 Caughey. W.S.. 498 Carloni. P.. 510 Caulton. K.G.. 48. 113. 140. Carlsen J.. 34 195. 196. 197 215. 224 253. Carlson. D.. 38 365 Carlson. K.D. 451 Cava R.J. 395. 400. 401. 407 Carlaon. K.E. 464 Cayton R.H.. 133. 375 Carlson. V.A.. 418 Ceccato A.S.. 301 496 Carmichdel. D.. 147 270 Cecconi F.. 160 191. 294 Carmona E.. 142. 143. 273. 3 64 Celik T.. 433 Carnahan. E.M.. 119 353 Cendrowski-Guillaume. S.M. 5 Carney V.J.,351 Ceriotti. A.. 384 Carpenter. J.D.. 420. 421 Cervantes-Lee. F.. 43 Carpenter T.A. 490 Cervilla. A.. 151 Carr. R.T..507 Cesarotti. E. 271 522 Cesljevic. V.I.. 285 Cetinkaya B. 253 Ceulemans A, 41 144 326 Chabach D.. 254 Chacko K.K. 334 Chacon.S.T. 137 374. 377 Chae S.J. 455 Chaffee. K. 358 Chahine. J.-M.E. 279 Chai. Y. 36 246 261 Chaillout C. 401 Chakrabarti P. 512 Chakrabarty D. 79 Chakrabarty P.K. 81 153 464 Chakravarty. A.R. 205 Chakravorty A, 159 180 228. 269 271 301 305. 496 Chalker J.T. 430 Challa G. 280 Chaloner P.A.. 21 1 Chaly T. 454 Chamberlain. R.V.. 444 Chambrette. J.P. 95 Chambron J.-C. 275 349 Chaminade. J.P..422 Champarnaud-Mesjard J.C. 245 Chan C.-W. 285 Chan. M.K. 162 276 306. 497 Chance B. 510 Chandler D. 474 Chandra P. 425 Chandra S.K. 301 496 Chandrasekhar S.. 78 314 316 476 Chang C.A..242 250 335 Chang. C.C.,25 Chang C.K. 180 182 191. 475 498 Chang J.R. 237 Chang R.C.487 Chang S.C.,203 448 Chang. T.-M. 34 Chang Y. 126 Changtian G.. 457 Changying Z. 457 Channing M.A.. 464 Chantrell R.W. 426 Chao I. 34 Chao. S.H.L.. 24 Chaplygin I.L. 396 Chapman. J. 320 Chapman. R.W.. 10 Chardin J. 416 Chardon J.. 417 Charkin O.P..4 245 Charland. J.-P.. 297 336 Charnock. J.M. 171 Charrier C. 66. 67 Chase D.B. 39 Chase H.J. 504 Chase S.J.. 404 Chassaing J.. 423 441 Chasseau D. 200 Chatani. N. 220 Chatlas J. 483 Chattopadhyay S. 228 Chau C.. 113 Chaudhry M.A.. 443 Chaudhuri M.K.. 120 Chaudhuri. P. 448 510 Chaudhuri. S.. 269 Chavasiri. W. 171 Chaves S.. 333 Chayat. R. 152 Che C.-M.. 76 166. 197. 198 218. 236 242. 279 285 287 3 18 476.477 Cheetham A.K.261 419 444 Chemotti. A.R.. Jr. 292 Chen. B. 164 292. 489 Chen B.-L.. 421 Chen C. 445 Chen C.-C. 37 Chen C.A.. 464 Chen. C.H.. 61 Chen C.P. 448 Chen D. 207. 508 Chen G.. 80. 219 Chen G.S. 395 Chen. H. 134 197 Chen J.. 389 Chen J.-D. 158 Chen J.-T.. 365. 367 Chen L.. 345 Chen P.. 133 475 Chen P.C.. 195 Chen. Q. 117. 125. 126 127. 146 Chen. Q.Y .. 428 Chen. S.-J. 135 Chen. T.. 34 Chen V.J.. 500 Chen W.-Q.. 248 259 Chen. X. 72 160 317 Chen X.-M.. 202 Chen Y. 405. 406 443 Chen Y.-C.J. 164 Chen Z.. 89. 346 Chen Z.Y.,30 401 404 Chenavas. J. 401 Cheng. A.. 38 Cheng B.. 181 Cheng C.H.. 213 Cheng C.-Y. 356. 433 Cheng H.-Y..287 Cheng. M.-C.. 166. 236. 285 367 Cheng M.-H. 356 Cheng P. 207 289 448 Cheng Q. 174 Cheng W.. 456 457 Cheng. W.-K.. 218. 287 Cheong S.-W.. 407 Cherkas A.A.. 381 Cherkasov. V.K.. 258 Chern. M.Y. 420 Chern S. 182 Author Index Chernega A.N.,63 Chernov. V.K. 401 Cheung. E. 473 Cheung M.C. 76 Cheung. P.Y.,242 Cheung T.T.P. 87 Chi K.M.. 195 Chi Y.. 390 Chiang L.C. 499 Chiang L.Y.. 38 451 Chiang. M.Y.. 151 253 364. 39 1 Chiba. K. 341 Chibante. L.P.F..39 406 Chiesi-Villa A.. 110. 121 289. 327 Chijimatsu T.. 321. 501 Chin R.M.. 375 Chin T.T.. 354 Ching W.Y.. 427 Chiorboli C. 318 Chiou Y.-M.. 500 Chippindale A.M. 244 Chirakal R..464 Chirico. R.D. 35 Chisdes S.J..508 Chisholm. M.C.. 133 Chisholm M.H.. 48 136. 137. 139 146 374 375. 376. 377. 387 Chisholm-Brause. C. 470 Chiu K.W.. 250 306 Chiumia. G.C.. 301 Chivers T. 77 8 I 83 84 Chmielewski P.J. 289 Cho C.H. 256 Cho. C.K. 173 Cho C.S. 61 Cho S.. 173 Choi M.-G.. 480 Choi. N. 255 339 Choisnet. J.. 413 Chojnacki J.A. 151 Chojnowski J. 94 Choplin A,. 116 Choppin G.R. 244. 250. 454 Choquette. D.M. 23 Chorley. R.W.. 48 Chotalia R.. 176 249 297 298 Chottard. J.C.. 183 285. 500 Chou. J.L.. 448 Chou L. 376 Chou. M.H.. 487 Choudhury. S.B. 180. 305 Chow M.-Y. 206 Chowdhury. S.K. 38 Choy J.-H..412 Christe. K.O. 53 85 86 87 Christen M.232 Christiaens L.. 464 Christian. J.F. 38 Christides C.. 36 Christidis. T.C. 36 Christie. P.D.. 512 Author Index Christie R.M. 314 Christou G. 122 135. 159 162 203 271 287. 449 497 Christou V. 50 113 Christuk C.C. 79 133 197 241 Chu S.S. 80 Chu S.Y.F. 347 Chu T.L. 80 Chubukov A, 429,430 Chudzynska H. 245 ChGj6 R. 498 Chujo Y. 102 Chun B.S. 467 Chun J.S. 256 Chun. K.M.. 376 Chun K.S. 455 Chung. C.-S. 202 Chung M.-K. 376 Church B.R. 416 Churchill M.R. 24 275 480 Chyn J.P. 448 Ciampolini M. 347 Ciani G.. 68 384 385 387 Ciano M. 281 283 Ciliberto E. 265 328 Cingi M.B. 207 Chi R. 164 292 Cioloca L. 466 Ciurli S. 79 191 505 Claasen J.H.428 Claeys E.. 315 Clague M.J.. 496 Claire K.S. 8 Claire P.P.K. 234 250 306 Clanton J.A. 467 Clark C.R. 174 482 Clark D.L.. 137 244 252 263 Clark P.A. 509 Clark R.J.H. 222. 233 Clark T. 212 Clarke A.J. 312 Clarke E.T. 28 Clarke. M.J.. 68 84 163 164 Clarke P. 346 Clarke S.J. 210 441 Clarkson L.M. 31 Clausen K.N. 433 Clearfield A, 197 Cleary. T.P. 23 Cleaver. M.B. 301 Clegg W. 54 55 56 58 91 118 134 146 150 171 237 313 353. 496 Clem R. 468 Cleroux. M.. 381 Cleynhens B. 466 Clin M.. 444 Cloke F.G.N. 256 Clore G.M. 510 Closs G.L. 37 Coan P.S. 195 253 Cobranchi D.P.. 489 Cockayne D.J.H. 35 Coda A. 507 Codd K. 506 Codjovi E. 434 Cody S.H.181 Coe. P.L. 234 Coene M. 462 Coenen H.H.. 462 464 Coey J M.D. 426 427 Cogneau M. 459 Cohan J.S. 226 Cohen B.I.. 197. 508 Cohen H.. 322 478 482. 490 Cohen. M.L.. 403 404 Cohen O. 397 446 Cohen. P. 467 Cohen R.E.. 397 Coichev. N.. 479 Colacio. E. 204 206 207. 437 Colbran S.B.. 272 278 Colcher. D. 468 Coleman J.E.. 509 510 Coleman. P.. 425 Collin J.-P. 285 Collins M.F.. 425 433 Collins. S. 363 Collins S.P. 428 Collins T.J.. 183 326 Collison D. 118 342 496 Collman. J.P. 182 213. 217 Colmanet S.F. 164 Colpas G.J.. 505 Colquhoun. L.A.. 196 Colton R.. 148 Colussi. A.J. 490 Comar. D. 462. 464 Comba. P. 174 204 273 285 305 32 1. 484 Comblin V.. 250 Comerlato.N.M. 47 57 Compton N.A. 56 Comptoii. R.N. 39 Conceicao J. 246 Connellj N.G. 356 372 Connolly J.W. 113 Conrad. D.W. 474 Conradson S.D. 470 Constable. E.C. 174. 176 196 227. 249 274 280 283. 285. 294. 295. 297 298 300 305 Constantinescu. O. 470 Constel N.,404 Conticello V.P. 257 Convery M. 202 Cook C.M. 136. 139. 377 Cooke J.A. 42 Cooks R.G. 38 Coolbaugh M.T.. 38 Cooper .4.S.. 430 Cooper C.E.. 499 Cooper M.J. 428 432 Cooper P.B. 463 Cooper S.R. 159. 269 314 Cooper T.H. 203. 294 488 Copley K.C.B. 242 Coppens. P. 160 Corain. B.. 27 28. 202 Corbett J.D. 109 244 247 Cordes. A.W. 83 84 Cordone. L. 498 Corfitzen. H. 480 Corkill. J.L.. 403 Corma A, 115 Corman.C.R.. 180 Cornebise M. 277 Cornell R.M. 169 Cornman. C.R. 278. 496 Coronado. E. 434. 435 449 Coronado J.M.. 437 Corradi. A.B. 54. 291. 448 Corraine. M.S.. 480 Corrigan J.F. 213. 382 Corriu. R.J.P.. 51 101 Corruccini L.R.. 446 Cortes R.. 202 206 276. 277 Cortes. S. 308 Cortopassi. J.E. 219. 391 Costa. R.. 207 303 448 Costantino LJ.. 114 Costas M. 167 Costello C.E.. 129 Costello M.T. 165 Costes. J.-P.. 204. 206. 287. 437. 448 Cot. u. 113 Cote C.E. 507 Cottam. M.G. 445 Cotton F.A. 109. 118 127. 134 135 136 137 138. 139 155. 158. 167 222 372. 448 Coucouvanis D. 123 191. 51 1 Coudret C. 275 Coughlan S. 11 Coulter. J.Y.. 256 Couret. C.. 44 47 Courter J.H.463 Coussens. B.. 144 Cousson. A,. 171 Coustel. N. 34 Covert K.J. 369. 493 Cowan J.A.. 498 Cowie M. 222 Cowley. A.H.. 25 66 70 71 21 1 Cowley R.A.. 425,437 Cowrie M.. 376 Cox. D.E. 39. 395 406 Cox D.M. 38 Cox. D.N.. 362 Cox M.. 455 Coyle. C.L.. 79 132. 156 Crabtree G.W. 451 Crabtree. R.H.. 160. 165 192. 224 281 329. 357 496 Cragg. P.J.. 340 Cragg. R.H.. 97 Craig D.C.. 278 Crane J.D. 39. 298 Creaven. B.S.. 269 Creegan K. 38 Cremer-Lober B. 87 Crespi V.H., 404 Crespin M. 413 Crespo M.C. 372 Crespo O. 241 Creutz C.. 197. 300 487 Critchlow S.C. 154 355 Crombe;.. D. 466 Cronje S. 379 Crosby R.C. 97 Crosnier M.P. 108. 416 424 Cross A, 481 Crouzel C..460,462 463 Crow J.E. 446 Crowder M.S.. 245 Crowley M.M. 488 Crowte R.J.. 55 116 Cruse R.W. 197 300 Cruywagen. J.J. 129 Csoeregh I. 250 Cucciolito M.E. 366 Cueto S. 203 206 Cukier. R.I. 475 Cukiernik F. 181 Cummins C.C. 110 173 Cummins W.J. 256 339 Cunha M.C.F. 244 Cunningham D. 289 Cupane A,. 498 Curnow O.J. 87 361 363 388 Curtis M.D.. 387. 388 390 Curtis N.F. 321 322 Curtui M. 71 Cusick J. 77 Cypryk M. 96 Cyrot. M.. 440 Cyvin B.N. 35 Cyvin S.J. 35 Czapski G. 490 Czerwinski. K.R. 261. 457 Czjzek M. 247 Czuchajowska J.. 139 Dabbagh G. 405 Dabbousi B.O. 50 332 Dabrowski B. 399 Dadiz. A.C. 317 Dahan F. 204. 287. 448 Dahl J.R.463 Dahl L.F.. 385 Dahl 0..261 Dahl T. 85 Dai. L. 174 Daikh B.E. 491 Dailey G.C. 160. 288 Daizheng L. 297 D’Alfonso G.. 384. 387 Dallinger. R.F. 355 Dalton H.. 502 Damerius R. 88 Damhaut P.. 464 467 Damoense. L.J. 166 Dance l.J.. 77. 107 Dance J.M. 423 Author Index Dando N. 26 DeBoer J.G.. 231 Daniel G.B. 464 467 de Boer J.L. 407 421 Daniels L.M. 118 134 137 de Bolster M.W.G. 491 Daniels M.A.M. 174 274. 29 15 DeBord J.R.D. 69 Danilovic Z. 124 De Bournonville M.B. 423 Dannals R.F. 462 Debrunner P.G. 180 181 502 Danyluk S. 210 Debuyst R. 326 Dapporto P. 344 347 De Cian A,. 11 1 254 451 Dardn J.C. 200 251 378 Deck W.. 510 Darby W.L. 175 Declercq J.P. 64 Darensbourg D.J. 147 149 De Cola L..283 151 195 Dedeaux H.,481 Darensbourg. M.Y.. 185 292 Dedieu. A,. 233. 386 334 Deeming. A.J. 375 Dargatz M.. 55 380 Deeth R.J. 316 356 Darkwa J. 178 De Felici V.,234 Darriet J. 415 422 434 Defotis G.C. 444 Dartyge. E. 182 498 DeFulvio J. 466 Das A, 154 267 Degn P. 269 Das R. 309 329 Degnan I.A. 27 Das S.K. 456. 51 1 de Graaf R.A.G. 204 DasGupta A.K.. 457 De Groff. C. 283 Dasgupta T.P. 485 de Groot. B. 314 Da Silva J.J.R.F. 333 495 de Groot P.A.J. 398 da Silva R.S. 318 Deguchi H. 435 438 Date M. 435 436 Dehai Z. 457 Dauter Z. 502 Deheer. W.A. 450 Dauth J.. 96 Deheng S. 465 David A.. 432 Dehnicke K. 54 68 80 82 83 David G. 70 84. 119. 120. 127 165 336 David V.P. 399 Dehua Y. 466 David. W.I.F.413 443 Dei A.. 448 Davidovich. R.L. 108 De Jaeger R. 95 Davidson M.G. 44 45. 306 Dejehet F. 326 Davies C.E. 79 de Jesus E. 386 Davies G. 197 205 De Jesus J.C.O. 442 Davies J.A. 117 128 DeJesus O.T. 454 464 Davies M.D. 503 DeJonge W.J.M. 437 441 445 Davies S.E. 70 De Kepper P. 481 Davis C.A. 35 Dekker. G.P.C.M. 365 Davis D.D. 98 Dekkers H.P.J.M. 475 Davis. H.B. 387 DeKock C.W. 131 Davis J.D. 306 Delacotte J.-M. 460 Davis J.H. Jr. 18 Delakowitz B. 470 Davis. M.J. 225 de la Rosa R.I. 301 496 Davis W.D. 110 173 de Larrdmendi J.I.R.. 206. 276 Davis W.M. 164 358 277 Davison A, 164. 277 Delavaux-Nicot. B. 264 280 Dawson D.M.. 158 Delcorde A, 468 Day. C.L. 216 Delgado R. 333 Day E.P.. 504 Delica. T. 437 Day P..35. 200 Della Pergola P. 384 Day R.O.. 59 76 505 Dellavia 1.. 109 482 Ddamba W.A.A. 178 Dellert-Ritter M. 479 Deacon G.B.. 72 252 258 del Mar Graciani M. 476 Deady. L.W. 343 Delpon-Lacaze G. 44 de Almeida. S.G. 235 Delpuech J.-J. 277 Dean B. 461 Demarcq M.C. 58 Dean J.C. 445 Demartin F. 57 384 Deane A.M. 469 Demazeau. G.. 412 De Angelis S. 12I 327 Dembowski. B.S. 461 de Barros Faria R. 481 Dernel V.S.J. 23 De Blas A, 110 294 320 Demetrius M.. 224 Deblaton M.. 468 Demkina. 1.1.. 89 Author Index Demou P. 151 De Munno G. 204 DeMuro R.L.. 34 Den T. 398 Dence C.S. 464 Deng D. 259 Deng H. 371 387 Deng R.M.K. 21 Dengel A.C. 90 Dengler J. 193 291 297 513 Denike J.K. 341 Denk M.68 253 270 Denning R.G. 244 Dennis T.J.S. 34 36 38 39 Dennis W.M. 442 Dent A.J. 371 Denti G. 281 de Paulis T. 467 Depero L.E. 248 Deptula Ch. 457 De Roo. M. 466 Derory A. 436 Desai C.N. 455 De Santis G. 238 320 Desbois A. 180 498 Deshayes L. 261 Deshmukh S.M. 456 457 Desideri A. 507 Desmarteau D.D. 239 de Souza A.J.F.,433 Desper J.M. 43 331 Desreuz J.F. 250 Detellier C. 248 336 489 Detsch R. 70 Dettelbacher C. 121 Deutsch E. 163 164 292 484 Deutsch K. 163 484 de Vaal P. 41 107 233 Devadoss C. 40 223 Devi P.S.. 407 DeVinney J.L. 462 463 De Visser. A. 425 Devora G.A. 220 de Vries E.G.E. 210 de Vries M.S. 36 245 de Vries N. 162 Dewar J.C. 284 De Wijn H.W.442 DeYoung J. 85 De Zuane F. 224 D’Halluin G.,95 Dhindsa K.S. 328 Dhingra S. 31 Dhiwar V.I. 455 Dholiya S. 476 Diaddario L.L. Jr. 331 488 Diamond G.M. 352 353 Diaz C. 285 Diaz M.R. 357 Di Bella S. 265 328 Dickens P.G. 244 Di Cola D. 447 Didier P. 301 Didillon B. 223 Diduszko R. 404 Diederich F. 33 34. 35. 38 Dielkus S. 19 Diemer S. 45 Diener. M.D. 36 261 Dietrich A. 252 258 261 Dietrich-Buchecker C. 196 349 489 Dietz J. 80 Dietz M.L. 455 Dietz S.D. 151 Dietzsch W. 32 Digenis G.A. 462 Dikarev E.V. 55 423 Dikshit S.K. 196 Dilbagi K. 248 Dilettato D. 38 Dilley. W.G. 467 Dillon K.B. 21 64 Dilworth J.R. 68 69 163 164. 165 166 219 272 294 DiMaio A.J..31 1 Di Meo J.J. 465 Dineen C. 399 Ding H.J. 460 Ding X.-D. 180 Ding X.-Q. 499 Ding Y. 215 Ding Y S.,464 Ding Z. 448 Dirnberger T. 221 DiSalvo F.J. 118 420 421 Disrnukes G.C. 496 Ditzel E.J.. 8 Di Vaira M.. 312 318 Divisia-Blohorn B. 196 Divjakovik V. 149 Dixneuf P.H. 360 Dixon A.J. 371 492 Dixon D.A. 40. 85 86 Djinovic K. 507 Do Y. 12 Dobbs D.A. 225 Dobbs. F.R. 462 Dobson. C.B.. 492 Dobson. C.M. 139 251 383 Dobson. G.R. 492 Dodgen. H.W. 480 Doring J. 125 126 Doherty N.M. 119 127 151 Doherty S. 213. 379 381 382 Doi. K. 337 Doine H. 172 Dolg M. 257 Doller I]. 171 Dolmella A, 163 Dolnik M. 482 Dolter T.J. 489 Dorn C.459 Dornanov V.P.. 265 Domen K. 124 Domenech A, 344 Dorningos A, 263 Dominguez S. 204 Dorninguez-Vera J.-M. 204 206. 437 Donaire A, 192 509 Donets E.D. 243 Dong N.. 248 Dongare M.K. 114 Donni A,. 445 Dooley. D.M. 507 Door A. 47 Doorn S.K. 475 Dorhout P.K. 37 247 Doring. J. 449 Dormann. J.L. 442 443 Dornberger E. 263 Dorner B. 435 437 Dorokhova. E.M. 460 Dorrity M.R.J.. 347 Dossi. C.. 223 Dsssing A, 483 Dou D.. 16 19 71 Doucet. J.-P. 279 Dougan H. 467 Dougherty G. 202 Douglas P. 73 Douglas W.E. 51 Douki K. 154 Dove M.F.A.. 54 Dovletoglou A, 213. 477 Dowding AS. 221 365 Downard A.J. 277 329 Downard. J. 179 Downey J.W. 397 Downs A.J.10 169 Dowsett. K. 463 Doxsee. K.M. 341 Doyle. M.P. 220 Drabent K. 289 Drabold. D.A. 41 Drager M.. 54. 61 Drago R.S..477 Drago V. 501 Drake S.R. 48 Draper S.M.. 6 388 Dray A.E. 102 Dreczewski B. 16 Dregval T.N. 469 Dresselhaus. M.S. 33 Drew M.G.B.. 8 204. 207 234 340. 342 347 Drews T. 79 170 Drexler. C. 479 Driess. M. 46 47 57 Driessen W.L. 203 204 280 292 297. 506 Drillon M. 205 303 436 451 Drljaca J. 469 Drornzee Y.. 115 202 Drozdov A.A.. 201 Drozdzewski P.M. 503 Drozdzynski. J.. 244 263 Drumheller J.E. 200 437. 448 Dryuchko A.G. 248 Du S.. 133 155 240 Du S.W. 195 Du Y. 130 Duarte M.T.. 333 Duatti A, 164 318 465 466 Dubbert. R.A.362 Dubicki L. 158 Dubler E. 110 312 511 Dubois. D.. 37 Dubois J.-E. 279 Dubost J.-P. 251 Dubourg A, 64 Duc N.H. 425 Ducasse L. 200 Ducau M. 422 Duchateau R.. 112 113 Duckingham D.A. 174 Duckworth P.A. 183 337. 339 Duclos S.J. 404 Ducommun Y. 482 Duczmal M. 446 Diirr H. 269 Duesler E.N. 16 19 71 195 Duff C.M. 288 Duffy N.V. 180 Dufour. P. 222 Dugautier C. 438 Duguet E. 102 Dulebohn. J.I. 153 223 Dumas J.. 226 Dunbar K.R. 135 137 158 167 221 223 Duncalf D.J. 256 Duncan M.A. 240 Dunham W.R. 503 Dunin A.G. 336 Duniun A.G. 183 Dunlap B.E. 499 Dunn B.B.. 462 464 Dunn R.C. 192 299 Dunne B.J.. 372 Dunne S.J. 159 Dunogues J. 48 Dunster K.R.337 Dupont J. 460 du Preez J.G.H. 163 262 Dupuis M. 160 Duran M. 176 197 245 486 Durcanska E. 170 175 Durif A. 417 Durrant M.C. 331 Dusek M. 185 Du Toit L.L.. 250 Dutremez S.. 117 128 Dutt A.K. 481 Dutta N.C. 456 Dutton. P.L. 474 Dvornic P.R. 93 Dworkin A. 192 Dye R.C. 256 Dyer P.W. 355 Dyer R.B. 475 Dyke A.F. 373 Dyke. J.T. 246 Dyson P.J. 382 Dzhemilev. U.M. 24 Eaborn C. 48 Eady R.R. 51 1 Eagle. A.A. 511 Earley J.E.. 481 Eaton G.R. 207 499 Eaton. S.S..207 499 Ebbesen T.W. 37 40 41. 217. 405 Eber. B. 378 Ebert K.H. 54 61 Ebii. S. 439 Ebsworth E.A.V. 79 Eccleston R.S. 425 Echegoyen. L. 36 346 Eckert J. 140. 177 Edelmann F.T. 45 254 262 Edelstein.N. 262. 447 Edema J.J.H. 149 150 327 Ederer B. 16 Ederle H. 16 Edlund U.. 149 Edward. J.B.. 469 Edwards A.J. 74 128. 314. 381 Edwards. C.F.. 75 165. 219 Edwards D.A. 275 Edwards H.G.M. 178 Edwards. J.O. 479 Edwards K.D. 19 Edwards M.. 83 84 Edwards P.G. 55 116 263 Edwards P.P. 29 30 395 401 412 421 Edwards S.D.. 275 Effendy A. 239 Efimova V.L. 460 Efros. L.L. 192. 329 Egan L.A. 461 Egan T.J. 488 Egawa T. 500 Egdell R.G. 397 446 Eger R. 247 Egert E. 158 Eggenkamp P.J.T. 445 Egger M.. 466 Eglin J.L. 127 134 Egorov Yu.V. 469 Ehler D. 262 Ehmann A, 399 Ehmann W.. 20 453 Ehnebohm. L. 250 Ehrenkaufer R.L. 461 464 Ehrhardt G.J. 457 Ehrlich.W. 468 Eichen. Y. 269 Eichhorn D.M. 161 296 Eichhorn E. 185 Eichorn B. 421 Eidsness. M.K. 500 Eilerts N.W.. 151 Eilmes J. 328 Einholz W. 10 Einstein F.W.B. 178 383 387 Author Index Eisen M.S. 265 Eisenhut M.. 466 Eisenstein O. 176 195. 196 374 387 Eklund H. 501 El-Absy M.A. 456 Elander N. 462 463 Elbaum N.C.. 97 Elder S.M. 249 285 Elders J. 109 Elding L.I.. 485 Elemes Y.. 38 Elerman Y. 186 Elgin. J.L.. 222 Elgren T.E.. 502 Elhaes. P.D. 77 El-Hendawy A.M. 90 Elias H. 183. 186 289 319 323 479 487 Elison M.. 166 El Khokh N. 251 Eller. P.G. 470 Ellern A.M. 259 Ellert 0..285 Elliot D.J.. 222 370 379 Elliott C.M. 37 207 283 475 499 Ellis A..174 Ellis D.E. 262 Ellis. J.E. 115 31 I 353 Ellis J.W. 227 Ellis W.R.. Jr. 506 Ellison 1.J.. 221 Elmaleh D.R.. 467 El Mansour A, 223 Elmore P.R. 35 Elmroth S. 485 Elms F.M. 24 El-Ouatib R. 65 El-Sayed M.A. 197. 205 El-Sayrafi O. 160 Elschenbrioch. C. 67 Elschner S. 11 1 Elsevier C.J. 21 1 216 365 El-Sherbini S. 507 El-Toukhy A. 197 Empson R.E. 261 Enderle M. 437 Enders M. 14 Endicott. J.F.. 144 Endo K. 394 465 Endo S. 444 Endoh Y. 428. 435 436. 437 439,440 Enemark J.H. 474 51 I Engbersen J.F.J. 261 Engelke R. 68 Engelskirchen G.. 465 Englert U. 3 10 14 16 354 361 Englich. U. 422 English A.M. 474 Ennis M.S.. 213 Ensign S.A.. 505 Ensling J.189 Author Index Entin-Wohlman O. 432 Ephretikhine M. 244 264. 265 Eppley D.F. 145 Epstein A.J. 451 Epstein I.R.. 481 482 Erasmus-Buhr C.. 301 496 Erata. T. 49 Eriks K. 480 Eriksen J. 143. 486 Eriksen K.A. 132 Eriksson H. 459 Eriksson O. 425 Erker G. 116 Erman L.Y. 256 Ermondi G. 250 319 Erneux T. 482 Ernst R.D. 352 353 356 358 492 Errington R.J. 54 55. 56 146 150 Ertel T.S. 147 380 Erthal S.M.D.,301 496 501 Esayed A.Y. 117 Escriche. L. 78 314 Escriva E. 205 303 Escudie J. 44 47 Escuer A, 207 303 308. 313 448 Eshuis J.J.W.. 116 Espenson. J.H. 317 322. 328 477. 478 490 Espinosa G.P. 430 Esposito F. 436 Esposito. U. 436 Esteruelas M.A.7 218. 359 365 492 Esumi. K. 241 Etemad-Moghadam G.. 65 Ettl R. 34 Ettorre R. 200 Etzbach T. 146 Evagorou E.G. 256 339 Evain M. 57 407 421 Evangelatos G.P. 467 Evangelatos S.A. 467 Evans C.H. 244 Evans D.A. 13 Evans D.F. 74. 11I 307 Evans. D.G.. 222 Evans D.H. 37 40 Evans. D.J. 176 277 312 Evans G.J. 469 Evans J.. 175 Evans M. 461 Evans. P.J.M. 187 Evans W.J. 45 56 68 244 259 260 Eveland. J. 98 Evens. G.G.. 116 Evic N.J. 285 Eydoux F. 509 Eyring E.M.. 489 492 Fabbrizzi. L. 238 320 FabihI. I. 481 Fabre J.M. 80 Fabretti A.C. 205. 303 Facchin G. 210 Fache E.. 215 Fachinetti G.. 492 Fackler. J.P.. 195 Fagan. P.J. 33 37 40 21 1. 351 Fager J..180 Faggin B. 467 Fainzilberg V.E. 207 499 Fairlie. D.P.. 233 487 Faithfull. D.L. 248 Fajer .I. 182 498 Fakhrayan. H. 279 Falconi M.. 507 Falconnet. P. 244 Falius H. 58 Faller J.W. 151 Fallis. K.A.. 391 Fallon. G.D. 205. 287 296. 297 Fally. F. 466 Falvello. L.R. 137 Fan H.-J. 41 1 Fan. M. 357 Fanfarillo M. 169 Fang N. 457 Fangjit. Z.. 275 Fanjat N. 442 443 Fann. W.-P.. 499 Fanning J.C.. 149 185. 289 Fanta A.D. 47 57 Fantin. G.. 97 Fantinato L. 466 Fanwick P.E. 86 112 117 122. 165. 167 178 214 351 357 Fares V.. 77 269 Farid R.S.. 474 Faridoon K.Y.. 474 503 Farina S. 132 Farkas. J. 195 Farmer B.L.. 98 Farmer P.J. 292 Farnan I.. 26 Farooq.A,. 197. 204 300. 306 497 508 Farrell. N.. 232 235 Farrell. R.P. 477 Farrugia L.J. 136 371 Fasth K.F. 463 Fastow. M. 38 Fatemi A, 28 Faulques E. 403 Faus J 201 204 206. 302. 303 448 Fava Ci.G.. 281 Favarato. M. 27 Favier. F. 245. 247 Fawcett. J.. 173 235. 248 Fawcett V. 178 Fawzi R. 64 218 Fayet. J.-P.. 65 Fazlur-Kahman A.K. 122 Fecher. B. 479 Fedelli F.. 250 319 Fedin V.P. 138 156 Fedorov. P.P. 247 Fedorov V.Ye. 138 407 Fedoseev A.M. 264 Fedushin I.L. 258 Feher. F.J. 16. 48 Fehlhammer W.P. 142 374 Fehlner. T.P. 6 388 Feist M. 422 Felc7an. A,. 180 Feld H.. 179 Felder C.. 191 Feldheim D.L. 37 Feliu. A.L.. 459. 462 Felix. V.. 333 Felner.1.. 446 Felten C.. 353 Femec D.A.. 123 Feng Q. 372 Feng. Q.R. 395 Feng S.. 406 Feng. S.G. 141 354 Feng S.Q.. 395 Feng T. 252 Feng. W.-C. 378 Feng. X. 109. 134. 138 Feng Z. 445 Fenske. D. 55. 79 80. 82 191 Fenton. D.E. 239. 294 340. 344 Fenton. R.R. 285 Feracin S. 358 Ferekides C. 80 Ferey G.. 29. 441 443 Ferguson. G. 11 83 320 Ferguson. J.M. 363 Fernandez B. 27 Fernandez. M.I.. 27 Fernandez S.. 469 FernandeL-Baca. J.A. 427 Fernander-Roy. E.. 476 Fernandez-Diar. M .T..410 Fernando. Q. 246 323 Ferrari. M.B. 281 Ferrenberg. A.M. 432 Ferrer M. 372 380 Ferrer S. 202 Ferrere S. 283 475 Ferretti. V. 164 292 Ferrieri R.A.. 454. 465 Ferris. K.F.. 68 Fester A.109 Fettouhi M. 360 Fiegenbaum P.. 374 Field J.S. 381 Field. L.D.. 71 176 361 Field R.J.. 90. 481 482 Fierro. J.I.G.. 232 Fife. W.K.. 95 Figg. D.C.. 192 Figgis B.N. 149 200 Filgueiras. C.A.L.. 226 Fillion. G. 440 Finazzi-Agr. A.. 507. 509 528 Findeisen M. 163 Findenegg H. 275 Fink M.J. 235 366 Finke R.G. 182 491,491 Finklea H.O. 474 Finn M.G. 18 Fiorani D. 442 Fiory A.T. 37 406 Firestone A, 340 Firman P. 489 Firnau G. 464 Firouzbakht M.L. 456 Firth S. 63 Fisahn P. 64 Fischer D. 412 Fischer E. 32 Fischer H. 480 Fischer J. 88 111 180 182 196 254 283 38 1 451 499 Fischer J.E. 39 404 406 Fischer P. 169. 263 444 445 Fischer R.A.30 Fischer R.D. 258 259 Fischer T. 32 Fish D.J. 401 Fisher G.A. 55 56 Fisk Z. 425 Fissekis J.D. 463 Fitzgerald J.P. 182 Fitzsimmons B.W. 187 Fjaertoft Pedersen B. 250 Fjellvaag H.J. 245 Flamini A, 269 Flassbeck C. 315 Flavell W.R. 397 Fleischer. H. 229 Fleischmann M. 209 Fleishaker J.C. 462 Fleming R.M. 37. 405 406 Flerov G.N. 243 Fleshier S. 397 451 Fletcher J.F. 203 Fletcher J.G. 415 Florke U. 189 229 376 384 448 Flood A.C. 171 Flood. T.C. 363 Floriani C. 110 121 289 327 Floruss A, 59 60 Flouquet. J. 425 Fluck. E. 63 66 Fluke R.J. 469 Flynn R.J. 54 Foerster P. 481 Forsterling H.-D. 482 Foglia C. 202 Fokina N.P. 401 Foldeaki M. 30 Folgado J.-V.200 205 303 Folman M. 38 Folting K. 10 48 136 137 139 146 162 197 203 215 224 365 497 Fong C.Y. 57 Font I. 185 334 Fontaine A. 182 498 Fontaine X.L.R. 8 11 Fontecave M. 501 Foo T. 364 Foote C.S. 35 38 73 Foote M.C. 397 Ford D.A. 335 Ford P.C. 198 221 493 Forgan E.M. 425. 428 Fornes V. 29 Fornies J. 88 212 Forsberg. J.H. 489 Forster G.E. 71 Forster K. 445 Forsyth C.M. 258 Forsyth G. 207 342 Forsyth J.B. 149 428 Fort A. 269 Fort D. 425 Fortenberry D. 481 Fortier S. 371 492 Forunier J.M. 447 Foss C.A. 37 Foster S.E. 244 Fouassier M. 143 Foucher D.A. 16 98 103 Fourmigue M. 178 Fourquet J.L. 108 142 410 422 424 Fowler C. 28 Fowler J.S.464 Fowler P.W. 35 36 41 Fox B.G. 183 500 502 Fox M.A. 473 Fragala I. 265 328 Fragnaud P.. 407 421 Franceschini R. 465 Francesconi L.C. 164 292 465 Francis J. 132 Franco R. 504 Franczyk T.S. 261 Frank W. 75 Frankcom T.M. 263 Franke A, 32 Franolic. J.-D. 294 Franse J.J.M. 425 Fraser K.A. 91 Fratiello A, 28 Frausto Da Dilva J.J.R. 165 Frazer A. 273 Frebel M. 65 Frechet J.M.J. 94 Frechette M. 248 Frediani P. 359 380 Freedman T.B. 498 Freeman A.J. 426 Freeman G.K.W. 153. 230 Freeman H.C. 506 Freeman J.W. 356 492 Freeman W.G. 399 Frei G. 272 Frei U.M. 485 Freire-Erdbrugger C. 48 Author Index Freiser B.S. 246 Freitag S. 44 Frenkiel T.A. 231 486 Frenking G.82. 120 157 Frenzen G. 200 336 423 434 Freud A. 467 Friebel C. 197 Friedman A.E. 213 Friedman A.M. 465 Friedrich K.H. 229 Friend R.H. 102 176 200 Frier M. 466 Fries A, 356 Friesen D.A. 318 Frink. M.E. 221 Frit B. 245 Fritz G.. 46 59 Frolik C.A. 500 Frommel T. 186 Fronczek F.R. 32 341 Froom S.F.T. 391 Frost M. 75 130 Frost-Jensen A, 160 Fruehling J. 468 Fryzuk M.D. 111 364 Fu G.C. 13 Fu. P.-F. 353 Fu W. 503 Fu W.T. 407 Fu Y. 261 Fuchita Y. 313 Fuchizaki K. 401 Fuchs J. 142 374 Fuchs R. 250 Fueki K. 458 Fiinfgelder. S. 297 Fueno. T. 432 Fuentes. M.J. 110 Fuertes A. 205 303 Fuess. H. 186 247 289 Fuger J. 244 244 Fuhrmann K.176 Fujihara S. 256 Fujihara T. 150 448 Fujii H. 180 500 Fujii. R. 462 Fujii T. 358 Fujiki Y.. 410 Fujimoto C. 204 273 508 Fujimoto T. 222 Fujino T. 262 447 Fujisawa K. 203 204 273 506 508 Fujita J. 183 270 272 Fujitani Y. 458 Fujiwara A, 403 Fujiwara N. 435 437 Fukahori T. 361 Fukuda Y. 403 435 Fukuhara C. 344 Fukui K.. 179 Fukumoto T. 210 Fukumura. T. 461 Fukunaga T. 40 Author Index Fukuoka. A, 222 Fukuoka M. 461 Fukushima N. 200 Fukuyama K. 179 Fultz A. 174 Fumagalli A,. 68. 384 385 Fun H.-K. 51 Funahashi S. 401 402 439 482 488 Funaioli. T. 492 Funaki S. 194 294 505 Furdyna J.K. 442 Fure J. 405 Furer N. 158 Furey W.F.203 Furrer A. 445 Furue M. 267 Furukawa. Y.. 439 Furuki R. 89. 90 Furumori K.. 100 Furusawa H. 336 Furuta H. 25 Fuse M.. 267 Fusek J.. 12 Fusi A. 223 Fusi V. 347 Futita. J.. 228 Fuxing G. 260 Fuyuhiro A, 150 448 Fuzeng Y . 460 Fyfe H.B. 102 Gabay M. 433 Gabbai F. 66 Gabe E.J. 152 329 Caber. M. 202 Gade L.H. 220 Cadet V. 436 Gaede W. 482. 490 Gaeggeler H.W. 265 457 Gaensslen M. 87 Gaewdang T. 422 Gage D.A. 191 Gagliano E. 429 Gagne G. 466 Gagne M.R. 257 Gahan L.R. 311 337 Gail R. 462 Gaillard J. 190 Gailus H. 120 513 Gair A, 477 Gajda T. 277 Gakh A.A. 86 Gale J.D. 41. 107 Gall. P.. 413 Gallagher J.F. 1 I 83 320 Gallagher R.T..38 Gallart. J.C. 434 Gallazzi M.C. 248 Gallois B.. 192 Gallop M.A. 382 383 Gallorini M. 454 Gallucci. J. 372 Gallup R.F. 57 Galons H.. 460 Gal’perin E.L. 256 Galsbsl F.. 224. 483 Galvao A.M. 263 Galyametdinov Y. 189 Gambarotta S. 112 113 149. 150. 327 369 Gamble AS. 354 Camper. S.F. 63 67 144 Ganapathisubramanian N.. 481 Gandour R.D. 32 Ganguli A.K. 418 Ganguly B.N. 169 Ganguly P. 402 Ganguly. S.. 227 228 Ganne. M. 418 Cans P. 180 Gansow O.A. 468 Gao H.. 230 259 Gao. S. 247 Gao W. 445 Gao Y. 108 160 Garcia. A. 203 Garcia. C.G. 475 Garcia. G. 277. 312 Garcia. J. 200 Garcia. M.E. 114 Garciii. M.P. 7 283 365 Garcia Alonso F.J.. 357 379 Garcia-Deibe A, 161 289 Garcia-Espatia.E. 344 Garcia-Granda. S. 155 357 Garcia-Munoz J.L. 445 Garcia SanL M. 379 Garcia-Vazquez A. 174 Garcia-Vazquez J.A. 197 Card G.L. 149 Gardiner M.G.. 24 Gardner P. 468 Garelli. N. 267 Garfinkel-Shweky D. I89 Garg P.K.. 467 Garg S. 467 Garito A.F. 33 Garland B.A. 489 Garland M.T. 448 Garlaschelli L. 384 387 Garmer D.R. 509 Garner C.D.. 118 128. 171 496 Garner. M.. 210 486 Garner. S.E.. 373 Garnett E.S. 464 Garniet F. 101 Garot. C. 64. 65 Garr C.D. 491 Garrett J.D. 425 Garrett T.M. 240 Garrigou-Lagrange C. 77 Garron J.Y. 466 Garvey J.F. 38 Garzarek P. 53 Gaspar. P. 263 Gaspar. V. 482 Casque L. 201 Gassman P.G.391 Gasyna Z. 38 Gates. B.C. 225 237 Gates. P.N. 53. 87 Gatley S.J.. 465 467 Gatteschi D. 125. 126 435. 448.449 Gatti. G. 507 Gaube W. 172 Gaulin B.D. 43 I 433 Caultier J. 200 Gaur. K.. 443 Gauss J. 157 Gautam P. 37 Gavezzotti. A.. 371 Gavney J.A. Jr.. 358 385 Gavoille G. 445 Gay R.R. 199 Ge Y.-W. 390 Gea Y. 132 156 Geanangel R.A. 43 Gecheng W.. 258 260 Geck M. 297 Gedridge R.W. Jr.. 61 Gedye. C.. 306 Gee A.D. 462 463 Geest C.G.. 481 Gehart G. 20 123 Gehlen J.N. 474 Gehring P.M.. 425. 440 Geib S.J.. 355 373 Geick. R. 438 444 Geier G. 485 Geiger D.K. 180 Geiger W.E. 18 363 Geisberger. G.. 5 Geiser U.. 451 Geissler B. 63 Gelerinter E.180. 477 Gelessus A, 67 Geleyn R.P. 370 Gellman S.H. 331 Gelmini L.. 306 Gemmler A, 10 Gencheva. G.. 183 233 Gene R.J. 487 Genglin W. 297 Geoffroy G.L. 327. 357 377 378 390 Geominne A.M. 316 George A.V.. 176 361 George C. 54 200. 203 George G.N. 51 1 George M.W. 145 371,492 George T.A. 69 145 George T.F. 3 34 41 Georges B.. 459 Georges. R. 434 Georgiadis M.M.. 512 Geraldes. C.F.G.C.. 250 308 312 Gerards L.E.H. 491 Gerasimchuk. N.N. 193 Gerasimenko A.V. 108 Gerasimova. G.A. 261 Gerbeleu N.V. 285 Gerber T.I.A. 163 Gerbier Ph. 101 Gerdes J.M. 467 Geremia S. 227 267 504 Geret-Baumgarten L. 16 Gerfin T. 272 Gerhard A, 479 490 Gerhardt R.88 Gerli A, 182 285 503 Gernon M. 153 Gerothanassis I.P. 182. 498 Gerrasio G. 370 Gerse J. 460 Gersonde K. 498 Gestin J.F. 467 Geue R.J. 348 Ghibaudi E. 490 Ghilardi C.A. 160 191 272 Ghiorso A. 243 Ghiselli A. 501 Ghosh M.C. 476 477 479 Ghosh P. 197 269 300 Ghosh P.N. 153 Ghosh S. 279 292 448 Ghosh S.K. 479 Ghyoot M. 459 463 Giandomenico C.M. 232 Giannelis E.P. 169 Giardello M.A. 257 Gibb T.C. 414 444 Gibbs C.D. 442 Gibbs D. 425 447 Gibson J.F. 79 172 190 271 304 503 Gibson J.K. 264 Gibson V.C. 54 74 117 122 128 353 355 Giebultowicz T.M. 442 Gier T.E. 114 415 Giering W.P. 480 Gignoux D. 425 Gilberd P.W. 30 Gilbert T.M. 355 Giles C.C.D. 482 Gilje J.W.261 Gillan E.G. 36 246 Gillard. R.D. 73 221 Gilletti P.F. 123 Gilli P.. 164 292 Gillon B. 451 Gimarc B.M. 3 57 Gimelseed A. 180 Gimeno M.C.. 88 241 Gindelberger D.E. 50 332 Ginley D.S. 396 Ginn V.C. 81 84 236 Giolando D.M. 68 Giordano N. 230 Giovanni M. 227 Girard L. 362 Girerd J.-J. 162 432 448 497 Giriat W. 445 Girolami G.S. 7 Gismelseed A.. 499 Giuffrida G. 283 Giunta N.. 72 Giusti A, 303 Gladfelter W.L. 362 Gladysz J.A. 358 Glarum S. 37. 405 406 Glaser J.. 221 Glassman T.E. 69 Glaubitt. W. 113 Glaum R. 114 124 146 Glausinger W.S. 109 Glegg W. 31 Gleisberg V. 265 Gleiter R. 63 Gleitzer C.. 439 Gleizes A, 201 Gleria. M. 97 Glerup J.131 143 144 207 276 316 Glickman B.W. 231 Glidewell C. 179 Glidewell S.M. 179 Gliemann G. 202 Glowiak T. 170 250 Glyn P. 145 Gmelin E. 445 Gober. M.K. 457 Gobi K.V. 217 Gochev G. 233 Godeneche D. 465 Godfrey M.J. 429 Godfrey S.M. 53 75 160 177 Godfrin H. 425 438 Goel S.C. 253 Goeminne A.M. 315 Goerissen. R. 216 Goesmann H. 59 82 Goethals P. 462 465 Goffart J. 264 265 Gogoll A, 227 Goh L.Y. 362 Gohdes J.W. 162 299 448 Goher M.A.S. 173 Gokel G.W. 23 346 Gold A, 182 500 Goldberg D.P. 162 171 Golden J.H. 20 Colder A.J. 187 Goldstein D.S. 464 Goldstein S. 490 Golinelli 0..436 Goll J.G. 477 Goller H. 288 Gomez M.E. 27 Gomez-Garcia C.J.434 449 Gomez-Romero P. 151 200 Gomez-Sal M.P. 382 Gomez-Saso M.A. 88 Gomory F. 428 Gonbeau D. 65 Author Index Gong J. 464 Gong J.K. 178 Gonzales S.L. 56 260 Gonzalez D. 170 Gonzalez H. 145 Gonzalez Calvet J. 439 440 Gonzalez Duarte P. 237 Goodall R. 455 Goodenough J.B. 30 394 398 444 Goodgame. D.M.L. 239 Goodloe G. 34 Goodman G.L. 262 Goodman M.M. 462 463 464 467 468 Goodreau B.H.. 5 8 Goodrich R.G. 341 Goodson. P. 166 Goodson P.A. 207. 276 316 Goodwin H.A. 192 Goodwin H.P. 64 Goodwin K.V. 206 281 Goossen L.. 61 Gopalan A.S. 309 Gopalkrishnan J.. 30 414 Goran N. 487 Gordon D.C. 88 Gordon G. 481 Gordon J.C. 86 137 148 Goretta K.C. 210 Gorlitz D.446 Gorlitz F.H. 24 252 257 258 26 1 Gorochov 0..398 Gorun S.M. 187 432. 501 Goryunov A.V. 247 Gorzellik M. 56 58 Goshorn D.P. 125 126 451 Goto A, 29 Goto H.. 337 Goto M. 42 50 233 Goto T. 435,437. 439,451 Gotoh F. 145 Gougeon P. 413 Gough C.E. 428 Could E.S. 476 477 479 Could R.A.T. 242 Could R.O. 176 183 207 314 342 Courier D. 115 354 Gouygou M. 65 Gouzerh P. 145 146 Govindaraju K. 474 Gowland R.J. 490 Goyunov A.V. 247 Gozlan H. 467 Gozum J.E. 7 Grace M.R. 172 483 485 Grachev O.G. 258 Graciani M.del M.. 490 Graczyk G. 164 292 Gradinaru D.I. 285 Gradoz P. 264. 265 Graetzel M. 213 Author Index Graham. S. 183 325 Gralla E.B..508 Gramlich V. 203 206 272 Grammatico J.P. 112 Grandi M. 250 Grandin A, 416 417 Grandjean D. 77 366 Grandjean F. 439 Granier T. 192 Grannec J. 200 422 439 Grannec N. 423 Grant G.J. 337 Graser S. 427 Crasser F. 140 511 Graul R.E. 181 Gravereau. P. 199 200 416 422 423 Graves L.J. 68 Gray C.P. 251 Gray G.M. 309 Gray H.B. 76 134 236 262 474 495 506 501 Gray. S.D. 353 Graziani R. 84 166 Greaney M.A.. 79 132 134 156 Greaves C. 199 401 419 Greb. T. 438 Grebenik. P.D. 214 Greedan J.E. 443 Greedan T.E.,431 Green J.C. 79 353 355 363 Green J.F. 463 Green. M. 210. 356 391. 486 Green M.A. 35 165 455 465 Green M.E. 54 Green M.L.H. 127 139 214 352 353 354 355 357 372 Greene R.421 Greene T.M. 169 Greenwood N.N. 3 8 Gregorich K.E.,457 Gregory T.P. 212 Gregorzik R. 273 510 Grein F. 81 86 Greiner S.P. 202 Greiwing H. 32 Grepioni F. 371 380 382 383 385 Gretenkord K. 75 Greth R. 53 Greulich N. 455 Grey C.P. 261 Gribben S.J. 466 Griesar K. 189 501 Griffith W.P. 90 165 219 Griffiths D.V. 68 164 294 Griffiths G.W. 111 307 Grifith W.P. 75 Grigereit T.E. 200 437 448 Ctrigg J.A. 20 Grigg R. 267 Grigor’ev A.N. 201 Grigor’ev M.S. 264 Grimes R.N. 3 18 Grimes R.W.,41 107 Grimmeiss A.M.H. 124 Grimmer S.S. 376 Grobe J. 62 63 70 Grochowski T.. 231 Groenke D.A. 399 Gronenborn A.M. 510 Gronsky R. 403 Groombridge.C.J. 185 341 Gross. M.E. 109 Gross U. 87 Grossel M.C. 32 341 Grossi L. 385 Groton C.T.,461 Groult D. 401 412 Grove D.M. 233 Grover. N. 269 Grubbs R.H. 360 Gruber. M. 105 Gruehn R. 114 124 146 Grutzmacher. H. 16 44 62 80 Grunkemeier J. 369 493 Grushin V.V. 89 Gruss D.. 32 Gschwandtner. G. 455 Gu C. 397 405 406 Gu J.S ,25 Gu Z. 406 Guadalupe A.R. 477 Guan J. 259 Guan %. 37 Guardado P. 173 Guarr T.F. 283 Guastini C. 121 Gubaidullin R.K. 442 Gubanov V.A. 265 Gudat A, 68 Giidel H.U. 158 169 272. 318. 449 Guedes Da Silva M.F.C. 165 Gueho C. 417 Guelec S. 54 Guelton M. 199 Guerchais V. 373 Guerin C. 101 Giirol I. 294 Guerriero P.330 Guerro J. 269 Guery J. 108 Gugel A, 34 Guglielmo G. 283 Gui M. 181 Guidi F. 485 Guigliarelli B. 504 Guilard R. 25 182 213 Guilhem J. 196 Guillaume M. 455 460 464 467 Guillot M. 202 207 308 448 Guillot-Edelheit G. 183 285 500 Guillou O. 207 308 448 Guimpel. J. 396 53I Guiqin D. 415 Guisti A, 205 Guizard. C. 113 Gulbis J.M. 174. 346 Guldi D. 318 Gulec S. 61 Gulin. A.N.,470 Gulino A. 265 328 Gultneh Y. 197. 300 306. 497 Gummow R.J. 413 Gunale. A.S. 388 Gundersen. S. 166 Gun’ko Y.K. 7 259 Gunn J.M.F. 429 Guntherodt H.J. 427 Guo B.C. 41 107 Guo C. 181 Guo T. 36 246 261 Gupta G.P. 181 498 Gupta K.S..480 Gupta N. 269 276. 279. 291 Guseva L.I.265 Guslander J. 482 Gusling H.J. 24 Gustafson W.G.,498 Gutierrez A, 449 Gutierrez E. 273 364 Gutierrez-Puebla E. 51 Gutlich P. 189 192 Guyomard D.,416 Guzi P.J. 132 Gyepes E. 170 Gyorgyi. L. 90 481 482 Gyorgy E.M. 37. 405 406 Gysemans M. 465 Haaland A, 26 61 112 120 166 Haanstra W.G. 203 204 280 292 Haas A, 82 Haase D. 191 Haase W. 189 289. 501 Haasnoot J.G. 202. 204 212 269 283 Habata Y. 333 Haberlen O. 262 Habiyakare A. 195 Hackwell T.P. 30 Hada Y.. 255 Haddon R.C. 37 83 404. 405 406 Haddy A, 161 295 497 Hadjikakou S.K. 195 Hadley S.W.,468 Haefeli U. 468 Haefner S.C. 221. 223 Hamalainen R.. 292 506 Haemers D.J.W.. 417 Haemers T.A.M..417 Haenel J.59 Hanggi G. 51 1 Hafferty B.S. 182 Hagd M. 283 475 532 Hagdorn K. 435 Hage R. 212 269 283 Hagen K.S. 120 125 156 187 188 189 501 502 Hagen P.M. 172 448 Hagen W.R. 190 503 513 Hagenlocher I. 458 Hagenrnuller P. 412. 422 423 434,439 Haggerty B.S. 6 129 131 311. 327 357 362 377 378. 387 390 Haghighi M.S. 254 255 Hagiwara M. 436 Hagiwara R. 423 Hahn C.W.,291 448 Hahn F.E. 257 354 Hahn G. 434 Hahnfeld D. 16 Haiduc I. 71 Haines R.I. 479 Haines R.J. 381 Hainfeld J.F. 457 Haire R.G. 264 Hajela S. 246 Haka M.S. 197 300 Hake D. 247 Hake R. 495 Hakornori S. 461 Hakonen P.J. 426 Halbert T.R. 132 Halcrow M.A. 78 183 314 331 Hale S.J.470 Halet J.F. 77 Hall C. 215 Hall C.D. 347 Hall C.F. 194 Hall H.L. 226 457 Hall I. 443 Hall J.R. 233 236 Hall K.A. 154 Hall L.D. 490 Hall M.B. 41 107 113 128 224 351 370 Hall S.R. 399 Halldin C. 459 461 462 463 Haller K.J. 180 181 Hallford R. 84 Hallinan N.C. 356 492 Halperin B.I. 429 431 436 Halvorson K. 200 Hamacher K. 462 464 465 Harnada K. 395 Harnann J. 42 Harnbley T.W. 121 159 176 204 285 305 321 322 484 496 Hambright P. 202 488 Harnkens W. 462 Harnley P.A. 223 Harnrnel. A, 26 61 Harnrnel D. 34 Harnrnerschrnitt P. 111 Harnrnond C.E. 376 Harnrnond M.E. 245 Harnon J.-R. 359 363 Harnon M. 467 Harnon P. 359 Harnpden-Smith M.J.137 195 375,377 Han H.X. 301 Han. J. 508 Han K. 173 Han P. 480 Hanaki A. 202 Hancock R.D. 322 Handa M. 134. 194 294 505 Hands M. 255 Handwerker H. 374 Hanke J. 88 Hanna J.V. 196 Hannakarn M. 292 Hannink N.J.,457 Hannon M.J. 196 283 285 Hannongbua S. 333 Ijanrahan S. 467 Hansen K. 33 Hansen L. 164 292 Hansen T.K. 342 Hanshew D.D. 474 Hanson G.R. 291 Hanson R.N. 467. 467 Hanssgen D. 47 Hansson S. 366 Hanton L.R. 179 272 277 Hanusa T.P. 45. 116 Hao S. 327 369 Harada A, 451 Haradahira T. 464 Hardcastle J.E. 32 Hardcastle K.I. 313 Harding C. 306 313 347 Hardy D.T. 234 Hare J.P. 38 39 Harkerna S. 261 Harlow. R.L. 39 Harrnan M.163 263 272 273 Harrnan W.D. 218 Harms T. 461 Harneit O. 199 Harpel M.R. 500 Harper J.R. 141 Harrap K.R. 232 Harris A.B. 430 Harris J. 376 Harris R.K. 53 Harris S.D. 331 Harris W.R.,488 Harrison A, 319 433 435 437 44 1 Harrison J.M. 465 Harrison K.N. 227 Harrison M.R. 399 Harrison P.M. 502 Harrison W.T.A. 114. 419 Harrod J.F. 97 115 Harrowfield J.M.; 248 Author Index Harshani de Silva D.G.A.,474 Hart E.J.,480 Hart I.J. 287 Hart J.R. 187 432 501 Hart R.D. 195 197. 206 Hart R.O.C.. 159 269 Hartenstein F. 292 Hartl. H. 197 Hartner H. 53 86 Hartshorn R.M.,213 269 Hartung H. 372 Hartweg M. 420 Hartwig J.F. 214 231 Harvey H.B.. 185 325 326 Haschke J.M.470 Hasegawa M. 26 Hasegawa T. 360 Hasegawa. Y. 100 114 Hasenbach J. 60 Hashirnoto K.. 133 Hashirnoto. S. 204 273 508 Hashirnoto V.. 313 Hashimoto Y. 26 468 Hashirnura M. 301 448 Hassan M. 462 Hassanzadeh P. 81 Hasselbring R. 77. 167 Hastings J.B. 428 Hastings J.J. 74 Hatano K. 464 Hatano T. 100 Hatfield G.R..97 Hatfield. W.E. 161 162 207 255 278. 295 497 499 Hathaway B.J. 204 Hathorn R.M. 116 Hattersley A.D. 6 388 Haufler R.E.. 36 246 261 Haupt H.-J.. 189 229 376 384 448 Hauptrnan. E. 363 480 Hauri D.J. 481 Hauser A, 192 193 Hauser. M.J.B.,481 Haushalter R.C.. 126 Havela L. 425 Havranek E. 466 Haw. J.F. 97 Hawkins J.M. 40 217 Hawthorne.M.F. 5 91 11 1 26 1 Haxell A. 131 Hay M.S. 390 Hay P.J. 164 264 Hay R.W. 487 Hayakawa H. 397 Hayashi A, 29 63 65 Hayashi M. 112 Hayashi R.K.. 385 Hayashi T. 13 51 100 143 Hayashi Y. 306 448 Haycock P.W.. 425 Hayden S.M.,440 445 Hayes J.C. 197 300 Author Index Hayes M.A. 267 Hayes W.. 200 Haynes A.. 480 Haynes G.R. 164 Hazell A, 150 Hazin C.A..470 Hazzard J.T. 474 He F.. 456 He R.Y. 443 He 2.. 387 Headford C.E.L.,207 283 475 499 Heagy M.D. 182 199 Healy. L.A. 196 Healy P.C. 195. 197 239 Heasley V.L. 87 Heath G.A. 37 Heath S.L. 74 170 190 291 Hebard A.F.. 37 406 Hebecker. C. 247 Heck J. 354 Heckrnann G. 56 63 147 Hedberg K. 149 156 Hedberg L.156 Hedge M.S. 414 Hedman B. 500 505 Heeg M.J. 78 109 163 164 292 489 Heflin J.R. 33 Hegernann M. 63 70 Hegenauer J. 474 Hegetschweiler K. 156 Heidberg J.. 38 Hein. B. 378 Heinekey D.M. 378 Heinernan W.R. 163 Heiney P.A.,404 Heintz R.A. 131 378 Heinze T. 82 Heinzel U. 315 Helgesen G. 446 Helgesson G. 253 Hellebrand B.. 397 Hellier P.C. 239 340 344 Helliwell M. 74 88 170 291 365 Hellquist B. 486 Helm L. 109 163 248 482 484 Helrnerich A, 113 Helrnholdt R.B. 407 417 Helus F. 455 463 Helvenston M.C. 491 505 Hernpstead P.D. 340 344 Hendershot D.G. 54 Henderson R.A. 158 176 354 457 Hendrich M.P. 187 287 306 501 502 512 Hendrickson D.N.159 162 172 189 192 287 299 306 432 448 449 497 501 Hendry G. 463 Henke H. 124 Henkel. G. 44 70 122 179 271 Henley C.L. 431 Henling L.M. 68 Henner B.J.L. 101 Henney R.P.G.,280 Hennion B. 443 Hennion M. 443 Henrot. P. 468 Henry B. 277 Henry J.Y. 441 Henry R.F.,256 Hensel B.A. 253 Hensel K. 492 Heppert J.A. 113 151 Heras J.V.. 273 Herber R.H. 192 Herberich G.E.. 14 365 Herbst-[rrner R. 19 44 82 158 Herdtweck E. 144 Herman G.G. 315 316 Heirnanek S. 3 Herrnann A.M. 30 Herrnann W.A. 253 Herr A. 436 451 Herren M. 169 Herrera J.V. 204 Herrero J. 492 Herrmann G. 455 Herrmann W.A. 68 166 257 270 31 1 Herro H.M. 210 Herron N. 39 Hertel T.53 Herve G. 127 129 Herve M.J. 65 Hervieu H. 407 41 1 Hervieu M. 395 396 401 407 412 Herz K. 443 Herzog P. 395 Herzog W. 447 Hesse W. 200 Hessen B. 400 407 Hetheririgton C.J.D.,414 Hettich R.L. 33 39 Heuer I-. 105 Heuer W.B. 182 199 Heyes. S.J. 139 383 Hey-Hawkins E. 45 70 Heyke O. 389 Heyn R.H. 216 235 378 Heyns J.B.B. 129 Hickmann U.,455 Hicks R.G. 83 174 Hidai hl. 143 145 230 Hidaka H. 407 Hidaka J. 197 271 Hien T.D. 425 Higaki H. 342 Higashida S. 97 HigashiJarna N. 256 333 High K G. 220 Higuchi A. 244 Higuchi K. 42 Higuchi T. 337 Higuchi Y. 438 Hikichi K. 97 Hikichi S. 510 Hikita T. 399 Hilbers M. 158 Hildebrand A, 167 Hildenbrand T.50 Hill A.F. 8 Hill A.L. 340 Hill C.L. 125 Hill C.W. 61 Hill J.E. 112 351 Hill K.W. 499 Hill M.N.S. 78 314 Hill R.H. 178 Hill R.W.,447 Hill S.A. 37 48 Hill Y.D. 246 Hilland S.P.W.,239 Hillebrecht H. 236 Hiller W. 24 43 68 218 294 Hillerns F. 121 Hills A, 139 158 176 305 Hilscher G. 446 Hilts R.W. 84 Hinatsu Y. 262 447 Hindahl K. 56 Hines J.J. 468 471 Hinks D.G.. 399 Hino T.. 47 Hinrichs K. 443 Hiort C. 261 Hipple W.G. 262 Hiraga K. 401 402 403 Hirai. M. 328 Hirai T. 401 402 Hiraka H. 436 Hirakawa K. 438 Hiraki K. 198 313 Hirata K. 26 Hirle B. 387 Hiro T. 185 Hiroi Z. 399 Hirosawa. I. 37 405 Hirose J. 233 Hirota N. 179 501 Hirotsu K.63 65 337 Hirpo W.. 31 Hirsch A, 37 39 40 Hirsch D.J. 497 Hirshfeld N. 467 Hirth U.-A. 65 147 380 Hirzmann J. 502 Hisada K. 466 Hissink C.E.,466 Hitchcock P.B. 39 45 48 66 67 115 165 170 253 305 Hitchrnan M.A. 124 159 Hitsrnan V.M. 451 Hiyarna. T. 85 Hiyama Y. 332 Hnyk D. 10 Ho J. 55 534 Ho J.C. 395 446 Ho P.C. 469 Ho Y.-H. 356 Hoad D.R.C.,397 Hoang N.N. 202 Hobbs J.L. 23 Hoberg J.O.,232 366 Hobson L.J. 275 Hock B. 444 Hockless D.C.R. 31 54 55 56 146 Hodeau J.-L. 33 401 Hodge S.R. 120 Hodgson. D.J. 207 276 316 Hodgson K.O. 500 505 Hoebel B. 56 Hogberg M. 308 Holscher M. 18 Homer M. 301,496 Hoernfeldt K. 461 Hoff C.D.371 Hoffman D.C.,457 Hoffman D.M. 165 108 Hoffman L.R. 206 Hoffman N.W. 127 Hoffman P. 88 453 Hoffmann B.M. 182 199 Hoffmann R. 198 492 Hoffmann R.-D. 245 417 419 Hoffmann T. 77 178 Hofmann F.P. 235 Hofmann J. 45 Hofmann P. 366 Hogarth G. 369 379 381 Hoggard P.E. 149 Hohmann H. 486 Hohn P. 68 Hoinkis M. 245 Hoke S.H. 11 38 Holah D.G. 222 370 379 Holcman J. 73 478 480 Holczer K. 39 449 Holden T.M. 425 Holder A.J. 183 314 Holdsworth P.C.W. 430 Hollander F.J. 351 Holligan B.M. 203 277 278 Hollman M.L.J.,442 Hollman P. 236 Holloway J.H. 39 74 79 89 211 212 219 Hollwarth A. 82 Holm R.H. 79 123 190 191 505 Holman T.R. 306 Holmes R.R. 59 76 Holmes R.S.353 Holschbach M.. 462 Holt E.M. 195 Holub J. 12 Holubar T. 446 Holwerda R.A. 160 476 Holwill C.J. 120 Holy P. 334 Holz R.C. 501 482 Holzer M. 389 Homberg H. 254 255 Homma Y. 468 Honert D. 170 Honeyman C. 98 Honeyman R.T. 269 Hong B. 134 Hong H.-G. 114 Hong L. 442 Hong M. 80 160 171 180 191 Hong R.-F. 100 Honggen W. 297 Honghui Z. 413 Hongliang Z. 461 Honig J.M.,440 Honk W. 26 34. 46. 420 Hop C.E.A.,378 Hope E.G. 39 74 158 211 212 219 Hope H. 126 Hopkins M.D. 134 355 373 Hopkins P.M. 372 Hoppe R. 124 412 Horakh J. 69 Hori H. 435 436 Horii H. 462 Horio T. 100 Horiuchi S. 396 Horn H. 20 Horney M.J. 87 Horton A.D.116 351 352 Horvath I.T. 364 Horwitz C.P. 160 267. 288 Horwitz E.P.,455 Horwitz T. 212 Hosain P. 466 Hoshino A,. 313 Hoshino T. 433 Hoskins B.F. 148 Hosmane N.S. 12 261 Hosoya S. 439 444 Hosoya T. 336 Hossain M.M.,79 360 Hosseini S.M. 395 Hostetler M.J. 224 225 480 Hotzelmann R. 189,448 Hou D. 125 Hou J. 403 Hou J.G. 404 Hou Z. 55 Houfu D. 457 457 Hourie R.A. 269 House D.A. 128 174 484 487 Housecroft C.E. 3 6 211 216. 382 388 Housmekerides C.E. 327 Houtman C. 222 Houtrnann C. 223 Hovemeier K. 126 Hoveyda A.H. 13 Hoveyda H.R. 271 Howard C. 275 Howard H.R.,461 Author Index Howard J.A.K. 165 352 353 355 Howard J.B. 34 Howarth O.W. 27 74 Howe D.A.451 Howells S. 34 Howes K.R. 490 Howie A.R. 415 Howie. R.A. 410 Howlader N.C. 128 Hoye P.A.T.,227 Hoyer M. 197 Hoz M.J.R. 358 Hriljac J.A. 417 Hrncir W.-D. 319 Hrusak J. 36 Hsu C.S. 38 Hsu D.P. 62 HSU H.-F. 390 Hsu L.Y . 222 Hu J. 165 259 Hu N. 250 Hu W. 445 Hu Z.G. 183 Huang B. 169 Huang G.-L. 365 Huang J. 127 409 410 418 Huang L. 124 160 191 364 Huang Q. 401,407 Huang S.P. 79 216 Huang T.-M. 365 367 Huang. W.-J..510 Huang Y. 5 246 358 Huang Y.H. 237 Huang Y.-Z. 61 419 Huang Z. 80 127 180. 191 Huang Z.H. 191 Hubbard C.D. 173 Hubbard J.L. 235 Hubbard K.M. 256 Huber C. 157 Huber R. 301 509 Huber V.J. 309 Hubert-Pfalzgraf L.G.200 251 253 Hubner K.F. 462 Hudon M. 467 Hudson S.A.,273 Hudson S.E. 295 Huebener R.P. 399 Hiiber M. 289 Hiickmann S. 147 380 Hiihn P.. 311 Huffman D.R. 34 Huffman J.C. 45 122 136 137 146 159 162 195 196 197 203 252 253 262 263 271 287 374 375 376 377 497 Hughbanks T.R. 109 247 Hughes A.K. 143 353 354 Hughes A.N.. 222 370 379 Hughes C. 371 492 Hughes. D.L. 128 139 155 158 165 176 305 331. 355 Author Index Hughes H. 269 Hughes J.M. 294 Hughes M. 120 Hughes R.P. 87 361 363 Hughes S.D. 30 Hull J.W. Jr. 362 Hull S. 413 Hullinger F. 445 Hulme C.E. 161 289 Hulsbergen F.B. 176 272 Humanes M. 132 483 Humrnel H.-U. 32 Hund H.-U. 358 362 Hung A.Y.C.232 485 Hunsch J. 445 Hunt B.D. 397 Hunt J.P. 480 Hunter A.D. 103 178 Hunter J. 204 347 Hunter M.K. 464 Huo Q.. 29 Huong D.Q. 247 Hupp J.T. 475 477 Huq L.N. 506 Hurlbut P.K. 79 Hurley D.P.F. 426 Hurst J.K. 73 Hursthouse M.B. 12 79 118 150 163 222 245 263 272 Huse. D.A. 430 430 Husebye S. 203 448 Huskowska E. 248 250 Hussain L. 483 Hussain-Bates B. 118 150 Hussonois M. 265 470 Huston P. 477. 490 Hutchings M.T. 447 Hutchinson J.E. 182 213 Hutson A.J. 163 272 Huttner G. 56 80 378 Huynh B.H. 181 499 503 Hvastijova M. 206 Hwang D.R. 464 Hwang. G.-Y. 147 Hwang K.C.. 37 Hwu S.-J. 124 416 420. 421 Hyde T.I. 183. 314 Hyla-Kryspin I. 63 Hynes J.T.474 Hynes R.C. 204 248 284 297 305 329 448 449 Ianelli S. 448 Iapalucci M.C. 57 Ibafiez R. 200 Ibberson R.M. 443 Ibers J.A. 35 79 80 84 133 156. 182 197 241 419 420 421 422 Ibina S. 228 Ibison P. 482 Ibragimov A.G. 24 Ibrahim A.I. 172 Ibrahirn M.I.M. 477 Ibrahim M.M. 445 Ichida H. 129 235 Ichikawa K.. 180. 500 Ichikawa M. 222 394 Ichirnara. A, 132 Ichinose A, 400 Ichiya Y.-I. 464 Ido T. 462 462 464,465 Ignatov V.P. 469 Ihara Y.,185 317 Iida J. 439 lijirna S.,172 Iio K. 433 437 Ijdo D.J.W. 417 Ijjaali. M.. 439 Ikeda I. 21 1 366 Ikeda M. 333 Ikeda S. 220 Ikeda T. 313 Ikernoto I. 34 36 306 404 449 Ikenoue S. 134 295 Ikoriya T. 270 Ilyukhin A.B.26 27 Imaeda K. 404 Irnahori Y. 462 Imai H 181,498 Irnakubo T. 50 Imamura A,. 14 Imamura T. 242 Irnanaka N. 244 Imhof W. 56 378 Imoto H. 138 In M. 113 Inabe T. 451 Inada Y.,488 Inagaki M. 467 Inarno M.. 488 Indelli M.T.. 318 Indrichan K.M. 285 Inglot. %. 443 Innocenti P. 294 Inoguchi K. 21 1 Inokuchi H. 404 Inoue. K. 297 448 Inoue hl.B. 323 Inoue R. 114 Inoue S. 499 Inoue Y. 230 Ionova. G.V. 261 Isab A.A. 238 Ishida T. 100 143 Ishigaki T. 398 402 Ishiguro.. S. 172 Ishihara. M.. 481 Ishihara. T. 242 Ishii M. 48 81 482 Ishii S.-I. 454 Ishii T.. 306 502 Ishii Y. 270 Ishikawa M. 100 101 450 451 Ishirnaru N.. 230 Ishimura D. 342 Ishirnura Y.500 Ishiwara N. 112 Ishiwata K. 464 Ishiwatari. N. 469 Isied S.S. 474 495 Isobe M. 409 Isringhausen-Bley S. 376 Ithakissios D.S. 467 Ito A. 439 Ito K. 436. 469 Ito. T. 151 374 Ito Y. 51. 488 Itoh F. 428 Itoh K. 33 40. 361 Itoh M. 407 414 Itoh O. 61 Itoh T. 332 Iuliano L. 501 Ivanov. I.A. 470 Ivanova G. 189 Iveson P.B. 313 Iwaizumi M. 182 Iwamoto M. 456 Iwata R.. 462 464 465 Iyer R.K. 28 Iyoda. M. 375 Izatt. R.M. 331. 489 Izumi F. 398 400 402 Izuoka A, 39 Jablonski. R. 404 Jachow H. 59 60 Jackels S.C.. 340 Jackson G.E. 250 Jackson H. 468 Jackson M.A.. 145 Jackson. W.G. 174 484 Jackson W.R. 72 220 Jacob E. 158 Jacobi R.163 Jacobini. C. 108 Jacobs H. 24 25 Jacobs J. 158 Jacobsen C.J.H. 149 Jacobsen C.S. 182 Jacobsen H.. 248 Jacobson D.M. 399 Jacobson R.A.. 69. 216. 288 Jacquet L. 301 Jaeger T. 371 Jagerovic N. 25 Jagner S. 253 Jain. V.K. 228 236 Jaiswal D.K. 460 471 Jaitner H. 444 Jakobi R.. 192 James B.R. 215 James C.A. 134 136 137 James. J.T. 355 James. M.W.. 291 Jameson. D.L.. 275 Jarneson. G.B. 195 273 507 Jameson R.F. 508 Jamieson W.R.E. 467 Janczak. J.. 199. 416 Janda K.D. 164 Jang H.G. 189 449 Janiak R. 34 Janoschek R. 46 57 JanouSek Z. 12 Janse E.W.,445 Jansen M. 34 72 89 416 Jansen R.-M. 374 Jarrett P.S. 56 Jarvis R.F. Jr. 81 Jarvis W.R.A.,444 Jaszbereny J.Cs.90 Javahery G. 38 Jay M.J. 38 Jayaraj K. 182 500 Jayasooriya U.A. 171 449 Jaynes B.S. 183 Jean A, 101 Jean Y. 245 Jeannin Y.. 79 115 127 129 145 197 202 378 379 Jeffery J.C. 154 203 277 278 Jeffrey E. 219 Jegat C. 143 Jehan D.A.,425 Jehoulet C. 37 Jeitschko W. 245. 419 Jelski D.A. 3 34 41 Jemil S. 28 Jemine X. 264 Jemmis E.D. 4 56 Jena P. 41 Jenkins A.A. 446 Jenkins H.A. 314 Jenkins J.A. 222 Jenkins Y.. 213 Jennings M.C. 320 Jennings P.W. 232 366 Jensen C.M. 224 492 Jensen J. 425 427 Jensen M.P. 388 Jeon K.S. 455 Jeon S. 478 Jervis R.E. 469 Jeske P. 110 31 1 312 Jessop P.G. 128 351 Jester W.A. 469 Jeung G.-H. 167 Jewett D.M. 465 Jha N.K. 61 279 Jhanji A.301 Ji L. 174 Jia G. 145 Jia L. 12 Jiang F. 191 Jiang J. 255 Jiang Q. 402 Jiang Z. 109 204 Jiang Z.-H. 207. 289 448 Jiaqi X. 466 Jiaxi L. 81 Jimenez H.R. 509 Jimenez J. 241 Jimenez M.V. 365 Jimenez R. 490 Jimenez-Becerril J. 454 Jiminez-Lopez A. 114 Jin C. 246 Jin D.M. 203 301 Jin S. 170 173 258 259 Jin T. 250 251 Jin Z. 256 259 406 Jin Z.-S. 248 259 Jingkui L. 415 Jinguji M. 481 Jinling H. 413 Jirong W. 195 Jivan S. 464 Jobanputra P. 69 166 Jobe D.J. 469 Jochem G. 62 Joh T. 229 Johannsen B. 425 466 Johansen H.S. 485 John C.S. 164 292 466 467 John. E. 465 Johnson A.W.S. 197 Johnson B.F.G. 102 219 220 370 380. 382 383 385 Johnson C.E. 443 Johnson D.C.,444 Johnson.F.P.A. 145 Johnson J.J. 165 Johnson J.L. 511 Johnson J.P. 81 86 Johnson L.K. 360 Johnson M.D. 212,477,479 489 Johnson M.E. 34 Johnson M.K. 503 Johnson R.D. 36 245 Johnson S.E. 91 111 261 Johnston E. 37 Johnston R.L. 41 Johnston V.I. 376 Johnston V.J.. 387 Joiris E. 466 Jolicoeur T. 436 Jolley W.H.,476 Jolly W.H. 172 Jona E. 175 Jones A.G. 164 Jones. B.D. 45 Jones C. 25 Jones C.D.,460 Jones C.J. 234 250 267 273 306 Jones C.M. 72 Jones D.L. 425,447 Jones D.R. 38 Jones M.M. 486 Jones M.T. 37 Jones P.G. 51 55 58 88 197 241. 372 380 Jones P.M. 199 Jones R.A.,45 71 Jones R.G. 97 Jones R.O. 57 Author Index Jones T.L. 334 Jones W.D. 215 221 357 375 Jones W.E. Jr.475 Jones W.M. 360 367 Jones-Skeens L.M. 477 Jongen Y. 459 Jongeward K.A. 493 Jordan K.D. 474 Jordan R.B. 476 Jordan T.A. 32 Jordanov J. 78 191 370 503 Jomgensen K.A. 160 288 Joerrgensen T. 342 Joselevich E. 269 Joseph-Nathan P. 358 Joshi A.M. 215 Joshi P.N.,29 Joshida M. 460 Jost D.T.. 457 459 Jost. M.B. 405 406 Joswig W. 413 Jouanneaux A, 418 Joubert O. 418 Journaux Y. 204,448 Jovanovic L.S. 285 Joyce J.J. 397 Juan H. 226 Juan S. 207. 289 448 Judd R.J. 121 496 Julbe A, 113 Julve M. 186 201 202 204 206 289 302 303,448 Jun H. 62 Jun Z. 466 Jung G. 500 Juntunen K.L. 207 330. 476 Juraanic N. 174 Juris A, 281 Ju-Song X. 258 Juszczyk S. 442 Jutland A. 227 Jutzi P. 12. 44 64 Kab H.65 Kabalka G.W. 462 463 464 467 468 Kabanos T.A. 121 269 291 Kabe Y. 48 81 Kabesova M. 201 Kabuto C. 42 Kacher C.D.. 457 Kaden L. 163 Kadish K.M. 25 37 Kadkhodayan B. 457 Kadowaki T. 48 81 Kadri M. 459 Kab H. 147 380 Kaemaeraeinen E.L. 464 Kaftajlov V.V. 469 Kahaian A.J. 385 Kahn. O. 192 308 434 448 Kahr. B. 38 Kahrizi M. 425 Kahwa I.A. 341 Author Index Kai T. 241 Kai Y. 150 Kaibin T. 412 Kairn W. 167 196 233 356 Kainosho M. 34 Kaiser U. 124 Kaitner B. 151 Kaizaki S. 144 150 448 Kajikawa Y. 220 Kajirnaru H. 366 Kajirnura K. 394 Kajitani T. 401 402 Kajiwara A, 153 190 Kajrnin E.P. 470 Kakabakos S.E.,467 Kakigano T. 215 379 Kakihana H. 455 Kakkar A.K.102 176 363 492 Kakurai K. 433 436 437 Kakuta S. 361 Kalies W. 172 Kaller R. 61 Kallert U. 338 Kallin C. 430 Kallrnunzer A. 67 Kaltsoyannis N. 79 353 363 Kalyanasundaram K. 213 Kamachi M. 267 451 Karnatani H. 42 Karnbayashi H. 191 Karnenar B. 151 Karnenicek J. 185 Karnenka J.-M. 461 Karnieniarz G. 436 Karnimura H. 428 Kaminski Yu.L. 460 Karniyama T. 402 Karnpf. J.. 14 61 197 278 388 390 496 Kanatzidis K.W. 230 Kanatzidis M.G. 31 79 80 191 216 Kanehisa N. 150 Kaneko I. 459 Kaneko K. 438 Kaneko T. 395 Kanellakopulos B. 258 263 264 Kaner R.B. 36 81 246 Kaneshiga M. 333 Kang B. 124 160 191 Kang B.-S. 361 373 Kang C. 171 Kang H. 153 Kang H.Y.,417 Kang S.-J. 158 222 Kankare J.308 Kanke Y. 409 Kannan S. 228 236 Kanner R.C. 73 Kanno H. 270 Kanornata T. 441 Kanters R.P.F.,297 506 Kanyshny A.L. 128 Kao C.C. 428 Kao M. 35 38 Kaobiro K. 185 Kapon M. 43 Kapoor R. 81 Kappen T.G.M.M.,389 Kappes M.M. 35 Kapsomenos G. 195 Kapustin V.K. 460 Karaghiosoff K. 67 Karagiannidis P. 195 196 Karas M. 466 Karasu. M. 341 Karaulov A. 12 Karbowiak M. 263 Karczewski D. 466 Karen. P. 199 245 Karfunkel H.R. 37 40 Karlin K.D. 197 204 207 300 306 497 499 508 Karpenstein I. 448 Karpishin T.B. 191 Karppinen M. 200 Karraker D.G. 170 Karunaratne V. 271 Karweer S.B. 28 Kasai N. 150 366 Kasamatsu K. 134 Kase Y. 199 Kashirnura S. 101 Kashiwabara. K. 272 Kaska W.C.124 Kasprowski J. 82 Kassner D. 413 Kastner K.A. 440 Kasuga K. 134. 255 Kata S.,457 Katada M. 36 306 Katayama T.. 133 Katen I-. 474 Kato A, 464 Kato. H. 151 444 Kato K. 409 Kato M. 40 175 203 297 399 Kato T ,36 94 245 246 433 Kato Y. 25 460 Katoh K. 7 Katori H.A. 439 Katou T. 158 Katsoulos G.A. 180 204 Katsurnata K. 436 Katti K.K. 466 Katti K.V. 166 466 Katzenel lenbogen J.A. 464 Kauffmann T. 238 374 Kaul B.B. 69 145 Kaupp M. 245 257 Kauzlarich. S.M. 57 Kawa H. 85 Kawabata K. 451 Kawafune I. 129 Kawaguchi K. 451 Kawaguchi T. 399 Kawai K. 468 Kawai S. 399 Kawai T. 399 Kawaizumi F. 226 Kawaji H. 414 Kawarnoto M. 34 Kawamoto T. 271 Kawarnura T. 432 Kawanishi T. 40 Kawano H.270 439 Kawashirna T. 196 Kawata J. 203 Kawata S. 36 170 246 306 Kawata. T. 297 Kawi S. 225 Kazarian S.G. 223 Kazurnov T. 88 Keady M.S. 363 Keane P.M. 421 422 Kearley. G.J. 171 449 Keck H. 62 Keder N.L. 124 Kee T.P. 122 Keeler J. 383 Keen D.A. 428 Keen F.I. 123 Keene F.R. 174 Keiichi K. 256 Keizer P.N. 37 Keki S.. 482 Kelland L.R. 210 232 Kelland M.A.. 214 Keller H. 428 Keller N. 261 Keller W. 10 Kelley C. 357 Kelley M.J. 225 Kello E. 180 Kelly D.G. 75 160 Kelly J.D. 68 163 164 256 272 294 339 Kelly P.F. 73 81 84 236 Kernmitt R.D.W. 235 236 Kernrnler-Sack S. 399 Kemp C.M. 316 Kemp H.J. 163 Kernp T.J. 163 Kernper K. 460 Kendall J.L. 255 Keneko T. 441 Keniry M.E..204 Kennard C.H.L. 236 311 337 Kennedy J.D.,8 11 12 Kensett M.J.,460 463 Kepert. C.J. 200 Kepert D.L.. 159 Kepler K.D. 255 Keramidas A.D.,269 291 Kergoat. R. 377 Kern J.-M. 196 Kerns K.P. 41 107 Kersten H.J. 84 Kersten J.L. 378 Keshavarz-K M. 276 538 Keske J.M. 474 Kessissoglou D.P. 162 207 278 29 I 497 Kessler R.M. 467 Kester J.G. 10 Keszler D.A. 131 415 Ketring A.R. 466 Kettenbach R.T. 364 Khadar R. 225 Khaidukov K.M. 423 Khaidukov N.M. 247 Khalaf S. 63 Khalil L.H. 174 Khalkin V.A. 457 Khan K.S. 457 Khan M.A. 353 Khan M.I. 125 126 Khan M.M.T. 213 285 289 304 Khan M.S. 102 176 Khan O. 202 207 Khan S.I. 91 150 Khanna R.K. 86 Khanna S.N. 41 Kharisov B.I.108 Khattar R. 6 261 388 Khemani K.C. 34 37 38 Khenkin A.M. 502 Khodakovsky I.L. 244 Khor L. 200 Khramenkov V.V. 257 Khwan K.K. 457 Kibala P.A. I38 Kida S. 172 279 297 329 344 Kidani Y. 233 Kidd C.E. 371 Kiefer G.E. 319 Kiefer J. 54 Kienze R. 258 Kiesewetter D.O. 462 464 Kieslich A, 438 Kihara N. 26 Kihlberg T. 463 Kihn-Botulinski M. 254 Kijima N. 403 Kikkawa K. 342 Kikuchi K. 34 35 36 246 306 449 Kikuchi M. 403 Kilbourn M.R. 454 464 Kilian H. 42 Killough P.M. 134 Kim C.G. 123 Kim D.W. 256 Kim G.S. 131 Kim H.-J. 111 474 Kim H.K. 324 Kim I.-S. 407 414 Kim J. 12 111 512 Kim J.I. 470 471 Kim K. 111 173 Kim K.W. 80 230 Kim M.A. 471 Kim M.J. 324 Kim S. 12 376 Kim S.-H.250 256 335 413 414 Kim S.J. 247 Kim W.-D. 319 Kim Y.H. 442 Kim Y.I. 475 Kimura E. 268 295 313 319 510 Kimura K. 333 Kindo K. 436 King G.S.D. 326 King H.F. 292 King R.B. 55 128 212 261 380 King W.A. 256 Kinnear K.I. 337 Kinoshita I. 42 236 Kinoshita K. 402 Kinoshita M. 450 451 Kinoshita N. 404 Kintzinger J.P. 196 Kinuya K. 466 Kipp C. 181 Kiprof P. 166 311 358 Kira M. 47 Kirchhoff J.R. 163 Kirchner K. 480 Kireeva O.K. 183 200 204 336 Kirilyuk A.I. 396 Kirk A.D. 318 Kirk J.M. 146 Kirk K.L. 464 Kirk M.L. 161 162 278 295 306 497 Kirschbaum K. 68 Kirsch-De Mesmaeker A. 301 Kirss R.U. 88 362 Kiseleva A.A.. 261 Kishii N. 267 Kishio K. 403 Kishita M. 451 Kiss G.371 Kiss T. 508 Kita M. 272 Kita P. 483 Kitagawa S. 197 Kitagawa T. 204 273 306 500 508 Kitaigorodski A.N. 149 Kitajima N. 188. 203 204 273 506 508 510 Kitami Y. 410 Kitamura T. 89 90 Kitamura Y. 158 Kitano K. 236 Kitazawa K. 403 Kitching W. 226 Kivekas R. 78 206 207 314 437 Kiymac K. 446 Kjekshus A. 199 Klabunde K.J. 21 1 Author Index Klaff N. 14 Klahn A.H. 357 Klapotke T.M. 16 53 82 89 238 Klapper H. 114 Klar G. 182 Klausmeyer K.K. 149 Kleck J. 454 Klein H.-F.. 376 384 Klein L. 446 Klein M.L. 38 Klein W. 365 Kleine M. 166 257 374 Klement U. 202 Klemperer W.G. 117 Klenze R. 470 471 Klepper S.J. 451 Klimek B. 250 Kliner D.A.V.. 475 Klinkhammer K.W.50 Klinkowstein R.E. 454 Klivenyi G.,465 Klosowski P. 442 Kmieciak A. 59 60 Knapp F.F. Jr. 457 465 Kniaz K. 39 406 Kniep R. 68 Knigge H. 463 Knight Castro H.H. 466 Knitter R. 406 411 Knobler. C.B. 5 91 111 261 Knoch F. 140 287 288 292 297 505 511 513 Knoechel A, 464 Knoeppel D.W. 387 Knorr K. 443 Knorr M. 387 Knosel F. 254 Knott A.F. 463 Knotter D.M. 198 271 Knox S.A.R. 373 381 Knuttel K. 513 Kobashi M. 451 Kobayashi A, 399 Kobayashi K. 73 175 321 Kobayashi N. 402 403 Kobayashi T. 398 436 Kobayashi Y. 456 Kobe S. 427 Kober E.M. 475 Kobiro. K. 323 Koborov M.M. 169 Kobuke Y. 306 Koch H.-J. 16 113 Koch J. 247 Koch P. 164 Koch S.A. 78 179 502 Kochanski G.P. 37. 406 Kochi J.K.176 272 Kocian 0..348 Kociok-Kohn. G. 68 252 260 Kockelmann W. 446 Koczon L.M. 178 Kodama T.. 36 245 270 Author Index Kodas T.T. 195 256 Kodera M. 329 344 Kodialam S.,417 Koe J.R. 222 Koefod R.S. 40 223 Kohler H. 206 Kohler J. 117 247 Kolle U. 216 361 365 373 Konig E. 291 Koenig M. 65 Koenig S.H. 308 Koenig. T. 369 493 Koenig. W.A. 461 Koepsel R.R. 169 Koert. U. 240 Kofod P. 486. 504 Koga. N. 127 Koga T.. 403 Koga. Y.. 461 Kogawa 0..468 Koh. H.J. 89 Kohgi M. 428 435 Kohrnoto T. 435 437 Kohn R.D. 246 Kohout J. 206 Kohutova M. 108 Kohzuma T. 201 297 506 507 Koide Y. 370 Koika Y . 403 Koikawa. M. 279 Koike. T.. 100 313 510 Koike. Y.. 399 Koine N. 144 Koizumi.M. 465 Kojic-Prodic B. 124 195 196 Kojima H. 440 Kojima M. 96 461 467 Kojima. N. 179 Kojima S. 72 Kolar-Anic L. 481 Kolasa K.A. 316 Kolesnikov N.N. 30 396 Koley A.P.. 279 292 448 Kolis J.W. 58 79 84 156 157 Koller M. 492 Kolomejtseva. I.V. 469 Kolsky K.L.. 457 Koman M. 175 Komarov V.F.. 469 Komiya H. 512 Komiyama M. 248 Komorita S.. 200 Komova M. 466 Komura K. 470 Kondo H. 327 491 Konetschny-Rapp S. 500 Kong P.-C. 163 Konidaris P.C.. 355 Konig E. 193 Konig. M. 64 Konigstein K. 416 Koningsberger. D.C.. 237 Konishi. H. 61 Konishi J. 465 Konishi K. 435 438 499 Kon’kov S.I.,469 Konno M. 39 Konno T. 163 197 271 Konstantinova L.I. 470 Kony. M. 195 Konya. G. 492 Konze W.V.242 KOO S.-M. 123 Koo Y.Y . 455 Koola J.D.. 363 480 Kopajtic Z. 469 Kopf J. 197 Kopinga K.. 437 Kopnin E.M. 412 Kopyczok. J.. 442 Kopylov N. 37 405. 406 Korall B. 115 Kornath A, 81 Kornilovich B.Yu. 469 Kornuc J.J. 512 Koroleva L.I. 442 Korotkov V.E.. 30 396 Korsakova. N.A.. 460 Korszun Z.R. 505 Kortan A.R. 37 404 405 406 Korthius V.C. 417 Koschmieder. S.U.,45 Koscielniak T. 467 Koskikallio J. 490 Kosorukov A.A.. 469 Koss V. 470 Kostadinovic A. 469 Kostic N.M. 474 Kostic P.J. 397 Kostikas A, 191 Kostiner E. 417 Kostka K.L.. 183 Kotani. A,. 427 Kotasthane A.N. 29 Kothari K.K. 465 Kotlyarov Y.,407 Kotzler J. 446 Koubek E.. 487 Koudelka. J. 334 Koulougliotis D. 497 Koutani.S. 445 Koutsantonis G.A. 24 Kovacs J. 457 Kovacs Z. 454. 456 Kovalev Y.G. 401 Kovba L.M.. 412 Kovert K.J. 48 Koy J.. 32 KOZ~W~I. K.. 203 Kozelka J. 236 Kozic V.S. 460 Koziol A.E. 250 Koziorowski. J.. 459 Kozirovski Y.. 38 Kozisek J. 201 Koziskova Z. 201 Koz’min. A.S. 88 Kozuka H.. 256 Kraatz H.-B. 156 Kraeutler B. 503 Kraft S. 54 71 Krajewski J.J. 395 400 401 407 Krakauer. H. 397 Kramer. K. 136 246 263 Kransz E.. 158 Kratschrner W. 35 Kratz. J.V. 4.57 Kratzer K. 456 Krause H. 220 Krause J.. 366 Krauss. M.. 509 Krautscheid H. 46 79 191 Krchnak. V. 334 Krebs. B. 32 63 70 75. 122 179 27 I Kreegan K.M. 38 Kreek S.A. 457 Kreilick R.W.. 202 Kreines N.M.. 396 Kreiter C.G..377 Krejcik. M.. 167 Krekels T. 395 Kremer. R.K.. 244,400 445 Krenek. P. 466 Kress. J. 354 Kresz. J. 179 Kretchmar Nguyen S.A. 292 Kretz C.M.. 327 Kriauciunas. A. 500 Krichevtsov B.B. 441 Krickemeyer E. 167 Krishnamurthy S.S.,70 Krogh-Jespersen K. 215 Krohn. K.A. 463 Krok-Kowalski J. 442 Kroll G.H. 39 246 Krot. N.N. 263 264 Kroto H.W.. 33 34 35 36. 38. 39 63 Krouse I.H.. 84 Krovich D.J. 444 Kruger. C.. 364 Kruger. T. 179 199 Krug. A.. 372 Kruger. P.E. 205 297 Krusic P.J. 37 48 Ku H.C. 446 Kubas. G.J.. 140 389 Kubat-Martin K.A. 140 Kubiak C.P. 178 Kubiak R. 199. 416 Kubin R.F.. 104 Kubo K. 394 399 Kubo. Y. 37. 405 Kubo-Anderson. V. 28 Kubota M. 174 Kucharski E.S.149. 200 Kuchen W.. 62 Kuchern. W. 186 Kuckel. M. 425 Kudelin B.K. 460 Kudinov V.I. 396 Kudo A, 124 Kiihn F.E. 166 Kiipper S. 10 Kueppers H.-J. 314 Kuersch R. 446 Kuga Y . 457 Kuhlman R.L. 151 Kuhlmann B. 44 Kuhlmann Th. 101 Kuhn A, 363 Kuhn N. 44 Kuipers P. 458 Kulakov M.P. 30 396 Kulkarni S.B. 174 Kulyukhin S.A. 256 Kuma H. 201 507 Kuma K. 405 Kumar M. 202 279 Kumar R. 23 197 Kumar S. 328 337 Kumar U. 94 Kumaravel S.S. 83 Kumon. T. 174 Kunai A, 100 Kunert C. 247 Kung H.F. 164 465 Kung M.P. 465 Kunimoto M. 435 Kupferschmidt W.C.H. 469 Kurczak S. 456 Kureshy R.I. 289 Kurihara H. 342 Kurimura Y. 490 Kuriyama H. 435 439 Kurrnoo M. 35 200 363 Kuroboshi M.85 Kurochkin V.K. 256 Kuroda K. 158 Kurogi Y. 295 Kurosaki H. 295 Kurosawa H. 21 1 366 Kuroshima S. 405 Kurozumi S. 460 Kurpiel-Gorgol R. 245 Kurtz D.M. 187 Kurtz D.M. Jr. 187 274 501 Kurz S. 70 Kurzawa M. 444 Kushi Y. 271 Kustin K. 480 481 495 Kusunoki M. 153 Kusz J. 442 Kutner W. 37 Kuwatani Y. 375 Kuzrnany H. 404 Kuznetsov A.M. 474 Kuznetsov Yu.V. 470 Kwiatowski M. 186 291 308 Kwik W.L. 71 219 Kwok D.-I.A. 340 Kwok W.K.. 451 Kwon Y.U. 191 Kwong. H.L. 198 Kyritsis P. 474 K’yung D.D. 459 Kyuno E. 181 498 Kyushin S. 42 Laang. H. 182 Laangstroem B. 462 463 Laasonen K. 36 Laban J.A. 435 Labar D. 462 Labarta. A, 444 La Bounty L. 376 Lacaze. R. 436 Lacerda A, 425 Lachiotte R.188 501 Lachkar M. 254 Lachmann J. 24 Lacorre P. 441 445 Ladd J.A. 43 Ladenstein R. 509 Ladetsky M.. 462 463 Lage M.. 158 Lafleur A.L. 34 Lafond. A, 407 421 Lage M. 63 70 Lagow R.J. 85 Laguna A, 88 241 Laguna M. 88 241 Lah M.S. 161 162 278 278 496. 497 Lahderanta E. 442 Lahiri G.K. 182 Lahiri G.T. 491 Lahoz F.J.. 218. 219 241 365 Lai C.K. 480 Lai T.-F. 218. 242 287. 476 Laibowitz R.B. 242 Laiho. R. 442 Laitinen R. 83 Lake C.H. 24 Lakin M.T. 54 245 331 342 Lakkis D. 366 Lakshminarayanan M. 202 285. 291 Lal G.S. 85 Lal H.B. 443 Lal T.K. 278 Lalancette R.A. 203. 358 Lalinde E. 88 Lam. H.W. 218 Lamb J.D. 331 Lamb L.D.. 34 Larnbert F. 465 Lambert J.B. 44 Lambert J.-M..34 Lambertsen T.H. 51 Lambrecht R.M. 456 462 468 La Monica G. 197 205 Lamrhari D. 477 Lancaster S.J. 116 Lance M.. 162 261 264 265 497 Lanchester P.C. 396 398 Author Index Landais P. 463 Landau D.P. 432 Lander G.H. 425 428. 440. 447 Landesman C. 456 Landron C.. 413 Lane J.D.. 139 155 Lanfranchi M. 207 269 386 Lang H. 56 Lang H.Y. 416 Lang M. 446 Lange G. 62 Lange. N. 25 Lange. T. 41. 446 Langer S.H. 209 Langley G.J.. 34 38 39 Langlois M.-H. 251 Langridge S. 447 Langstroem B.. 461 Lannin J.S. 404 Lannoo M. 404 Lanza S.. 485 Lapinte C. 359. 363 Lapkowski M. 196 Laplante J.-P. 482 Lappas D. 165 Lapperet. M.F. 115 Lappert M.F. 45 48 253 Lappin A.G. 475 Laramay M.A.H.69 Larbot A.. 113 Larkin P.J. 498 Larkworthy L.F. 185 187 193 291 Laroque D. 186 289 Larrabee J.A. 508 Larrarnendi. J.I.R. 202 Larsen J. 462 Larsen K.S. 510 Larson E. 161 278. 289 295 497 Larsson R. 182 482 Larter. R. 481 Lartiges. S. 50 Laschi F. 176 Lashkul A.V.. 442 Laslo N. 193 Lasne. M.C. 462 Latinen. R.S. 77 Latos-Grazynski L. 180 Latronico M. 178 Latten. J.L.. 337 Lau T.-C. 477 Laude. D.A. Jr. 37 Laughlin L.J. 51 1 Lauher J.W.. 39 Launay S. 410 Laurenczy G. 482 Laurent J.-P.. 204. 206. 287 Laurent J.P. 437. 448 Laval J.P. 423 Lavender I. 58 Lavender M.H. 379 Lavenne F. 463 Author index Laverty J.R.. 241 Lavery A.J. 207 342 Lavi N.. 455 Lawless G.A.115 Lawrance. G.A.. 159 321. 322. 484 Lawrence. D.S. 488 Lawson. D.R. 37 Lay. P.A.. 121 218 477 487 496 Lay. U. 44. 56 Layh. M. 24. 43 50 Layher E. 46 Lazar. D.. 149 Lazir. I. 312 319 Lazich S. 469 Lazraq. M.. 44 Lazziz. I.. 113 Le L.P. 436 Leach. J.B. 214 Leahy. D.J. 68 Leal. J.P. 263 Lear Y. 343 Leask M.J.M.. 447 Le Bail A,. 108 410. 422 Le Bars D. 463 Lebech B. 425 Lebender. D. 481 Le Berre-Cosquer N.. 377 Leblanc M. 142 Le Bozec. H. 360 Le Breton. C. 460. 463 Lecas-Nawrocka. A, 498 Leccabue. F. 427 Lechner P. 287 Leclaire A, 416 417 Lecuyer. C. 116 Leduc P. 183 285 500 Lee. B.S. 469 Lee C.. 456 457 Lee. C.H. 451 Lee D.M. 457 Lee. F.L.. 152 Lee. G.-H. 356 390 448 Lee H.Y.129 Lee J. 110. 173 Lee J.C.. 24 Lee. J.D. 455 Lee. J.M. 455 Lee. J.W. 40 223 Lee. K.-W. 149 Lee M.S. 510 Lee S. 4 108 Lee S.C. 123 Lee. S.L.. 425 Lee T.W. 465 Lee U.. 129 Lee. W.-0.. 477 Lee W.L.. 191 Lee Y.J. 180 Lee Y.W. 71 Leeaphon. M. 357 Lees. A.J. 145 Leeuwen. P.W.N.M.. 229 Ixfebre F.,116 Lefebvre F. 5 Le Flem G.. 199 416 Le Floch. P.. 147. 270 Le Fur Y. 247. 423 LeGall. J. 503 Legendziewicz J. 248 250 Leger J.-M.. 251 Legin V.K. 470 Legras L.. 423 Legzdins P. 69. 354. 390 Lehmann W.D.. 466 Lehn. J.-M. 196. 240 298 Lehtonen. A.. 204 Lei X.. 80. 133 160. 180 191 Lei. Y. 73 Leibnitz. P.. 163 163 Leidner C.R.. 214 Leigh G.J. 68. 117. 127 128 277 312 511 Leininger.T. 167 Leipoldt J.G.. 164. 166 480. 484 Leis. C. 144 Leites L.A. 3 Lelievre D.. 204 448 Lelj F.. 327 Lemaire. C. 455 460 464 467. 481 Leman J T. 26 Le Marechal J.-F.. 264 Le Mercier T. 423 441 Lemmetyinen H.. 490 Lemos M.A.N.D.A. 165 355 Lernpers. H.E.B. 283 Lengyel I. 481 Lennhoff D.. 53 Lentz D. 42 88 Lenz. R.W. 93 Leondiadis L.. 498 Leone. M.. 498 Leong V S.. 68 260 Leoni. P.. 229 Leonov. V.V.. 460 Leovac V.M. 285 285 Leparulo-Loftus M.. 129 Lerchen M.E.. 119 Lerke S.A. 37. 40 Leroi. G.E. 475 Leschke H.. 437 Lessmann K. 90 Lettko. K. 130 Leu L.-C. 147 Leung K -H. 203 294 488 Leung W.-H. 287 Leurs. G.4.J. 458 Leute A, 179 Le Van D.. 62 63 70 Levanon H.37 Levason. J. 175 Levason. W. 158 159 211 Lever A.H.P.. 21 1 Levy J.P. 401 Lewis FA. 209 541 Lewis. J. 102 176. 219 220. 380 382 383. 385 Lewis. N.S. 217 Lewis. R.. 363 Lewis. T.A.. 40 217 Lewkebandara. T.S.. 109 Lexa D.. 475 Ley S.V.. 341 Leyba J.D. 457 Lezama L. 276 L'Handon P.. 377 L'Her. M. 182 Lhuillier C.. 430 Li C.H. 433 Li. C.-K. 285 287 476. 477 Li C.S. 213 Li D. 197 198 Li G.Q. 160 Li J. 123 127 421. 481 LI. J.-B. 509 Li L.-M.. 247 Li Q.. 34. 37 38 39. 162 449 497 Li Q.Y.. 45 Li S.H. 61 Li X.. 161 162 278 399. 497 Li Y. 346 Li Y.F. 30 401 404 Li Y.-J. 132 483 506 Li. Y.W. 55 380 Li 2.. 237 386 Li Z.W. 217 Li Z.-Y. 279 Liang H. 258 Liang J.. 503 Liang.J.K. 419 Liang. M. 98 Liang S.. 433 Liang W. 269 Liangren H. 204 305 Liao D.. 204 289 Liao D.-Z. 207. 301 448 Liao F. 457 Liao F.L. 199 416 Libby E. 162 203 497 Librnan J. 191 Licchelli. M. 238 320 Lichtenhan J.D. 151 Lickiss. P.D. 43 128 Liddell G.F. 174 482 Liddell M.J. 384 Lieb K.P.. 443 Lieber C.M. 37 Liedle S.. 71 Lieser K.H. 453 Lifson. S. 191 Lii. J.-C. 386 Lii K.H. 416 417 433 Limbach H.-H. 142 Lin. B. 102 Lin. C.-T. 487 Lin. G.-Y. 259 Lin H. 425 425 Lin H.C. 199 416 Lin H.Q. 429 542 Lin J. 199 420 Lin M. 391 Lin Q. 182 446 498 Lin R.-C. 390 Lin S. 171 Lin S.C. 25 Lin Y. 258 259 Lin Y.-C. 367 Lin Z. 41 107 351 Linck R.G. 357. 489 Lincoln D.M.362 363 480 Lincoln F.J. 197 Lincoln S.F.. 346 489 Lindahi P.A. 505 Linder L. 458 Lindgren J. 248 Lindmark A.F. 489 Lindner E. 64 127 218 Lindner J. 438 Lindoy L.F.. 183 339 Lindsay D.B. 461 Ling H. 251 Ling J. 204 508 Ling J.R. 463 Link J.M. 463 Link M. 258 Linn K. 27 177 214 Linsday R. 397 Linse K.H. 466 Linti G. 5 L.iou K. 182 199 Liou Y.-L. 202 Lippard. S.J. 118 119 162 171 183 189 231 353 497 Lippens W. 315 316 Lippmann E. 358 Lipscomb J.D. 500 502 Li Rukang 400 Lis T. 291 Lisek C.A. 288 Lissner F. 247 Liu B.L. 465 Liu F.-q.,48 Liu H. 80 133 160 180 191 395 Liu J. 250 482 Liu L. 207 508 Liu L.-K. 25 356 390 Liu M. 456 503 Liu P. 171 Liu Q. 124 Liu Q.-T.132 Liu. R.-S. 30 356 395 397 Liu S. 35 118 130 162 183 189 197 297 306 497 Liu S.-X. 203 Liu S.T. 197 Liu W.-D. 171 Liu X. 205 Liu Y. 256 437 Liu Y.-J. 421 Liu Boli 467 Liufang W. 275 Livaniou E. 467 Llamazares A, 357 Lledos A, 176 245 486 Llopis. E. 151 Lloret F.. 201 202. 204 206. 302 303. 448 Lloyd E. 474. 503 Lobana T.S. 203 Lobkovsky E.B. 113. 136 146 159 162 287 Lobo. R.C. 199 Lochmann L. 45 Lockhart J.C. 78 313 314 337 Lockwood D.J. 445 Loeb S.J . 314 Loehneysen H.V. 446 Loehr T.M. 180 204. 508 508 Loennecke P. 58 83 Losch S. 399 Loewenhaupt M.. 443 Loffler J. 254 Loragager T.. 73 478 Logvinova V.B. 108 Loiseau T. 29 Lokaj J.. 180 Lomis T.J. 169 Lomprey J.R.360 Lonergan. M.C. 253 Long C. 269 Long E.C. 270 Long G.J. 371 372 439 Long N.J. 274 Long X. 456 Longato B. 28 Longford C.P.D. 462 463 464 467 Longoni G. 57 385 Longridge E.M. 195 Loock. B. 182 498 Looney A, 277 509 Loos-Neskovic. C. 470 Lopez A.M. 7 492 Lopez C.A. 195 Lopez J.A. 218 Lopez M.A. 182 213 Lopez R. 27 Lopez X. 205 283 Lopez-Mut A, 250 Lorenz. H.,163 Lorenz. I.-P. 389 Lossin A. 250 Lothian A, 248 Lough A.J. 11 16 44 Lounasmaa O.V..426 Loupy A. 490 Love C.P. 200 Lovesey S.W. 428 432 Lovinger A.J. 98 Lowe C.B. 170 Lowery M.D. 199 203 506 Loy D.A. 38 Lu. C. 127 Lu J. 68 84 124 127 132 155. 160 163 164. 467 509 Lu J.X.. 195 Author Index Lu K.-J. 12 Lu K.-L..377 378 Lu S.. 127 Lu T.-H.. 202 Lu Y. 508 Lu. Y.-J. 35. 156 421 L.u. Z. 367 Luan L.. 141 354 Lubecka M. 442 Lucas C.R.. 297 338 Lucas E.A. 377 Lucente S.. 224 Luchinat C. 109. 318 507 508 509 Lucier G.. 423 Luck R.L. 137. 155 Lucke J.. 69 Lucken E.A.C.. 195 Ludden P.W.. 505 Ludi. A,. 218 Ludwig M.M. 149 Ludwikow. M. 283. 475 Lugan. N.. 280. 357. 387 Luger P. 88 Luic M. 195 196 Luinstra G.A. 115. 351 Luke A.W. 83 Luke G.M.. 436 Lumini T. 362 Luna S.A. 318 Lunniss J.A. 385 Luo H. 442 Luo J. 493 Luo s.,375 LUO X.-L. 165. 224 281 357 Luthra S.K. 463 Lutz H.D. 25 247 Lutz. M.. 180. 190 Lutz T. 467 Luxen A, 459 Lyard P. 34 Lykke K.R. 36 246 Lynch T.J. 492 Lynch V.261 335 340 Lyne. P.D. 77 Lynn J.W. 446 Lynn M.H. 207 Lyons K.B. 404 Lyons T.J.. 508 Lyster D.M. 467 Lytle F.W. 36 246 Ma H. 261 Ma. Q.Y. 242 Ma R. 478 Ma Y. 151 Ma Z. 251 Maarmann H.. 105 Maas G. 63 Maatta E.A. 130 Mabbs F.E. 128 Mabrouk H.E. 202 Mabry T.E. 460 McAfee. J.G. 466 Author Index Macartney D.H. 489,492 Macaskie L.E. 261 McAuley. A, 78 314 316. 476 McAuliffe. C.A. 53 75 160 161 174 177. 185 289 468 Macca. C.. 28 McCann. M. 202 McCann V.H. 435 McCarley R.E. 124 McCarron E.M.. 114 McCarthy. C.J. 204 McCauley J.P.. Jr. 38 404 Macchioni A,. 480 McCleverty J.A. 154 234. 267. McClinton D. 146 McClure S.M. 36 McConnachie J.M. 80 McConnell A.A. 202 McCormick W.D.481 482 McCracken J. 507 509 McCusker J.K. 172 189 192 448 449. 501 MacDonald M.A. 79 McDonald R. 103 178 McDonald. W.S. 8 McDonald Ruscitti T. 181 McDowell. K.A. 32 McElfresh M.W. 425 McElroy W.J. 480 McElvany S.W. 36 246 McElwee-White L. 69 McEwan K.A. 427 McGeary M.J. 195 McGhie A.R. 39 406 McGinley J. 289 McGovern J.J. 471 McGowan P.C. 353 McGrady. J.E. 37 McGreevy. R.L.. 428 McGregor K. 148 Macgregor S.A. 8 McGuire. M.E. 213 477 McGuirl M.A. 507 McGurie M.J. 210 Mach K. 115 Mach R.H. 461,464 Machado F.L.A. 442 Machell J.C. 229 Macherone D. 121 Machida K. 255 Machida M. 197 Macias. A,. 174 Macicek. J. 233 Macintosh A,. 427 McIntyre G.J. 425 441 Mack J.255 McKeage. M.J. 210 McKee M.L. 4 McKee V. 306 329 347 McKelvey M.J. 109 McKenna A.G. 149 Mackenzie A.P. 30 McKenzie D.R. 35 Mackie A.G. 53 160 177 McKinnon J.T. 34 Mackintosh A.R.. 425 McKusker J.K. 299 306 MacLachlan D.J. 114 McLain M.E. 471 McLain. S.J.. 492 MacLaughlin S.A. 379 McLean. A.J. 73 McLendon G. 495 McLoughlin M.A. 124 McMahon I.J. 362 McMahon R.J. 361 McManus A.V.P.. 419 McManus N.T.. 364 McMillin D.R. 509 McMorrow D.F. 425 McNamara M.A. 484 McNerlin C.J. 194 McPartlin M. 68 74. 117 128 164 183 220 250 256 306 339 356 McPhail A.T. 23 I28 McPherson D.W. 465 Macpherson K.A. 381 McQuillin F.J. 210 MacRory P.P. 160 McWhan D.B. 428 McWhinnie S.L.W. 273 McWhinnie W.R.194 Madariaga G. 206 276 Madaule Y. 71 Maddox P.J. 223 Madelmont J.C. 465 Madelung O. 427 Miicke H.R. 164 Maeda M. 461 464 465 Maeda T. 400 Maeda Y. 193 279 296 Maeder M. 321,484 Maeder U. 272 Maeding P. 465 Maegawa S. 435 437 Maelger H. 197 Maelia L.E. 78 179 502 Maenhoudt M.. 396 Maestri M. 274 Magarshak Y.. 474 Magata Y. 467 Magde D.. 192 299 493 Mager M. 229. 376 384 Maggi L. 469 Magill J.H. 96 97 Magnon. L. 292 Magnuson V.R. 370 Magon L. 164 454 Mague J.T. 227 228 366 Maguire J.A. 12 Magull J. 255 Magull S. 80 Magyar 1.. 482 Mahan C.A. 32 Mahapatra S. 276 Mahe P. 410 Maher E.T.. 212 Maher J.P. 154 203 277. 373 Mahfouz R.M. 459 Mahon M.F. 16 Mahootian F.481 Mahroof-Tahir M. 197. 204 306 508 Mahu-Rickenbach A. 273 Maia J.R.S. 226 Maier J. 400 Maier. R.. 258 Maier S. 389 Maier-Borst W. 455 463 465 Maignan A, 396 398 401 Maigret N. 66 67 Mailman R.. 467 Maiorova A.F. 199 Mairles-Torres P. 114 Maitlis P.M. 376 480 Majima K. 297 497 Majoral J.-P. 117 127 Mak T.C.W. 173 197 202 206 263 269 279 318 Makarovsky Y. 34 Makhija A.V. 404 Maki H. 468 Maki J. 432 Makino R.. 500 Maklachkov A.G. 455 Maksymowicz L. 442 Malachowski M.R.. 306 Malaman G.,439 Malar E.J.P. 66 Maldotti A. 109 224 Maleknia S.. 335 Maletka K. 263 Malfait M. 466 Malhotra R.. 328 Mali T.N. 322 Malik. S.K.,425 Malinovskaya S.A.. 432 Malinovski T.I. 285 Malinovskii Yu.A.248 Malinsky J. 474 Malisch W. 56 65 147 Malish. W. 380 Malkiman V.I. 469 Mallah T. 200 Mallela S.P. 43 Mallouk T.E. 114. 475 Malm J.O. 178 Malmborg P. 461 463 Malmstrom B.G. 499 Malone B. 33 21 I 351 Malone J.F. 347 Maloney S.D.,225 Malouf E.Y. 176 Maltese P. 196 Malyarik. M.A. 26 27 Manabe K. 460 Manassero M. 384 Manchanda R. 160 Mandal. S K. 138 174 203 304 305 309 449 Mandolini L. 314 Mandon D. 182 500 Manek E. 248 Manfei P. 457 Manfrin M.F. 339 Mangani S. 510 Mangano C. 320 Manheimer M.A. 442 Mani F. 312 318 Maniukiewicz W. 448 Maniwa Y. 405 Mann B.E. 225 362 Mann C. 362 Manna J. 355 Manners I. 16 93 97 98 103 Manning M.J. 261 Manning R.G. 467 Manning T.M.484 Manocha S.K. 148 Manohar. H.. 285 Manoharan P.T. 292 448 Manojlovic-Muir L. 382 Manolopoulos D.E. 35 36 Manorahan P.T. 279 Manotti- Lanfredi A. M . 202 Manoussakis G. 202 Mansuetto M.F.. 421 Mansuy D. 182 Manthiram A.. 30 394 398 Manuel G. 101 Manzur C. 145 Mao L.F. 417 Mao Z. 207 508 Maple M.B. 396 Mar A. 421 Marcalo J. 263 263 Marchaj A, 322 328 478 Marchi A, 84 164 166 292 465 Marchon J.-C.. 180 181 Marco J.F. 444 Marcos. M. 105 Marcus R.A. 474 Marder T.B. 13 102 220 363. 492 Mardones M.A. 71 Marecaux A, 185 Marek M. 482 Marezio M. 395 401 Margenau W.H.,455 Margerum. D.W. 90. 481 Margouleff D.,454 Margulis T.N. 31 1 Maria C.R. 221 Marinetti A, 58 Marinez E.28 Maringgele W. 19 Markert J.T. 394 Markies B.A. 227 Markiewicz A, 287 Markl G.,66 67 Marko L. 179 Marks J.E. 93 Marks L.D. 411 Marks T.J. 116 244 256 257. 265. 328 Marmocchi. F.. 507 Maroney. M.J. 187. 191. 505 Marooka. Y. 215 Marquart. T.A. I17 Marques. H.M. 483 Marques N.. 263 Marquez A,. 160 Marrs D.J. 204. 347 Marschall R.. 88 Marsden. C.J.. 149. 157 Marsden I.R.. 200 Marsden P.J.. 471 Marsh R.E. 246 Marshall W.G. 187. 425 Marsmann. H. 42 Martell A.E. 28. 172 304 312 344 467 509 Martin. A. 196. 285. 381 Martin. B.D. 182 491 Martin. C.R. 37 54 Martin J.D.. 136 Martin L.L.. 285 Martin M.. 283 Martin R.L.. 37 164. 264 Martin S. 62 Martin. T.P. 41 Martin. W.R.. 275 Martineau P.M.446 Martinelli M. 382. 383 Martinengo S. 68. 384 385 Martinez A,. 115. 201 Martinez B. 440 444 Martinez. F. 88 Martinez. J.L. 440 Martinez. M. 321 322. 484 Martinez. P 476. 483 Martinez-Ferrer M.J. 509 Martin-Frere. 129 Martin-Llorcnte. J.M.. 437 Martins. J.L.. 405 406 Martinsen K.-G.. 26 Marty W.. 174 484 Martynenko L.I.. 201 Maruya. K.. 124 Maruyama K. 267 288 Maruyama S.. 268 319 Maruyama Y. 361 451 Marvelli L. 84. 164. 166. 292 Marx. H.. 455 Marzilli. L.G. 164. 182. 285 292 503 Masaki N.M. 458 Mascarenhas Y.P.. 301 496 Mascetti J. 143 Mascharak. P.K.. 79 191 192 295 505 Masciocchi. N. 68 197. 205 384 385 Maseras F. 176 Mashima K. 134 Mashino T. 288 Mashuta M.S..189 306 501 Author Index Masi D. 27 177 214 Masiker M.C. 489 Mas’ko A.N. 469 Mason J. 120 185 Mason M.R. 288 Mason. S.. 235 236 352 Mason. T.E. 431 433. 440 441 Massa W. 67. 197. 200 422 423,434 439 Massabni A.C.. 200 Massarotti A.. 238 Masschelein A, 189 Massey J. 98 Massing S. 406. 41 I Massoud. S.S.. 204 Massous. S.S.. 305 Masters A.P. 144 Mastrorilli P. 178 Masuda H. 170. 200 297 506 Masuda. K.. 361 464 Matacchieri R.. 454 Matano. Y. 61 Matear. P.P. 160 Mateev D. 402 Matern E.. 46 Mathai C. 455 Mathakar A.R. 456 Mather S. 471 Mathew. E.J.. 207 Mathews 1.1.. 201 Mathey F. 58 62 66. 67. 147 264. 270 272 Mathias C.J.. 455 464 467 Mathias S. 336 Mathieu. R. 117 127 214 280 387 Mathis.C.A.,467 Mathis H. 146 Mathur. P. 79 279. 287 Matonic J.H. 135 Matos J.R. 245 Matsubara H.. 190 Matsubayashi G.. 33 80 129 I54 Matsuda. H.. 466 Matsuda. M. 440 Matsuguchi A,. 100 Matsuhashi. Y. 50 Matsui Y. 396. 402 Matsuki K. 448 Matsumara. K.. 332 Matsumiya. S.. 404 Matsumodo. N.. 329 Matsumoto A,. 301 Matsumoto H.. 42 Matsumoto K.. 337 Matsumoto M. 451 Matsumoto N.. 172. 297 301. 303 344. 448 497 Matsumoto T.. 49 Matsumoto Y. 13 Matsuo M. 414 Matsushirna H.. 465 Matsushita H. 322 Author lndex Matsuyuki J.-i. 89 Matsuzawa N.. 40 Matt D. 366 Mattar. S.M. 83 Mattausch Hj. 244 247 Mattenberger K.. 447 Mattes. R. 158 207 315 338 Mattfeld. H. 247 Matthews D.M..6 Mattice W.L.. 95 Matyjaszewski K. 96 98 Matysik B.E. 331 Matzke. Hj. 244 Matzku S. 465 Maurny M. 289 Maunder G.H. 355 Maury F. 24 Mausner L.F. 456 457 Mautner. F.A. 173 Mauzerall. D. 37 Mavunkal I.P. 5 Mawby. R.J. 215 May H.J.. 443 May K.. 466 May. L. 182 Mayer A.J.. 391 Mayer B. 46 59 Mayer. J.M. 128. 154 166 355 Mayer. M.J. 203 294 488 Mayouf. A. 490 Mays M.J. 381 382 Mazid. M.. 79 222. 273 Mazieres M.R. 63. 226 Mazighi H. 11 Mazzi F. 312 Mazzi. U. 466 M’Barki M.A. 227 Meagher. N.E.. 207 330 476 Mealli B.. 372 Mealli C. 27 177 178 214 Mease. R.C.. 465. 467 Mebel. A.M. 4 Meckel C. 267 Mederos A. 204 Medger G. 53 Mediati M.. 224 492 Medici A, 97 Medvedev V.A.244 Meenakurnari S. 205 Meerschaut A.. 407 421 Meese-Marktscheffel J.A. 261 Meetsma. A.. 84 116 150 407 42 1 Mega I. 145 Meguro K. 241 Mehnert C. 363 Mehrotra R.C. 110. 196 253 Mehrotra. R.N. 476 Mehrotra V. 169 Meidine M.F.. 38 39 63. 70 165 Meijboom N. 260 Mciklyar V.. 37 Meinken. G.E. 457 467 Meinrath G. 470 Meiwes J. 500 Meizhong. W. 465 Mekata M. 435. 436,439 Melanson R. 163 Melchior F. 381 Meli A, 359 365 Melichariik. M. 481 482 Melikhov I.V. 469 Meller A,. 19 Melnyk A.J. 469 Mernmzsheirner. H.. 64 Menage S. 162 187 287. 497 501 Mendiara. S.N. 490 Menescal R. 98 Meng Q. 250 Meng Y.,18 464,467 Mengalti J. 456. 456 Mengchang S. 204. 305 Menovsky A.A. 425 Mensing C.26 Mentzafos. D.. 269. 291 Menz D.H. 26 Menzinger M. 481 481 Merabet. K.E. 170 Merbach. A.E.. 109 163 248. 473. 482 484 Merciei- F. 58 Merciny E.. 250 Merkert. J.W.. 18. 283 475 Merrnillod-Blardet D.. 65 Mertelj. T. 402 Mertens J.. 465 Merwin R.K.. 363. 480 Merz K.M.. ju 486 Merzweiler. K.. 24. 56. 84 Mesa. J.L.. 202 277 Mesbah. K.. 483 Meshularn A,. 322 478 Meskers. S.C.J.. 475 Mesrnan J.. 78 Messerschrnidt. A,. 509 Messori L.. 495 Mestnik S.A.C.. 456 Mestroni G..267 Mesziros C. 149 Metacotta. F.C. 402 Metcalf P. 440 Metcalf. S.G.. 454 Metternich H.J.. 381 Metwally S.A.M.. 467 Meumueller B. 336 Meyer A, 40. 217 Meyer. D.. 251 Meyer. F. 10 Meyer. G.. 246 247 248 250. 263.461 Meyer.J. 190 Meyer. K.E.. 165 Meyer. T.J.. 213 475. 477 Meyer. U.. 64 Meyer-Koscher B. 182 Meyerstein D.. 318 322 478. 482 490 Mezyk S.P.,318 Miao L.. 340 Michaeli A, 37 Michaelis. C. 247 Michalczyk M.J. 235 Michalowicz. A, 182. 498 Michel. C. 395. 396 401 407 412 Michelin R.A.. 210 Micheloni M. 339. 344 347 Michelsen K.. 131 207. 276. 316 Michinobu K. 448 Michiue Y.. 410 Michos D. 165 28 1. 357 Mickelson J.W. 391 Midollini. S.. 80 160 191 272 294 Miertschin. C.S.. 138. 155 Miguel. D.. 155 Mihailovic. D.. 402 Mihaly. L.. 39 Mihichuk. L.M. 148 Mikami H. 435 Mikeska H. 437 Mikheev. N.B. 256 Mikheev. V.L. 243 Miki H. 500 Miki. K. 366 Mikolaewsky S.. 457 Mikulcik. P. 31 Mikuriya.M.. 134. 161 194 294 295 296 297 329. 448. 497. 505 Milani. B.. 227 267 Millar J.M. 38 Millar. M.. 78. 179 294 502. 505 Miller D. 277 341 Miller. D.A. 456 Miller G.J.. 244 247 Miller. J.R.. 219 Miller. J.S. 451 Miller L.L.. 288 Miller. M.M. 217. 263 Millevolte. A.J. 43 Milliken. J. 36 Millington P.L. 71 Millis A.J.. 440 Millrear. M.. 179 Mills A,. 73. 215 Mills. D.K. 185. 334 Milne. J. 490 Milne J.B.. 77 Min K.S.. 36 246 Minami K.. 132 Minarni. T. 197 Minamigawa. S.. 400 Minchin N.J.. 274 Mindach. L.. 34 Mindrul. L.F. 256 Minelli M. 151 Ming. L.-J.. 189 501 508 Author index Minghetti G. 271 Mingos D.M.P.. 77 229 242 Minhas R. 112 Minkwitz R. 53 81 86 Minto F.97 Min-Yu T. 245 Mira I. 237 Miravitlles C. 205 283 Mirebeau I. 443 Mirkin. C.A.,377 378 Mironov A.G. 454 Mironov A.V. 412 Mirzadeh S.,457 468 Misawa S. 394 Mishra K.D. 291 Mishra. L. 323 Mishra S.P.,459 Miskowski V.M. 134 Misra. G.P.,482 Missfeldt M. 466 Mistry P. 232 Misurkin I.A. 432 Mitani T. 170 Mitch M.G. 404 Mitchel. M. 341 Mitchell A.W.. 399 Mitchell G.K. 349 Mitchell J.C. 123 Mitchell K.M. 75 Mitchell T.R.B.,362 Miteva M. 183 233 Mitra P.P. 431 Mitsuda S.. 439 Mitsui T.. 433 437 Mitsumi. M. 172 342 Mittag E. 461 Mittal J.P. 262 Mittelbach A, 34 Mitzel N. 45 Miura S. 341 Miyahara I. 63 65 337 Miyai A. 100 Miyake C. 244 Miyake K. 438 Miyake S. 260 Miyake Y.34 Miyamae H. 183 Miyamoto T.K. 25 235 Miyazaki T. 458 Miyazaki Y. 401. 402 Mizobe Y.. 143 145 230 Mizogami S. 451 Mizoguchi K. 405 Mizra S.A.. 285 Mizuhara Y.. 242 Mizuki. J. 37 405 Mizumachi K. 267 Mizutani H. 199 Mizutani. Y. 306 Mo D. 460 Moberg. C. 273 Moch P. 438 Mochida K.. 42 Mochida M. 403 Mochizuki K. 329 Mochowska E. 446 Modder J.F. 280 Mody T.D.,335 340 Mockel A,. 372 Moezzi A, 3 19 20 Moffat M.R. 220 Moggi L. 339 Moghadam G.. 64 Moghaddas. S. 477 Mogias J.. 88 Mohan M. 279 Mohan T.. 59 Mohialdin-Khaffaf S.N.,85 Moinereau M. 466 Mokhtari M. 404 Molander G.A.,244 Molchanov. V.N.,30 396 Molinari H. 384 Moll M. 140 287 292 297 505. 511 Mollar M.201 202 206. 302 303 Mollard P. 169 Molloy K.C.. 16 23 Molsbeck. W. 53. 86 Molstad J. 38 Momenteau M. 182 498 Monari M. 57 234. 385 Monceau P.. 33 Moncrieff D. 45 Monet M. 387 Moneti. S.. 272 Monge. A. 51 273 364 449 Mongeot H. 5 Monichino A, 238 Monien. H. 440 Moninot G.. 37 Monnanni R. 192 Momsted L.. 143 224 483 486 Mo~rnsted.0..143 224 483. 486 Montague R. 96 Montarroyos E. 442 Montenegro F.C.,442 Montevalli M. 245 Monthoux. P. 429 Monti D. 480 Montoneri E. 114 Monzyk M.M. 160. 476 Moodley K.G. 375 Moody. T.D. 255 261 Mook H.A. 440 Moon R.M. 425 Moore C.P..239. 283 342 Moore E.J. 376 Moore G.R..28 Moore M.H.. 357 Moore M.R. 236 Mooie P.. 268 312 313 504 Moore S.R.254 Morales L. 113 Moran. E. 414 Moran G. 158 Moratal J.-M. 192 509 Mordkovich V.Z. 209 Moreau B. 462 Moreau. C.M. 275 Morelle J.-L.. 459 463 Moreno J.M. 204 207 Moreno M.T. 88 Moreno-Esparza R. 201 Morere A, 45 Moresco A, 466 Moret E.. 275 Moret M.. 197 205 Morgan K.R. 114 Morgan L.W..201 281 Morgan M.W.. 206 Morgan R.J. 283 Morgan T. 174 Morgat J.-L.,460 Morgenstern-Badarau I. 186 289 Mori H.. 466 Mori N. 435 Mori T. 134. 504 Mori. W.. 451 Mori Y. 170 301 497 Morii Y.. 401 402 Morimoto H. 460. 471 Morin B.G.,451 Morino Y. 114 Morishima I.. 180 478 500 Morishima Y. 451 Morita M. 340 Moro G. 178 Morokuma. K. 127 Moron M.C. 439 442 Morooka. M. 175 183 Moro-oka. Y..188 203 204 273 361. 373. 378 379. 506 508 510 Morosin B.. 396 Moroz A. 21 Morozov A.B.. 24 Morris B.C. 397 Morris D. 464 Morris D.E.,39. 395. 470 Morris D.G. 89 Morris J.H. 3 Morris K.B. 262 Morris R.. 419 Morris R.C. 37 406 Morris. R.H. 128 139 145 351 Morrison J.A.. 21 Morrow. J.R. 316 339 Morss L.R.. 246 Mortimer R.J. 348 Mortishire-Smith. R.J..510 Mortlock R.F.. 29 Morton D.A.V.,381 Morton J.R. 37 37 Morton S. 163 272. 294 Morton T.E. 461 464 Morvan V.. 35 Moschalkov V.V.. 412 Moscherosch. M. 167 Moser. C.C..474 Author lndex Moser I.M. 370 Moskwa J.J.. 454 Moss J.R. 352 Mosset A, 113 Mostafa S.I. 90 Mostovoy R. 404 Motekaitis R.J.,172 304 312 344 Motoda K.301 497 Motokawa M. 436 438 Motomura S. 230 Motoya K. 439 Mouallem-Bahout M. 274 Moubaraki B. 205 296 297 Moulay el Moustapha H. 109 Moulis J.-M. 190 Mountford P. 127 214 353 355 372 Moura I. 503 504 Moura J.J.G.,503 504 Mouron. P. 413 Mousley D.P.,78 314 Moussa N.A. 174 Moutet J.-C.,503 Moya M.L. 476 490 Moya S.A. 269 Mozzon M. 210 Mrakavova M. 482 Mrozinski J. 206 207 291 448 Mtetwa V.S.B. 372 Mu. Y. 97 Mudretsova S.N. 199 Muedas C.A. 66 Miiller A. 65 66 125 126 127 167 449 513 Mueller B.G. 247 Mueller B.L. 149 388 Miiller E. 202 Mueller H. 458 Mueller H.-M. 314 Miiller H.S.P. 158 Miiller J. 10 390 Muller. L. 186 289 Mueller M. 79. 191 Mueller R. 425 Miiller U. 54 58 80 84 165 170 Mueller V.80 Miiller-Buschbaum H. 199 Miinck E. 500 512 Muenster A.F. 482 Muenze R. 163 Mui H.D. 137 Muir A.S.. 53 Muir K.W. 382 Mujsce A.M. 404 Mukhail S. 174 Mukherjee A.K.. 153 Mukherjee M. 153 Mukherjee. P. 39 Mukherjee R.N. 185 276 278 279. 287 301 Mukherjee S. 276 Mukhin A.A. 438 Mukkala V.-M. 308 Mukopadhyay P.K.. 398 Mukund S. 51 1 Mul W.P.,21 I 216 Mulder N.H. 210 Mulholland G.K. 454 465 Mullen K. 34 Muller D.A. 35 Muller G. 24 Muller J.G. 317 Muller T.E. 239 Mulley S. 385 Mullica D.F.. 202 248 Mulliez E. 183 285 500 Munakata M. 197 Munck E. 183 Munezawa K. 448 Mufioz. E. 490 Munoz J. 455 Muiioz M.A. 143 Munoz M.C. 201 Munzenberg J. 82 Mura P.224 Murafuji T. 61 62 Murai S. 220 366 Murakami Y. 288 Murali D. 464 Muraoka Y. 403 Murase H. 101 Murase. Y. 468 Murasik A, 263 Murata I. 14 Murata K. 451 Murata. T. 230 Murchie M.P. 81 86 Murillo C.A. 118 Murphy C.P.,212 Murphy D.W. 404,405 Murphy. E. 202 Murphy K.A. 343 Murphy. M. 11 Murray A.M. 122 271 Murray H.H. 132 Murray K.S. 205 280 287 296 297 Murrell J.N. 41 Murrer B.A. 217 232 Murthy. N.N. 204 306 508 Murtiashaw M.H. 461 Musin R.N. 432 Musselman R.L. 182 199 Mustoo. L. 371 Mutin P.H. 101 Mutka H. 449 Muto Y. 175. 203 448 Muttik I.G. 412 Myasoedov B.F. 470 Myasoedov N.F. 460 Mydlarz. T. 442 Mydosh J.A. 446 Myers B.E. 109 Mylrajan M.. 180 Nabeshirna T.336 Nafie L.A. 498 Nag. K. 309 329 Nagai H. 469 Nagamatsu M. 297 Nagamine K. 428 435 436 Nagao H. 191 214 Nagasawa A.. 151 Nagase S. 63 Nagashima H. 31 33. 40. 361 Nagashima U. 206 Nagashio T.. 271 Nagata K. 89. 433. 437 Nagler S.E. 437 Nagoshi. M. 403 Nagy. A, 482 Nagy-Magos Z. 179 Naiki M. 267 Naillon C. 25 Naim A, 34 38 Nair. A.G.C. 456 Nair. V.S. 189 Naito M. 13 Nakadaira Y. 14 Nakadera. K. 329 Nakagawa S. 181 498 Nakahanada M. 150 448 Nakahara N. 34 Nakahashi H.. 462 Nakahigashi. K. 400 Nakai I. 114 Nakajima K.. 101 436 437. 439 Nakamara 1.. 313 Nakamaru K.. 267 Nakamoto K. 180 Nakamoto. M. 191 Nakamura. A, 134. 150 153 179 190 204 260 273 502 508 Nakamura K..172 Nakamura. M. 306. 323 Nakamura N. 201 507 Nakamura. T. 407 414 451 Nakanishi N. 197 Nakano F. 230 Nakano H.. 134 Nakano K. 361 Nakano M.. 432 451 Nakano. Y. 468 Nakao K. 407 Nakaoka. A. 40 Nakashima M. 175 Nakashima S. 501 Nakasuji K. 432 Nakasuka N.. 250 Nakata H. 72. 402 Nakata K.. 151 374 Nakatani K.. 434 Nakaya. C. 61 Nakayama A.. 185 323 Nakayama. Y. 150 301 Nakazawa T.. 481 Nakazawa Y. 450 451 Namavari M. 464 Nambaru S. 461 Namimoto H. 432 Nanda K.K. 309 329 Nanthkumar A. 499 Nara A. 400 Narasimha Rao C.V. 398 Narayan K.S. 451 Nardi N. 347 Narendranath P.K. 101 Naritomi M. 469 Nasa A, 400 Nascimento A.B. 244 Nascimento O.R. 200 301 496 Nasir M.S.197 207 499 508 Nasreldin M. 132 483 Nasri H. 180 181 499 Nasu M. 306 502 Nasu S. 444 Nathankumar A, 207 Nation C.B.M. 356 Nation D.A. 196 292 Natu G.N. 174 Naumann D. 87 88 Naumov N. 407 Navratil J.D. 244 Nazarenko A.Y. 331 Nazeeruddin M.K. 213 Ndifon P.T. 160 Nebeling B. 454 464 Necklesa A. 397 Nectoux F. 171 Nedez C. 222 Needels M. 404 Nefedov A.O. 220 Nefedov V.D. 460 Negri F. 36 Neilbecker D. 387 Neilson R.H. 95 Neiteler C. 238 Nelson H.H. 36 246 Nelson J. 204 306 347 Nelson J.E. 263 Nesbitt G.J.,260 Nestor. K. 12 Neta P. 202 Nethaji M. 70 201 Neubacher M. 199 Neubert K. 461 Neubrand A, 480 Neuburger N. 95 Neuhaus A, 120 157 Neumann B. 64 65 Neumann O. 444 Neumiiller B.83 165 Neuschiitz M. 14 Neves A, 301 496 501 Neves M. 466 468 Nevodchikov V.I. 258 Newbound T.D. 353 Newcomb T.P. 182 Newlands M.J. 204 329 Newton M.G. 55 274 380 Newton M.S. 277 312 Neyhart G.A.. 269 475 Ng B.K. 5 Ng D.K.P.,357 Ng L.-L.. 5 Ngo D.C. 96 Nguyen. L.L. 236 Nguyen M.T. 65 Nguyen N. 407 41 1 Nguyen. S.-B..378 Nguyen S.T. 360 Nguyen-Trung C.. 261 Ni J. 256 Ni Y.. 98 Nianbao Z. 460,461 Nianyong. Z. 81 Nicasio M.C. 273 364 Niccolai G.P. 378 Nicholas K.M. 353 Nicholls S.M. 373 Nichols. A.L. 468 Nichols S.J. 56 Nicholson B.K.. 389 Nicholson T.. 164 Nickel S. 252 Nickerson D. 479 Nickles. R.J. 454 464 Nicklow R.M. 425 437 Nicolini M. 27. 466 Niecke E.. 70 381 Niedenzu K.16 19 Niedrich H.. 461 Nief F. 264 Nieger M. 70 Nielsen C.M. 463 Nielsen K.N. 276 Nielsen P.E.. 261 Nielsen-Marsh S. 55 I16 Niemann A. 137 448 Nierlich M. 162 264 265 497 Nierlich. N. 261 Nietlispach D. 362 Nieuwenhuyzen M.. 170 173 Nieva G.,396 Nieve. I.. 173 Niinisto L. 200 Nikolov. GSt.. 202 Nikolov. 0..444 Ning T. 245 Nirmala R. 279 Nisar M. 461 Nishi M. 428 435 Nishida Y. 170 297 300 306 502 508 Nishijima K. 336 Nishinaga A,. 288 Nishio J. 344 Nishioka. T. 236 Nishiyama K. 436 Nissel. T.. 399 Nitschke W.. 183 285 500 Nitta S. 73 175 Niu C. 250 Niven M.L. 129 Nixon J.F. 63 66 67. 70 165 38 I Author Index No K.S. 256 Nobile C.F. 178 Noble M.E.132 Noble R.W. 498 Nocera. D.G. 153. 475 Nocker. B. 24. 25 Noda Y. 193 296 Noth H.. 5. 16 19 Noguchi S.. 435. 438 Nogues M.. 442 443 Noheda. P.. 220 476 Noirot M.D. 79 Noji. T. 399 403 Nojiri H. 436 438 Noll B.C. 79 180 192 387 466 Noltemeyer M. 16 48. 77 86 113. 166 167 261. 262 Nomura A, 471 Nonell S.. 38 Noodleman L. 162 432 449 49 7 Norante G.de M.. 312 Nord G. 476 Norden. B. 261 Nordin A. 28 Nordlund P.. 501 Nordstroem L.. 425 Norenberg J.P. 462 Norgett. M.K. 278 Norman N.C. 31 54. 55 56 Norman R.E. 231 Norman R.L. 385 Norman. T.J. 319 Noro. T. 432 Norrby. P.-0.. 366 Norseev Yu.V. 459 Northcott S.J. 479 Northwood D.O. 117 Norton J.R. 161. 217 486 Norvell. C.J.. 182 498 Noszticzius Z.481 482 Noth H. 45. 67 71 Nothig-Hus D. 124 Novak-Hofer I. 456 Novet. T. 444 Novgorodov A.F. 456 470 Nowatari H. 468 Nowicki. J. 81 86 Nowotny. M. 67 Nozaki H. 407 420 Nozaki. K.. 283. 475 Nozaki. T.. 454 Nozar. P. 402 Nuber. B. 20 30. 56 58. 110. 123. 137 258 31 1 312 315 510 Nuel. D. 375 Nummila K.K. 426 Nunez L. 256 Nufiez. P.. 200 434. 439 Nunez. V.. 428 Nudist R. 40 217 Nurmia. M.J.. 457 Author Index Nusshar D. 119 120 Nuttall S.. 173 Nuyken O. 96 Nuzzi F. 160 Nyulaszi L. 69 Oakley R.T. 83 Oberdorfer F. 460,463 Obergfell P.. 458 Oberhammer H. 71 87 Oberhausen K.J. 189 306 448. 50 1 Obermeyer A. 69 Obers W.J. 463 Obradors X. 439 440 444 O’Brien P.278 477 O’Brien R.J. 189 448 Occhuicci G. 20 Ochenbein. P. 182 Ochrymowycz L.A.. 78 203. 207 294 330 331 476 488 O’Connell. T.J. 376 O’Connor. C.J. 137 Oda M. 375 Oda. Y. 306 502 Odani A,. 297. 506 Odenkirk W. 214 288 Odier P. 413. 440 Oehlert W. 46 59 60 Oehlke J. 461 Oesen H. 55 Ofele K. 257 Ofori-Okai G. 153 Oganessian. Yu.T.. 265 Ogawa M.Y.. 495 Ogawa S. 328 Ogborne D.M.. 396 Ogden J.S. 158. 21 1 Ogden. M.I. 248 252 Ogilvie K.E. 176 Ogino H.. 7 306 455 Oglieve K.E.. 354 Ogoshi S.. 366 Ogrady. K.. 426 Oguni T. 267 Ogura H.. 144 Ogura T. 500 Ogutveren U.B. 173 Oh K.Y. 324 O’Hare D.M. 143 363 Ohba M. 297 303 Ohba. S. 174. 175. 183 200 203. 297 448 Ohba. Y..182 Ohbayashi K. 397 Ohe K. 220 Ohe T. 61 Oh-Kim. E.O. 412 Ohkochi. M.. 36 245 Ohkubo. S.. 297 Ohkubo. Y. 456 Ohmae N. 451 Ohman L.O. 28 Ohrnomo Y .. 467 Ohmori H. 322 Ohms G. 59 Ohnishi N. 402 403 Ohno T.. 36 283,475 Ohno T.R. 39. 246 405 406 O’Horo M.P.. 169 Ohsaki M. 301 Ohsawa Y. 36 Ohshira J. 100 Ohta. Y.. 313 Ohtaki. H. 170 200 Ohuchi. F.S. 80 Ohya T. 207 488 Ohya-Nishiguchi H. 179 501 Oi T.. 455 Oii S. 236 Oikama. A. 462 Okada M.. 101 Okagawa S. 469 Okahara. K. 449 Okai. B. 396 Okajirna K. 490 Okarnoto K. 197 271 Okawii H. 172 194 279 294. 297. 301 303. 329 344 448 497. 505 Okataki R. 49 50 O’Keefe. M. 41 Oki A.R. 261 Okonska-Kozlowska I. 442 Oku H.. 179 Oku T.373 401 Okuda J. 116 364 Okuda K.. 435 438 Okuda. T. 442 Okumura M. 432 Olazcuaga. R.. 199 416 Olbrich F.. 121. 197 O’Leai-y M.A. 484 Qles A,. 442 Olexova A. 482 Olivan M. 365 Oliveberg M.. 499 Oliver. J.P. 23 197 0liver;i-Pastor P.. 114 Olivier D. 116 Olivier H. 115 Olivier-Lilley G.L. 501 Olk. B. 77 Olk. R.M.. 77 Olmos E. 241 Olrnstead M.M. 3 19 20 40. 79 180 191. 192 197 223. 295. 387 505 Olsen L.F. 481 Olson C.G.,397 Olson W.L.. 397 Olsson. A, 486 Olynyk J.M. 469 471 O’Mahoney. C. 11 I. 307. 341 Omata T. 439 Omichinski J.G. 510 Omori H.. 215 379 Onaka. S.. 25 Onan K.D. 128 Ondrejkovicova. I. 170 Ondrejovic. G. 170 Ondrias. M.R.. 499 O’Neal. S.C.. 58. 84 156 Ong E.W.109 Ong K.K. 219 Onggo D. 192 Oniki T. 193 Onishi M. 198 Onishi T.. 124 Onitsuka K. 229 Ono Y. 399 Onoda M.. 407. 420 Onoe S. 435 Ontko A.C. 363 Onuchic J.N. 474 Onyszchuk M. 45 Oohara Y. 437 Oohashi K. 461 Opiela S.. 64 Oppermann H. 247 Orbach R. 429 Orbin M. 481 Oreilly. J.W. 446 Oriol L. 105 Orlandi G. 36 Orlandini A, 160. 191 272. 294 Orlando L.R. 8 Orme-Johnson W.H. 512 Oro L.A. 7 218. 283 359. 365 492 Orosz. R.D.. 180 Orpen. A.G. 55 56. 116 227 229. 260. 352. 356 371 372 373 381 Orrell K.J.. 274 Orth S.D.. 218 Ortiz. J.V.. 264 Orton D.M.. 210. 486 Ortweth M.F. 364 Orvig C.. 271 306 Orville A.M. 500 Osakada. K.. 228 Osborn J.A.. 196 283 354 Osborn R..447 Osborne. A.G. 274 Oshio H.. 193 206 296 Oshita. H. 145 Osiadacz D. 466 Osman R.. 215 Osquiguil E.. 396 Osso J.A.. Jr. 456 Osterholr A, 461 Ostovic D. 499 Otomo. M.. 337 Ott. K.C. 256 Ott. R.J. 455 Ouahab L. 360 449 Ouhammou L. 398. 398 Oushoorn R.L. 207 308 Ouvrdrd G. 109 Ouyang Q. 481 Ourzine K. 360 Ovchinnikov I. 189 Ovchinnikov S.G. 401 Overmyer D.L. 396 Owen S.M. 382 Owens B.E. 158 357 489 Ozaki S. 322 Ozawa F. 228 Ozawa S. 180 500 Ozawa T. 202 Ozcelik B. 446 Ozeki T. 129 Ozin G.A. 127 Ozkar S. 127 Ozutsumi K.. 172 196 Paajanen A, 464 Pabst I. 247 Pabst T. 438 Pacchioni G. 385 Pace J.M. 14 Pace M.D. 36 Packard A.B. 466 Packirisamy S. 101 Pacyna A.442 Padda R.S. 358 Paddon-Row. M.N. 474 Padgett H. 463 Padiou J. 77 Paeng I.R. 180 Paetzold P. 10 16 Page C.J. 200 253 Page E.M. 156 Page J.B. 41 Paglia P. 364 Paik C.H. 466 467 Paillaud. J.L. 451 Pain H.M. 274 Paine R.T. 16 19 71 102 Pajerski A.D. 23 Pal C.K. 228 Pal D. 402 Pal S. 162 276 299. 448 497 Pala M. 185 334 Palacio F. 434 439 442 Palacios J.M. 232 Palanca P. 151 Palaniandavar M. 202 285 29 1 Paldus B.A. 77 Palin J. 74 110 332 Palke W.E. 198 Pallavicini P. 238 320 Palmer A.J. 464 Palmer B.J. 178 Palmer D.A. 261 Palmer S.B. 425 426 Palmisano A.J. 34 Palson A. 469 Palstra T.T.M. 83 Pambiero A.J. 146 Pampaloni G. 3 353 354 Pan Y.. 366 Pandey A.K. 323 Pandey O.P.291 Pandey R.K. 182 Pandiyan T. 285 Pandley H.N. 287 Paneque M. 273 Pang L.S.K.. 33 34 Pang Z. 200 256 279 448 Pankhurst Q.A. 443 Pankowska H. 398 Panneerselvam K. 334 Pannell K.H. 43 391 Pannetier J. 441 Panunzi A, 234 Paoletti P.. 344 Paoli P. 250 344 347 Paolucci G. 295 Papaefthymiou V. 191 Papenberg M. 374 Paranthaman M. 30 398 Parashar G.K. 253 Pardi L. 126 448 449 Parise J.B.. 415 Parish R.V. 185 Parisini E. 370 383 Park H. 455 Park J.B. 502 Park J.T. 376 Park K.M. 129 Parkanyi L. 43 391 Parker D. 319 320 Parker D.G. 210 Parker D.H. 36 246 Parker S.J. 463 Parkin G.,68 128 156 277 509 Parkin. I.P.. 146 Parkin S.. 360 Parking S. 126 Parkinson B. 37 Parkinson B.A.40 80 Parks T.M. 58 84 Parmon V.N. 230 Parola A.J. 339 Parrinello M. 36 Parrott S.J. 69 166 Parry J.S.. 263 Parsons J.P. 38 Parsons L. 174 Parsons S. 77. 83 Partridge M.G. 88 365 Parvez M. 23 83 144 156 230 Pasanen P. 308 Pascal J.-L. 109 245 247 Pascali C. 462 Pascard C. 196 Pasha N.A. 102 485 Pashalidis I. 470 Pasin S.F. 199 Pasquali M. 229 Pasqualini R. 164 465 466 Passing G. 19 Passmore J. 58 77 81 83 86 Pastene. R.. 269 Pasternack R.F. 202 Author Index Pasynskii A.A. 285 Patalinghug W.C. 484 Pate J.E. 204 Patel A, 218 Patil M.D. 174 Patnaik S.S. 98 Patricio L. 466 468 Patt J.T. 454 Patterson C. 425 Patterson J. 306 Patzelt H. 499 Pauer F. 45 58 82 Paul P.120 285 304 329 Paulikas A.P. 397 Pauling L. 107 Paulo. A, 466 468 Paulson S.. 166 Paulus H. 186 289 Pavlosky M.A. 500 Pavlotskaya F.I. 470 Pavlov V.V. 441 Pdvlyuk V.V. 250 Pawelec Z. 16 Pawlak. K. 489 Payne M.W. 247 Payne N.C. 237 Pazik J.C. 54 Paz-Sandoval M.A. 358 Peacock R.D. 136 173 Pearson A.J. 362 Pearson G.H. 19 Pearson J.M. 480 Pebler J. 54 Peck W.F. Jr. 395 400 401 407 Pecoraro V.L. 161 162. 278 289. 295. 496. 497 Pedersen E. 149 152 Pedersen J.Z. 501 507 Pedersen T.. 73 478 Pederson D.O. 30 401 404 Pedrini P. 97 Pegg G.C. 461 Peisach. J. 507 509 Pelissier M. 176 Pelizzetti E.. 473 Pelizzi C.. 281 291 Pelling. S.. 362 Pellinghelli M.A. 207 380 Pelosi G. 291 507 Pena O.77 404 Pence L.E. 158 Peng C. 204 297 Peng. J.-L. 421 Peng S.-M. 166 182. 191 214 242 285. 287 329 356 390 Peng T.-S. 358 Peng X. 456 Pengji Z. 457 Penicaud A. 34 Penner-Hahn J.E. 161 289 497 Pennington. W.T. 24 58 79 84 149 156 157. 185 201 206 239 281 289 385 Author Index Peraio A, 114 Perel A.S. 451 Perera A, 468 Perez P.J. 142 143 364 Perez-Benito J.F. 477 Perez-Cordero E. 36 Perez-Martinez J.A. 155 Perez-Moya. L.A. 366 Perez-Pariente. J. 29 115 Perez-Torrente. J.J. 234 Peric A, 469 Perissinotti L.J. 490 Perkovic M.W. 196 283 Perlepes S.P. 135 203 Perlrnutter P. 220 Pernarnbucowise P. 446 Pernet M. 440 Perpinan M.F.. 449 Perrigan R. 28 Perrin C. 404 Perring T.G.437 Perry R.J. 175 Perthuisot C.,357 Perutz R.J. 215 Perutz R.N. 88. 357 365 Peruzzini M. 27 84 166 177 178 214. 359. 365 Pervova Y.V. 169 Pessoa J.C. 278 Pestana D.C.. 71 Peters E.-M. 196 Peters G.,34 Peters J.A. 28 250 Peters K. 20 42. 57. 196 Peters T.B. 178 Peters W.. 186 Petersen J.D. 201 206 281 Peterson E.J. 256 Peterson J.R. 244 Petit M.A.. 269 Petri. W.R. 348 487 Petricek V.. 185 Petrie. S. 38 Petrosyants S.P. 26 27 Petrov E.S. 259 Petrucci S. 489 Petrunin V.A.. 256 Petruzzelli. R. 509 Petter W. 206 Pettersson L.G.M. 200 227 Petty D.M. 404 Pfeffer. J.Z.. 446 Pfeffer W.-P. 20 Pfeiffer K. 56 Pfeil. A,. 298 Pfennig B.W.. 238 Pfister-Guillouzo G. 65 Pgawa M.402 Pham A.Q. 396 407 Phelps D.K. 474 Phillips. C.R. 470 Phillips D.A. 388 Phillips D.J. 301 Phillips M.L.F. 114 Philoche-Levisalles M. 206 302 Philouze C. 162 497 Piacenti F. 380 Piccioli. M. 508 Picher T. 151 Pickardt. J. 203 257. 261 Pickett C.J. 69 331 503 Pickett W.E. 397 Pidcock A.D. 43 Piel 14.. 42 Pieper G.. 413 Pieper U. 254 Piepgrass K.W. 18 Pierattelli R. 318. 509 Pierce D.T. 363 Pierik A.J.. 503 Pierloot K. 144 157 Pierpont C.G. 81 172 448 Pierre L. 430 Pierrot M. 509 Pietzsch H.-J. 163 Piffard Y. 416 Piggott B. 273 Pignolet L.H. 242 Piguet C. 196 275 284 299 Pike. V.W. 460 462 463 Pil. P.M. 231 Pilato R.S. 79 327. 364 Pilette D. 360 Pilkington M.J. 75 236 Pillai B.P..28 Pillai M.R.A. 465 Pirnentel I.R. 429 Pirnrn M.V. 466 Pina. F.. 339 Pines D.. 429 Pinilla E.. 449 Pinkerton. A.A. 154 291 Pinot M. 442 Pippin C.G.. 468 Piraino. P. 269 Pires de Matos A. 252 263 Pirio. N 360 Pirotte R. 468 Pisarev R.V. 441 Pislyakova N.P. 442 Place. H. 437 Planalp R.P. 23 Plass W. 287 Platt. A.W.G. 248 Plattner D.A. 314 Plecas I. 469 Plenevaux A,. 455 460 464 467 PleSek J. 3 Plimley R.E. 173 Plitt H.S. 195 Plouffe. R.Y. 215 Plumer M.L. 431 Plumier R. 443 Poat. J.C. 76 Podberezskaya N.V. 175 Podder. D. 153 Poeppel R.B. 210 Poeppelmeier K.R. 399 411 551 Porschke K.R. 366 Poettgen R. 245 Poganiuch P. 162 171 Pohl E. 19 Pohl. J. 443 Pohl S..42 191 Pohlmann K. 67 Poinsot R.. 451 Poirier D.M. 405 406 Poirier M. 51 Pojrnan J.A. 481 Pokryzwnicki S. 446 Pola. A, 177 Polarn J.R. 173 Polborn K.. 45 Poli N. 269 Poli R. 86 137 148 158 357 489 Poliakoff M. 223 371 492 Poll W. 50 Pollitte J.L. 86 Polo A. 295 365 Polo E. 109 Polshin E.V. 348 Pornbeiro. A.J.L.. 165 355 Porneroy R.K. 383 387 Pompeo M.P. 219 391 Pomper. M.G.. 464 Pon G. 448 Ponce Y.Z. 467 Poncelet O. 200 253 Ponchant M. 467 Pons J. 205 283 442 Pons S. 209 Pooke D. 403 Poole. A.D.. 353 Poon C.-K.. 279 Pope. M.T. 127 129. 476 Popov A.1.. 247 Popovkin B.A. 55 423 Porai-Koshits M.A. 120 Porte Lopez J.M. 112 Porter L. 173 207 Portrnan R. 469 Portner R.. 466 Pospelov Yu.N.470 Postelmans D. 144 Postnov. V.N. 502 Potekhin K.A. 88 Potenza J.A. 192 215 Potgieter I.M. 166 Poths H. 94 Potin Ph. 95 Potter F.H. 397 446 Potter G.A 455 Potter P.E. 244 Pottgen R. 419 Potts K.T. 276 Pouchard M. 422 Pouget S. 442 Poulton J.T. 196 215 224 Poupeye E. 462 Poveda M.L. 142 143 364 Povey D.C. 69 166 185 187 Powell A.K. 74 170 171 190 291 Powell A.V. 244 413 414 445 Powell D.R. 47 57 Powell D.W. 487 Powell H.R. 220 229 Powell N.I.. 375 Powell R.D. 326 Power M.B. 24 Power. P.P. 3 19 20 71 78. 159 172 179 197 Powers L. 510 Powls. R. 474 Pradeep T. 39 Prakash A,. 476 Prakash G.K.S. 4 Prakash S. 456 457 Prakasha T.K. 70 76 Pramanik A, 269 Prandl W.435 443 Prasad D.S.N. 480 Prasad L.S. 279 292 448 Prasilova J. 456 Prassides K. 36 Pratico D. 501 Prato M. 34 Pratt F.L.. 200 Predieri G. 217 Preetz W. 236 Prelesnik B. 174 Prenant C. 460 462 Presland M.R. 30 Pressprich M.R. 160 Prestana D.C. 19 Preston J.R. 37 Pretzer W.R. 376 Preugschat D. 88 Preut H. 53 86 Price A.C. 137 Price G.J. 97 Priebsch W. 120 513 Prince R.C. 511 Pringle P.G. 227 Pringle T.J. 275 Prior N.D. 219 Pritchard R.G. 53 75 160 161 174 177 185 289 Pritzkow H. 14 44 46 47 62 Probst R. 144 Prock A. 480 Procyk A.D. 326 Prokop J. 466 Prokopenko V.K. 442 Prokop'ev S.I. 230 Prokopowicz R.A.. 127 Pronin A.Y.. 438 Proschia J.W. 109 Prosvirin A, 189 Protasiewicz J.D.118 Prouse L.J.S. 173 Proust A, 127 Prout K. 139 Provost J. 396 401 Prozorova L.A. 433 Prusakov. V.E. 502 Pryka M. 82 Psaro R. 223 Pshinko G.N.. 469 Ptalinghug W.A. 258 Pu J. 358 Pu L. 360 Puddephatt R.J.. 105 222 229 237 370 379 Puga J. 6 388 Pugh S.. 363 Pulham C.R. 10 61 Pulukkody K. 319 Puranik D.B. 61 Purcell W. 166 Purches G.R. 361 Purdy A.P. 200 204 Purnell J. 41 107 Purohit S. 292. 448 Purves L.R. 488 Putilina E. 165 Pyle A.M.. 270 Qaim S.M. 455 456 Qian C. 257 259 Qian J. 406 Qian Z. 85 Qimin L. 456 Qin J.. 79 Qin. Z. 445 Qingzhen H. 415 Qinhui L. 204 305 Qiu X. 259 Qiuying W. 275 Qu M. 445 Qu X. 219 Quaim S.M. 454 Quarton.M. 410 423 441 Quast H. 34 Quattropani A. 196 284 Que L. Jr. 187 189 287 306 500 501 502 Quignard F. I16 Quivy J. 468 Quyourn. R. 367 Rabai G. 480 481 Rabenau A, 68 Rabinovic D. 156 Rachmaouni N. 196 Radaelli P. 399 Rader J.. 34 Radhakrishnan T.P.. 432 Rading D. 179 Radke. C.J. 29 Rad'kov. Y.F. 257 Radom L. 4 Radu N.S. 260 Radulovic S. 173 Radzki. S. 255 Rae A.D. 301 Raghavachari K.. 35 Ragunathan K.G. 176 304 347 Author Index Ragunathan. N.. 498 Rahim M.M. 23 Rahimian K. 48 Rahmouni N. 283 Rai R. 291 Raithby P.R. 102. 176 196 219 280 285 381 382. 385 Raj P.. 71 Rajagopalan K.V. 51 1 Rajasekharan M.V. 202 Rajendran U. 202 291 Rajput R.S. 466 Raju N.P. 445 Rarnachandraiah D.285 Rarnachandran R. 237 Ramage D.L. 327. 390 Ramakrishna. B.L.. 202 Ramaraj R. 217 Ramarao K.V.S. 262 Rarnarohetra M. 71 Ramasarny R. 255 312 Rarnaswami A,. 457 Rarnaswamy M. 469 Ramesh K. 185 278 279 Ramesh S.,414 Ramirez. A.P. 37 83. 404. 405 406,425. 430 Ramirez. J.A.. 151. 344 Ramirez M.C.. 385 Rarnpi M.A. 318 Rana. M.U.. 443 Ranaivonjatovo H. 44. 47 Rancel A, 204 Randaccio. L. 227. 267 504 Randall L.H. 381 Randolph B.B.. 239 Ranford J.D. 231 280. 486 Rankin D.W.H.. 10 Rao A.P. 285 Rao C.N.R.. 30 Rao C.P. 118 Rao K.L.N. 455 Rao K.M. 216. 367 Rao M.N.S. 83 Rao M.R. 101 Rao M.S.R.. 398 Rao N.N. 213 Rao. S.P.S.. 201 Rapp M. 465 Rapp 0..397 Rappe A.K. 187 217 432 501 Raptopoulou C..162 207 278 291. 497 Rardin R.L.. 119 162. 171 Raselli. A, 218. 272 Rashid R.S. 79 Rashidi M.. 229 Rashes I. 437 Rasmussen P.G. 291 448 Rastogi R.P. 482 Rastomjee C.S. 397 446 Raston C.L. 24 25 Ratcliffe C.I. 341 Rath. N.P. 198 391 Author Index Rattan. S.S..457 Rau A,. 432 Raubenheimer H.G. 379 Rauch. P.E. 68 Rauchfuss. T.B. 79 103 153. Rauschmann H. 438 Raveau B. 395 396 398 401 407 41 1 412 416 417 Ravert H.T. 462 Ravi N. 499 503 Ravidran P.V.. 101 Ravindran K. 437 Rawle C.J. 313 Rawle S.C.. 268 312 Rawson J.M. 58 83 Ray D. 305 Ray M. 276 287 Ray R.K. 285 Raymond K.N. 191 261 264 349. 500 Rayne J.A. 437 Raynor J.B. 74 115 163 219 Razbash A.A.455 Read M.C. 221 Real J.-A, 192 201 204 303 Reba. R.C.. 466 467 Rebelsky L. 425. 425 Rebenstrof B. 182 Rebizant. J.. 263 264 265 447 Recatto C.A. 235 Reck G.. 163 163 Reddmann H.. 258 Reddy A.C. 56 Reddy B.V. 41 Reddy D.R. 160. 288 Reddy K.B. 492 Reddy N.P. 100 Reddy V.S.. 70 Redfern C.M. 79 Redmond M.E. 200 Redshaw C. 118 146 150 Reed. C.A. 34 180 Reed. J.W. 479 Reed R.A. 180 500 Reedijk J. 176 202. 203 204 210 212 269 272 280 283 292. 297 486 506 Rees C.W. 221 Rees D.C. 512 Rees J.E. 6 Rees W.S.. 200 Reffy J. 69 Refosco F. 163 318. 466 Regev. A, 37 Regitz. M. 62 63 64. 69 Reglier M. 509 Regnault L.P. 433 436 441 Regueiro M.N. 33 Rehder D. 120 121 353 513 Rehr. A.. 89 Reibenspies.J.H. 147 149. 151 171 185 195 292 334 Reichard P.. 501 Reichenbach. G. 480 Reichert F. 70 Reid. Ci.,31. 207 240 338. 342 Reihl J.-F.. 176 Reimers. J.N.. 431 443 Reina R. 380 Reindl J. 66 Reinen. D. 197 Reinhard. G.. 387 Reinhold J. 77 178 372 Reinhoudt D.N. 261 314 455 Reinsborough V.C. 212. 489 Rej H. 442 Ren T. 136. 167 183 448 Renard J.P. 433 436 Rende D.E. 199 Rending L.M.. 234 Renkma J. 116 Renner M.W. 180. 498 Ressouche E.. 451 Rettig M.F.. 232 485 Rettig S.J. 69 111 215. 271. 306. 364. 390 Reuhl. K. 109 Reutel C.. 334 Reuter H.. 117 Rexwinkel. R.B.. 475 Rey P. 451 Reyes. A. 55 Reynolds J.G.. 122 271 Reynolds P.A. 200 Rezende S.M. 442 Rheingold A.L. 6 57 79.116 128. 129 130. 131 141 182 214. 216 251 260 288 311 327. 352 353. 356 357 361 362. 377 378 387. 388. 390 492 Rhine. W.E.. 109 Rhodes B.A. 466 Rhodes. C.J.. 45 Rhodes. L.F. 197 Rhyne J.J. 442 Riblir. B. 149 Ribas .I.,207 285. 303 308. 313,148 Ricard L. 66 67 147 270 Riccardi G. 327 Ricci A,. 20 Rice D.A.. 120 156 Rice D.E. 457 465 Ricevuto. V. 281 283 Richards R.L. 120. 139 155 305. 331 355 Richardson J.F. 58 84 132 189 306 448 501 Richardson J.T. 445 Richey H.G. Jr. 23 Richmond M.G. 148 Richmond T.G. 238 Richter M.M.. 281 Rickard C.E.F. 20 183 217. 360 Rico T. 449 Rieck. D.F. 385 Riede. J. 31. 257 366 Riedel R.. 19 Rieger A.L. 356 Rieger D.. 142 Rieger P.H. 203. 277 356 Riehl J.P.475 Rieker A.. 185 Riera. V. 155. 357. 379 Riesel L. 59 Riesen H.. 287 Rietveld M.H.P.. 227 Riggs P.J. 161 289. 497 Righi. S. 380. 382 Rihela T. 467 Riley R.L. 475 Rillema D.P. 196 283 Ringrose. S. 69 Rink B.. 56 Ripmeester J.A. 341 Risch G.A. 210 Riseman T.M.. 436 Ritschl A, 42 Ritter G.. 193 291. 297 513 Rius J. 283 Riviere-Baudet. M. 45 Rizkalla E.N. 171 244 Rizzoli C.. 110 289 327 Robbins. J.L. 38 Robbins L.. 240 Robbins W.K. 38 Robe S. 238 Robein. M.. 510 Robert F. 115 127 129 146. 197 410 Roberto D. 223 Roberts A.J. 397 Roberts. J.D. 232 Roberts N.K. 24 Roberts. Y.V.. 314 Robertson D.W. 462 Robertson G.B.. 362 Robertson H.E. 10 Robertson R.J. 148 Robinson G.H..24 Robinson. N.P. 116 Robinson. O.B. 74. 128 Robinson S.D. 212 Robinson W.T.. 48. 166 170 173 321 348 Robl C. 130 Robles J.C. 306 Rocchi L. 3 354 Rochon F.D.. 163 Rockenbauer. A. 206 Rockliffe D.A. 344 509 Roddick D.M. 363 480 Roden W. 462 Rodgers K.R.. 180 500 Rodgers M.A. 73 Rodriguez. A.. 476 Rodriguez T. 294 Rodriguez-Carvajal J.. 439. 440 445 Rodriguez-Castellon E. 114 Roduner E. 36 Roe J.A. 508 Roe S.M. 27. 113 Roecker L.E. 174 213 477 Roeggen I. 85 Roemer J. 465 Roper J.R. 183 319. 323 487 Roesch. F. 465 Roesch N.. 385 Roesky H.W.. 3 16 48 58 73 77 82. 86 113 166 167 261 Roesler S. 455 Rotzer M. 379 Rogers L.M. 256 Rogers R.D. 55 142. 256 262 263 332 Rohl C.75 Rohlfing C.M. 35 Rohlfing R. 126 Rohmer M.-M. 41 107 115 Rohrs B.R. 207. 499 Rohwer H.E. 262 Roi C. 109 Roitershtein D.M. 259 Rojo. T. 202. 206 276 277 Rokita S.E. 317 Roland P. 463 Rollason A.J. 425 Roman E. 25 Roman H.A. 26 Romanenko V.D. 63 226 Romeo R. 485 Romero A. 360 Romero J. 174 197 Rommel J.S. 201 Romstedt H. 189 192 Rong C. 476 Rongzhen C. 460 Roobeck C.F. 229 Roodt A, 164 166 480 484 Roof L.C. 79 157 385 Roos B.O. 157 Root A. 53 Root D.E. 204 Root D.R. 165 Roper G.C. 371 Roper W.R. 217 360 Rorabacher D.B. 78 203 207 294 330 33 I 476 488 Ros R. 210 Rosair G.M. 356 Rosato G.C. 109 Rosch N. 262 Rose D.J. 69 Rose E. 498 Rose J.P. 203 448 Roselli M..468 Roser. M.R. 446 Rosov N. 446 Rospendowski B.N. 202 Ross D.C. 488 Ross J. 481 Ross M.M.. 36 246 Ross P.K. 79 191 Rossat-Mignod. J.. 436 441 447 Rosseinski M.J. 404 405 Rossell. O. 380 Rossi A, 509 Rossi R. 84 164. 166 292 Rossmanith K. 246 Roth E.K.H. 191 503 Roth. G. 406 41 1 Roth. S. 427 Roth T. 356 Rothaler M.. 438 Rothe J. 381 Rothermel G.L. Jr. 340 Rothfuss H. 218 Rothwell I.P. 112 117 122 35I Rotilio G.. 501 507 Rotondo E. 269 Rotter H. 170 Rotter L.D. 442 Rottgardt. D. 512 Rottink M.K. 359 Rouillon T. 412 Roulet. R. 225 362 Roundhill D.M. 128 227 228 Rousseau B. 461 Rousseau. J. 467 Rousseau R.J. 205 Rousseau R.R. 279 Rousseau R.T. 204 Rousset A,.169 Routledge C.A. 483 Rovinsky A.B. 482 Rowe J.E.. 37 406 Rowlands D.L. 202 Roy A.K. 82 99 Royan B.W. 58 84 Roychoudhury P. 269 Royle L. 319 Royo. G. 51 Rozenberg S.G. 460 Rozga K. 94 Rubenacker J. 200 Rubezhov A.Z. 21 1 Rubin Y.,33 Rubinsztajn S. 95 Rubtsova T.B. 204 336 Rucaud N. 423 Ruchand N. 200 Ruchardt C. 35 Rudd M.D. 327 Rudiger S. 87 Rudinger C. 44 Rudkevich D.M. 261 Rudolf M.F.. 289. 291 Rudolph F. 24 Ruettimann S. 275 Ruf M. 509 Ruffo F. 234 Rufinska A, 24 Ruggiero C.E. 195 273 507 Rugmini V. 79 Author Index Ruhlandt-Senge K.. 54 170. 179 Ruiz E. 380 Ruiz J.. 70. 204. 205 206 207 437 Ruiz M.A. 379 Ruiz N. 7 Ruiz R. 201. 202 206 302 303 Ruiz-Ramirez L.201 Rukang. L. 412 Ruminski R.R. 201 283 Runnacles J.D. 120 Runsink. J. 10 Ruoff P.. 482 Ruowen W. 245 Russel. T. 73 Russell D.K.. 24 Russell D.R.. 173. 235. 236 Russell M.J.H. 210 Russell M.W. 169 Russo R.E. 403 Russo U. 269 Rutenberg A.D.. 430 Ruth T.. 464 Ruttimann S.. 196 Ruzic-Toros. Z. 124 Ryan D.H. 427 Ryan E.J.. I15 Ryan R.P. 35 36 Ryan R.R. 255 Rybakov V.B.. 248 Rybakov V.N. 248 Rybakova L.F. 259 Ryder K.S. 503 Rypdal K. 61 112 120 166 Rys. F.R. 203 206 Rys P. 203 206 Ryu C.K.. 198 283 475 Ryzhkov M.V. 265 Rzaczynska. Z. 250 Saad A.K. 21 1 Saad Z. 349 489 Saak W. 42 191 Saavedra P.J. 358 Sabat M. 18. 182 257 503 Sabathier F.. 468 Sabatino P. 229 371 382 Sabbioni E.454 Sabin F. 198 Sable D.B. 118 448 Saburi M. 270 Saccavini J.C. 466 Sachdev S.. 429 430 Saderholm M.J.. 174 Sadler N.P. 485 Sadler P.J. 231 486 Sadykov R.A. 442 Saegusa. T.. 102 Saeki K. 190 Saeki M. 458 Saez I.M. 376 Saez-Puche R. 437 Safo. M.K. 180. 181 498 Author Index Saghi-Szabo G. 421 Saha. A. 269 Saha N. 269 Saha S.K.. 479 Saigo K.. 26 Sailer C. 220 Saillard. J.Y. 448 Saito K. 34 36 Saito R. 233. 428 Saito. S. 405 Saito T. 138 Saito Y. 36 39. 40 174. 200. 245 399. 403 Saji H. 467 Saji T.. 36 Sajjad. M. 456 462 Sakabe Y. 144 Sakagami N. 144 Sakaguchi K. 510 Sakai N. 400 Sakaiyama. H. 344 Sakaki H. 199 Sakaki. S.. 316. 327 491 Sakamoto H.337 Sakamoto K.. 358 Sakamoto M. 301 448 Sakamoto Y. 230 Sakane G. 132 133 Sakiyama H.. 301 329 497 Sakka S. 256 Sakuraba S. 21 1 Sakurai. H. 42 47 358 428 Sakurai T. 73 175 321 394 Salazar K.V. 256 Salem G. 272 Salem J.R. 36 245 Salerno J.C. 499 Salgado. J.. 192 509 Salhi C.A. 207 330 476 Salifoglou A, 191 Salijoughian M. 471 Salter D.M. 217 Saltrnan. P. 474 Salzer A, 362 Sarnarth N. 442 Sambre J. 462 Samochocka K. 231 Samoilov P. 407 Sampson M.L. 132 Samuel E. 97 1 15. 354 Samuels J.A. 113 Sanada N. 403 Sanchez C.. I13 Sanchez F. 476,490 Sanchez J. 360 Sanchez J.L.. 427 Sanchez J.P. 447 Sanchez M. 63 226 Sanchez-Ocampo A. 456 Sanchis M.J. 200 Sander J. 374 Sanders J.C.P.54 75 Sanders-Loehr J. 204 508 Sands R.H. 161 295 497 503 Sandstrom M. 200 221 Sanekata H. 451 Sanipelli G.G. 469 Sankar S.G. 427 Sankey O.F. 41 Sanmartin. J. 174 Sanna G. 448 Sano H.. 306 Sano. M. 200 Santana M.D.. 277 312 Santarsiero B.D.. 68. 103 Santiago J. 216 Santini C.C. 215 222 Santoro A.. 401,407 Santos. I. 263 Sanyal I. 197 Sanz V. 151 Sapina F. 205 303 Sapina R.. 200 Sappenfield E.L. 202 Sara V. 466 Sarala R. 311. 476 Saravmrnuthu A, 142 Sarda. C. 169 Sargeant S.J. 101 Sarges R.. 461 Sargeson A.M.. 218 348 487 Sarid. D. 34 Sarina. T.V. 63. 226 Sarkar B. 456 Sarkar S.K. 262. 51 1 Sarson M.I. 444 Sartori. R. 269 Sasai. H. 253 Sasaki K. 114 403 Sasaki S. 465 Sasaki T.295 454 Sasaki Y. 151 374 Sasakura H. 400 Saslow W.M. 433 Sasse K. 463 Satake Y. 185 317 Satge J.. 44. 47 Satija S.K. 437 Sato H. 36 245 Sato. M. 207 488 Sato N. 241 Sato T. 340 469 Satoh M. 182 Satoh T.. 394 Satoh Y. 306 Satorie Z. 456 Sattelberger. A.P.. 134 137 244 262 263 Sattler. E. 45 Satyalakshmi K.M. 414 Satyarnurthy N. 454 464 Sauer. N.N.. 262 Saulys. D.A.. 21 Sauvage J.-P. 196 275 298 349 489 Sauvageat P.-Y. 482 Savarino P.. 213 Saveant J.-M. 475 Sawai H. 328 Sawodny W. 53 81 86 Sawtelle S.M. 292 Sawyer D.T. 171 Saxena S.K. 455 Sayouri S. 442 Scandola. F. 318 475 Scapacci G. 272 Schadel M.. 265 Schadler S.E.. 475 Schaedel M. 457 Schaefer A. 42 Schafer H.N.124 Schafer. M. 251 336 Schaefer. R. 167 Schaefer W.P. 68 246 Schafer. M.. 54 Schafer W.. 446 Schake. A.R. 162 Schall O.F. 346 Schappacher M. 102 Scharbert B. 254 Schastnev. P.V. 432 Schatz. E. 154. 203. 267 277 218 Schatz P.N.. 38 Schaudy. G.. 446 Schauer C.Y. 370 Schauer S.J.. 24 Schaverien. C.J. 260 261 Scheer. E. 446 Scheer. M. 55 58 380 Scheffold R.. 491 Scheibe 0..456 Scheidt. W.R. 180. 181 202 498 Schemm. R. 56 Schenk. K. 362 Schenzel K.. 55. 380 Schepartz. A, 291 Scheper. W.M. 90 481 Scherberg N.. 468 Scherer O.J. 56 69 147 Scherer. U.W. 457 Scherer W.. 166. 257 Schermerhorn E.J. 121 Schiebel H.-M. 105 Schier A, 45 Schilling G. 247 Schilling R.C. 98 Schillinger H.505 Schillinger. S. 288 Schimpf E. 457 Schindler. S. 197 300 Schiontt B. 160 288 Schirber J.E. 396 Schlebos P.P.J.. 389 Schleid T. 247 248 Schleiffer J.J.. 459 Schlernper E.O.. 466 Schleyer D.J.,454. 456 Schleyer P.von R. 4. 10 89 245 257 Schlichenmaier M. 399 556 Schlick S. 109 Schliephake. A, 58 Schliinken C. 7 218 Schlueter S.A. 77 Schluter M. 404 Schluter R. 66 Schmalle H. 110 312 511 Schmehl R.H. 269 283 475 Schmid B. 272 435 Schmid G. 14. 385 Schmid H. 444 Schmid R. 113 Schmidbaur H. 31 44 45 63. 67 239 241 Schmidpeter. A, 62 67 Schmidt D.E. 467 Schmidt. G. 124 Schmidt H. 75 Schmidt H.-G. 16 48 113 167 Schmidt K. 163 Schmidt K.J. 77 81 Schmidt M.71 Schmidt R. 269 Schmidt W.. 122 271 438 Schmitt E.A.. 162. 189 192 306 432,449 497 501 Schmitz G. 481 Schmutzler R. 51 105 Schnabel R.C. 480 Schnautz N.G. 262 Schneider A,. 152 Schneider F.W.,481 482 Schneider K. 513 Schneider K.J. 480 Schneider R. 63 Schneider R.F. 466 Schneider U. 55 Schnick W. 69 Schnockel H.. 195 Schobinger P. 444 Schoch T.K. 69 Schoeps. K.-O.,463 Schoettel G.,229 Schofield P.J.. 16 Scholes C.P.. 125 Schollenberger. M. 30 Schomburg D.. 58 Schonherr S. 29 Schoonover. J.R.. 475 Schott D.. 460 Schrebler R. 145 Schreier C. 20 Schrobilgen G.J. 75 464 Schrock R.R. 69 110 173 358 Schroder M.. 31 78 176. 183. 240 Schroder A. 374 Schroeder D. 66 Schroder M.207 314 331 338 342 Schroeder R.R. 78 Schubert U. 113 387 Schubiger P.A. 456 468 Schuetz M. 14 Schugar H.J. 215 Schuhmacher J. 465 Schuler M. 77 178 Schulke. U. 417 Schuller I.K. 396 Schultz M. 391 Schultze H. 258 Schulz C. 471 Schulz C.E. 180 Schulz H. 14 258 Schulz J. 63 Schulz L.D. 296 Schulz M. 365 492 Schulz W.W. 454 Schumann D. 456 Schumann. H. 24 252 257 258 261 Schussel L.J. 182 491 Schuster G.B. 40 223 Schuster H.U.. 425 Schuster M.. 246 Schwartz D.J. 102 Schwartz M. 148 Schwartz S.W. 467 Schwartz V.. 109 Schwartzenbach D. 35 Schwarz A, 89 Schwarz. H. 33 35 36 66 75 Schwarz. K. 109 Schwarz R. 269 Schwarz. W. 24 43. 45 50 71 Schwarzl A, 466 Schweikert H.. 456 Schweitzer C.T.145 Schweizer J. 451 Schwenner E. 463 Schwerdtfeger P. 242 Schwertmann U. 169 Schwochau K. 466 Schyler D.J. 465 Sciani V.. 456 Scolaro L.M. 485 Scott B. 207 448 Scott. C.J. 356 Scott F. 379 Scott J.D.. 105 Scott M.J. 79 191 505 Scott P. 353 363 Scott R.A. 474 500 Scott S.K. 482 Scott S.R. 84 Scripko. J.G. 464 Scrivens W.A.. 34 Scuseria G.E.. 36 261 Seaborg G.T. 243 Searle G.H. 174 Sebastian M.T. 114 Sebastiani G.V. 109 Secco. A.S.. 173 Secheresse F. 79 127 197 Sechovsky V.. 425 Seco M. 380 Seddon K.R. 170 Sedov V.M. 410 Author Index See R.F. 275 Seebach D.. 314 Seebold U. 19 Seehra M.S. 445 Segalas I. 239 Segre A. 224 Sehested K. 73 478 480 Seidler N.71 Seifert G. 57 Seifert S. 163 Sekiguchi A. 42 Sekiguchi M. 504 Sekine T. 459 Sekizaki H.. 174 Selegue J.P. 360 Seligson A.L.. 228 Sellmann D.. 140 287 288 292 297. 505. 511 513 Selmeczy A.D.. 221 Seltzer M.D. 104 Sembiring. S.B. 272 Sen A, 251 Senda H. 185 317 448 Senda M. 454 Sendlinger S.C. 122. 271 Senegas J. 422 Senge M.O. 26 Sengupta S.J. 291 Senocq F. 215 Senoussi S.. 432 Sens I.. 165 Seo. Y.S. 455 Seok W.K. 182. 477 Seppelt K. 74 79 81 88 170 Serfass R.E. 215 Sergent M. 404 Sergeyeva. E.I. 244 Sergi S. 485 Sergienko V.S. 120 Sernal C. 459 Serr B.R.. 207. 499 Serra. D.L. 124. 416 Serrano J.L. 105 Serrette A, 289 Serroni S. 281 Serwatowska J. 16 Serwatowski J.16 Sessler J.L. 255. 261 335 340 Seto H. 85 Setsune K. 394 Setzer W.N. 337 Seuss T.D. 24 Sevast'yanov Y.G. 455 Severing A, 447 Severns J.C. 509 Severs L.M. 8 140 Seyam A.M. 265 Seyler J.W. 214 Sgambatti E.M. 456 Shabana A.A. 180 Shabunina G.G..442 Shaffer. S.J.. 151 Shaikh S.N. 197 204 306 508 Shaikh Z.A.. 285 289 Author Index Shakhtshneider T.P. 175 Shamrikov V.M.,469 Shang M. 109 138. 139 Shankland E.G. 465 Shanzer A. 191 Shaofang L. 415 Shaowu D. 81 Shapley J.R.,40 223 384 Sharif. I. 85 Sharma. H. 43 Sharma H.L.. 455 468 Sharma M. 480 Sharma P. 61 Sharma V.S.,493 Sharma. Y.S. 287 Sharp C. 475 Sharp K. 94 Sharp P.R. 390 Shashukov E.A. 470 Shatkov. V.M. 470 Shaver.A. 215 Shaviv R. 170 200 Shayegan. S.. 28 Sheen N. 435 Shefer R.E. 454 Sheikhosman A.A. 27 28 Shekhtman L. 432 Sheldrick. G.M.. 19 44 48 58. Sheldrick. W.S. 54 381 Shellhamer D.F.,87 Shelly K. 5 Shelnutt J.A. 202 Shelton V.M. 339 Shemyakov A.A. 442 Shen J. 203 Shen J.K. 356 492 Shen. Q. 258 259 Shen Z.X. 241 Shender E.F. 430 Sheng Q.. 431 Sheng T. 182 Sheng Z.Z.. 30 401. 404 Shepherd R.E.. 169 478 Sheridan A, 347 Sheridan J.B. 358 Sheridan P.S. 109 Sherrington D.,432 Sherry. A.D. 255. 308 312 319 Sherwood R.D. 38 Sheu C. 38 Sheu H.S. 451 Shevelkov. A.V. 55 423 Shevlin P.B. 34 38 Shi H. 397 Shi S. 38 Shiba K.. 466 Shibaeva R.P. 30 396 Shibahara T.. 127 132 133 Shibasaki M.253 Shibata M. 458 Shida T. 36. 245 Shieh K.J. 448 Shieh S.J..242 Shiga Y. 321 Shigematsu S. 194 294 505 Shigematsu T.. 197 Shih G.-Y. 146 Shih K.-Y. 167 Shilliday L. 178 Shillington D.P. 226 Shilov A.E. 502 Shimada T.. 80 344 Shimakawa Y. 37 405 Shimizu I. 361 Shimizu Y. 488 Shimoi M.. 7 306 Shimura T.. 407 Shin. H.K.. 195 Shin W.,505 Shindo K. 301 497 Shinguhara K. 289 Shinohara H.. 36. 39 245 Shinozuka K. 328 Shiokawa Y. 471 Shiomi D. 450 451 Shionoya M.. 268 295. 313 319. 510 Shioya. J.. 100 Shiozuka M. 303 Shiping Y. 297 Shipley J.A. 387 Shiraishi. K.. 101 Shiraishi S.. 267 504 Shirakawa N. 450. 451 Shiralkar V.P.. 29 Shirane G.. 425 440 Shirin %. 74.213 301 Shiro. M. 51. 295 313. 510 Shiromaru. H. 34 36. 246 Shishkov A.V. 471 Shively. R.J. Jr. 362 Shklover V. 140 200 Sholl A F. 346 Shoner S.C.. 78. 159. 172. 197 Shongwe. M.S..6 Shono T.. 101 Shonrong Z.. 204 Shontz. J.T.. 327 Shore S.G..222. 258. 371. 387 Shoukry M.. 486 Shoup. T.M. 468 Shourong. Z.. 305 Showalter. K. 482 Shraydeh. B. 173 Shriver. D.F. 388 Shuangxi W.. 275 Shugang S.. 460 Shuiquan. D.. 413 Shukla R.. 203 304 Shukla US.. 285 Shul’ga. Yu.M.. 242 Shulgin A.T.. 467 Shum. D.P.. 170 ShunLhong. L. 457 Shvets I V. 427 Shweky. I.. 162 497 Siddarth. P.. 474 Siddons. D.P.. 428 Sidorov. L.N.. 169 Siebert. U. 14 Siegbahn H.O.G. 227 Sieghahn P.E.M. 200 21 1 Sieger. D..438 Siegrist T.. 109. 191. 405 Sieker. L.C.. 502 Siemens. T.. 182 Sierra M.L.. 23 67 Siewert. B. 54. 58 84 Sigalas M.P. 204 44X Sigman M.S. 104 Siivari J. 83 Sik. V. 222 274 Sillanpaa. R. 78. 202. 204 207 Sillanpaa R. 314 Sillence M.N.,461 Silva J.A.L.. 278 333 Silver. A,. 179 505 Silverman S.K.. 38 Silvester. D.J.. 460 Silvestru. C.. 71 Simerly. S.W..384 Simoes J.A.M.. 263 Simon. A. 68. 69. 88 117. 244. 247.255 Simon. J. 204. 269. 448 Simon. J.A.,493 Simon J.D.. 192. 299 Simon. T.. 34 Simonis U.. 181. 182. 498 Simonov. V.I. 30 396 Simonov Y.A.. 285 Simons. B.D.. 429 Simonsen. K. 483 Simopoulos A,. 191 Simoyi. R.H.. 481 Simpson. C.Q.. 11. 370 Simpson. N.R. 462 Simpson. S.J.. 353.355 Sinclair. R.R.. 510 Sindelar. Z.. 185 Singaram. B.. 20 Singh. A.. 153 Singh. D. 489 Singh. D.J.. 397 Singh. H.. 337 Singh. I.J. 469 Singh. J. 459 Singh K.K. 39 Singh. P. 114. 269 Singh. P.R.. 466 Singh R. 196. 337 Singh R.J..457 Singh R.R.P..430 Sinha. A.P.B. 39. 395 Sinha C.. 228 Sinotova. E.N. 460 Sirio. C.. 200 Sironi A.. 68 384. 385. 387 Sishta. C. 116 Sisley. M.J..476 Sita L.R..42 Sitlani A, 270 Sitran S. 295 Sivasanker S. 115 Sjogren M. 366 Sjoestrom J. 432 Skagestad V. 354 Skakle J.M.S.,415 Skarnulis A.J. 261 Skaugset A.E. 375 Skelton B.W. 159. 197 206 248 269 274 321 322 384 484 Skibsted L.K.,485 Skjeltorp. A.T.. 446 Skopenko V.V. 193 Skoulika.S.. 195 Skowron A, 420 Skrzypczak-Jankun E. 154 Stater P.R. 419 Slawin A.M.Z. 73 74 75 76 84 121 236 341 Sleeman M.J. 461 Slegers G. 465 Sleight A.W. 409 410 417 418 Sletten J. 201 204 303 448 Sligar S.G.,498 503 Slingerland S.. 204 Slip I.H.M.,361 Smalley. R.E.. 36. 39 261 405 406 Smeets W.J.J. 149 150 216 Smith A, 456 Smith A.B. 111 38 404 Smith A.K.,254 Smith B.E. 511 Smith D.A. 291 Smith D.C. 262 264 Smith D.D.S. 502 Smith D.P. 119 353 Smith. F.A. 471 Smith G.T.,464 Smith G.W.. 185 187 Smith J.L. 425 Smith K.D.L.,200 256 Smith K.M. 26 182 Smith L.A. 174 Smith M.B. 227 Smith M.E. 28 Smith M.G. 394 Smith M.R. 444 Smith N.K. 35 Smith P.H. 255 309 Smith P.K. 170 Smith P.M.87 Smith R.D..461 Smith R.G.. 253 Smith R.W.,415 Smith S.J. 283 Smith W.E.,202 Smits J.M.M.,78 370 389 Snead T.E. 377 378 Sneddon L.G.. 10 11 Snetkova E.V. 460 Snow M.R. 348 487 Snyder K.S..478 Sobhia ME. 334 Sobolev B.P.,247 Sobota P. 117 Sockwell S.C. 116 Soderholm L. 36 246 Sodnomdordi G. 481 Sodupe M. 246 Salter D. 167 Sogabe K.. 255 Soglowek W. 297 513 Soi A.. 37 Sokolov M.N. 138 156 Sola. E. 365 Sola J.. 91 Sola. M.. 486. 498 507 508 Solan G.A.,381 Solans X. 201 202 207 303 448 Solari E. 110 121 289 327 Solin O. 454 Solinas C. 291 Solomon E.I. 74 191 199 203 204. 306 500 506 509 Soloveichik G.L. 7 196. 259 Somarwardhana C.W.,462 Somer M.. 57 Sommovigo M. 229 Son T.I..228 Song H. 180 Song J. 128 Song J.-I.. 173 233 Song L. 363 387. 480 Song S. 148. 259 Song. X.. 6 144 217 Sonn I. 390 Sonnberger. B. 31 1 Sonnichsen S.H.,261 Sono. H. 134 Sood V.K. 467 Sorai M. 451 Sorantin P.. 109 Sorensen K.L. 119 Sorensen T.S. 144 Sorling. A, 262 Sorokin V.D.. 88 Sosna M.H.. 209 Sosnowska I.. 443 Sostero S.. 224 Sotoodeh M. 86 Soubeyroux J.L.. 199 416 434 439,443 Soufiaoui M. 44 Sougi M. 443 Souletie J.. 432 Soum A, 102 Sousa. A, 161 174 197 289 377 Sousa L.R. 227. 280 Soutar I.. 185 325 326 Southerington G.. 71 Soutome Y.. 461 Sowa J.R. Jr. 147 391 Sowerby D.B. 54. 71 Author index Soyama S. 482 Spahn M.. 63 Spalding T.R. 11 Spaniol.T.P. 216 361 Sparks L.D. 202 Sparn G. 449 Spartalian. K. 207 499 Spasenova L.N.,469 Speer T.M. 23 Speier G. 206 Speiser B. 185 Spek A.L. 149 150 216 227 280 Spence R.E.v.H..62 Spence T.G. 246 Spencer J.T.. 5 8 Spencer P. 348 Spiccia L. 287 Spicer M.D. 159 Spiering H. 192 Spies H. 163 466 Spiliotis D. 365 Spirlet J.C.,447 Spirlet M.R. 263 264 265 Spiro. T.G.. 180 500 Spodine E. 448 Springborg. J. 483 Springer. B.A..498 Sreelatha C. 285 Srinivas B. 207 301 448 Srinivas D. 285 Srivasta A.M.,424 Srivastava D.K. 5 198 Srivastava. G. 196 Srivastava. S.C.,456 457 467 Stabb M.. 174 Stabnikov P.A.. 175 Stach J. 163 Stack T.D.P.. 191 264 349 Stacy A.M.. 418 Stahlhut E. 47 Stalke.D.,44 45 82 254 Stamatakos T.C. 153 Stammer. A,. 98 Stammler. H.-G. 12 64 65 Stanbridge I.A. 480 Stanbury D.M. 31 I 476 Stang P.J. 87. 88. 89 90 237 366 Stanger A, 43 Stanger. G. 212 Star L.E. 3 Starnes J.K. 174 Stary J. 456 Starynowicz P. 291 Stassis C. 440 Stastny P. 402 Stathis M. 283 Staulo. G.. 438 Stauthamer W.P.R.V. 261 Stavrov S.S.,285 Stearns D.M. 206 Stebbins J.F. 26 Stebler S. 204 273 Author Index Stebter. S. 305 Stecher H.A. 251 Stedman G. 490 Steele W.V. 35 Steggerda J.J. 78 370 389 Steglich F. 446 Stehr J. 259 Steifel E.I. 79 Steigelmann O. 239 366 Steigerwald M.L. 191 Steimann M. 64 Steiner H.-J.. 247 Steiner M. 80 435 437 Steiner S. 273 Steinitz M.O.425 Steinmetz C.G.. 481 Steinmetz H.J. 466 Stella R. 469 Stelluto S. 295 Stelzera O. 381 Stenger H. 68 Stepanova M.L. 502 Stephan D.W. 55 108. 115 Stephens A.K.W.,346 489 Stephens F.S.. 285 Stephens P.J. 505 Stephens P.W. 33 39 449 Stephenson G.R. 210 Stepniak F. 405 Stepniak K. 250 Stern C.L. 116 257 388 Sternlieb B.J. 435 436 Sterns M. 234 Steudel R. 49. 75 Steward O.M. 175 Steward O.W.,203 297 448 Stewart D.E. 474 Stewart M.W. 381 Steyn G.J.J..480 Stibr B.. 3 11 12 Stiefel E.I. 132. 134 156 Stillman M.J. 255 510 Stirling W.G. 425 427 428 447 Stochel. G. 483 Stocker J. 67 Stockheim C. 510 Stockman K.E. 18 Stoeckli-Evans H. 174 216 272 484 Stoecklin G. 454 455 456 462 464 465 Stoffels A.L.E..280 Stoll. H. 257 Stoltzenberg A.M. 182 491 Stone-Elander S. 459 461 462 463 Stoner T.C. 373 Stoppioni P. 312 318 Storch W. 45 Storm S.L. 164 Stout B.E.,454 Stoutland P.O. 475 Stoyanov A. 196 Stoyanova R. 436 Strahle. J. 68 127 250 389 Strampfer M. 390 Strange R. 199 507 Stranger R. 158 311 Stranks D.R. 172 476 Strasak. M. 466 Stratemeier H. 124 159 Stratford S.E. 55 56 371 Straughan B.P. 134 Straumann H.-P. 203 206 Strauss. S.H. 79 180 240 Street A.C. 145 Streib WE 10 48 136 162 196 203 215 376 377 387 497 Strekas. T.C. 283 Strelets. V.V. 351 Streltsova N.R. 183 200 204 336 Strickler J.R. 353 Stringer G.H. 79 363 Stringfellow G.B. 61 Strobel K. 438 Strong St.Clair C. 506 507 Struchkov Yu.T. 63 88 138 257 258 259 264 Strukan N. 151 Stry J.J. 38 Stryker J.M. 365 Strzelski A.R. 253 Stubenrauch S. 44 Stuckey. J.A. 163 Stucky G.D. 114 419 Stuczynski S.M. 191 Stueckl A.C. 202 Stuk L. 482 Stumpe R. 471 Sturge K.C. 103 178 Stutzer A. 241 Su A.F. 466 su c.,474 Su F.M. 457 SU,G.-M. 356 Su S.Q.,248 su Y.0 180 500 Suard. E:.,398 Subba Rao M. 407 Suber L. 77 Subhani. M. 466 Subramanian G. 4 466 Subramanian L. 198 Subramanian M.A. 396 410 418 456 Subramanian R. 464 Sucheck S. 291 Suckut C. 410 Suehiro M. 454 Suelzle 13..66 Suenaga M. 448 Suenkel K. 228 Suez-Panama F. 192 Suffert J. 347 Sugano. T. 451 Sugars K.E.. 159 Sugawara.T. 39 Sugihara Y.. 14 Sugii N. 394 Sugimori T. 297 506 Sugimoto H. 451 Sugimoto S. 361 Sugiyama J. 407 Suh I.-H. 31. 334 Suh J. 509 Suh K.S. 422 Suh M.P. 324 Suisalu A.P. 128 248 Sullivan B.P. 166 Sullivan E.P. Jr. 166 180 474 Sullivan J.C.. 164 484 Sullivan. M.J. 314 Sulzle D. 75 Sumaoka J. 248 Sumida. T. 439 Sumiya J.B. 456 Summers M.F. 502 Sun H. 426 Sun J. 474 Sun K.S. 213 Sun L.J. 174 Sun S.,456 Sun W. 190 390 Sun W.-Y. 179 502 Sun Y. 172. 304 312,467 Sun. Z.S. 138 139 Sund. C. 308 Sundberg M.R.,202 204 206 207 437 Sunderland J.J. 454 464 Sundermeyer J. 381 Sunkel K.. 45 Sunley G.J. 376 Sur S.K. 253 Suran J.. 456 Surerus K.K. 512 Suryanarayanan R.398 Suryavanshi P.M. I14 Suss-Fink G. 215 216 Sutcliffe H. 108 Sutherland G.W. 81 86 Sutherland. 1.0.. 346 Sutin N. 487 Sutter T.P.G.,202 488 Suwa M. 323 468 Suzuki H. 61 62 378 379. 454 Suzuki I. 203 Suzuki K. 481 Suzuki M. 185 306 317 448 Suzuki N. 398,427 Suzuki R. 403 Suzuki S. 34 36 201 246 404 427 449 507 Suzuki T. 37 38. 228 253 441 Suzuki Y. 39 235 Svensson G. 117 178 Svoboda I. 186 Swaddle T.W. 172 476. 483 Swager T.M.. 289 Swagten H.J.M. 441. 445 Swain A.C. 97 Swann. I.L.. 337 Sweany R.L. 21 Swepston P.. 237. 386 Swinney H.L.. 481 482 Swirczewski J.W.,38 Syaygues M.J.. 439 Sychttchikova. I.. 490 Sykes A.G. 132. 474 483 503 Syono Y_.403 Syuch Z.. 459 Syvret R.G.75. 85 Szabo L.. 206 Szakacs A, 179 Szalda. D.J.. 197 300 Szamejtat J. 62 Szczepaniak. W. 263 Sze. T.-H. 263 Szeglowski Z.. 265 Szelecsenyi. F. 456. 457 Szuecs Z. 457 Tabard. A,. 25. 182 Tabata M. 207. 488 Tabuchi. J. 37 405 Tabuchi Y.. 436 Tabuteau A,. 244 Tachibana. G.N. 224 492 Tachikawa. E. 458 Tachikawa T. 39 Tachiyashiki. S. 267 Tachon. C. 65 Tada. M.. 462 Tadokoro. M. 329 Tafeenko V.A. 250 Taft K.L. 189 Tagawa. M.. 465 Tagaya H. 341 Tait. B.K.. 226 Tajik. M..81 86 Tajima S.. 40 Tak. W.W. 219 Takacs J. 179 Takada S. 468 Takagi H.. 172 395 400. 476 Takagi S.,25 Takahara Y.. 49 Takahashi K.. 255 442 Takahashi. K.N. 222 Takahashi. M. 114. 129 450. 45 1 Takahashi S.229 Takahashi T.. 241 462 465 Takai Y. 397 Takalo H. 308 Takano M. 399. 444 Takano S. 398. 399 Takao T. 378 Takashima Y.. 193 296 Takasyo Y.. 321 Takata A. 451 Takaya H.. 134 Takayama. T.. 95 Takayama-Muromachi E. 409 Takeda J. 207. 488 Takeda. K. 101 435. 438 Takeda M.. 114 Takeda Y. 399 444 Takegoshi K. 97 Takemura K.. 256 333 Takeuchi K. 457 Takeuchi K.J.. 275 Takeuchi T. 436 Takeyama. T. 222 Takita Y. 242 Takusagawa F. I1 3 Talarmin. J.. 331 Tallon J.L.. 30 Tam. K.-K. 166 Tamaki H. 172 297 Tamao K. 51 Tamazyan R.A. 30 396 Tamburini S. 330 Tams. G.. 199 Tamura H. 154 Tamura M.. 450. 451 Tamura N.. 188 Tan G.O. 505 Tan J.D..295 Tan. R.P.. 47 57 Tan. S.S..343 Tan X.L.125 Tan. Y.Y. 116 Tanaka A. 124 461 Tanaka H. 214 433 436 437 Tanaka I. 97 440 Tanaka. K. 101. 191. 214. 449. 451 Tanaka M.,100. 101. 188. 203. 250 378 428 439 482 488 506 510 Tanaka. S.. 80 394 398 400 Tanaka T.. 460 Tanaka Y. 404 Tanase T.. 73 175. 230 Tandon S.S.,204 284. 305 329. 341 448 449 Tang A.M.. 248 Tang. B.Z. 103 Tang C.C.. 425 447 Tang J.S.,69 Tang. W.. 207 508 Tang. W.-T. 285. 477 Tang Y.. 337 Tang Y.J. 446 Tang. Y.Q.. 30. 401 404 Tanigaki K. 37 40 217. 405 Tanigawa Y.. 193 Taniguchi. H.. 89. 90 Taniguchi. K. 488 Tanimura. T. 197 Tanner P.A.. 263 Tanner. P.S. 116 Tao R.J. 301 Taotao M. 457 Tapparo A,. 27 Taqui Khan M.M. 14 Author Index Tarasconi P..281 Tarasov B.P.,204 336 Tarbet B.J. 489 Tarkanyi F. 454 456 Tarrach G.,427 Tasdelen E.E. 220 Tashiro H. 457 Tashiro K. 63 147 Tasker P.A. 183 339 Tasset F. 428 Tatehata A,. 475 Tatsumi K. 273 508 Tatsuo. J. 462 Tattershall B.W.. 58 83 Tattershall C.E. 354 Tatur V.Yu. 460 Taube D.J.,493 Taube H.. 217 360 Tavakkoli K. 54 Tavano E. 455 Tavares. P.. 503 Taylor A. Jr. 164 292 Taylor A.D.,427 Taylor B.F.. 354 Taylor D.M. 244 Taylor J.S.,301 Taylor M.J. 20 21 87 Taylor M.R. 196 292 Taylor. N.J. 200 213 379 381 382,492 Taylor. R. 34 35 36 38 39 41 Taylor. S.A..97 Tchoubar. B.. 490 Tchougreeff A.L. 432 Tebbe F.N. 39 40 Tebbe K.-F.. 59 Teillet. J.. 443 Teixidor. F. 78. 283 314 Tejada.J. 442 Teller B.G.. 417 Tellgren R. 397 Templeton. J.L. 141 354 354 3 56 Tenhaeff. S.C.. 104 Tennant D.A.,437 Tenthal T. 456 Teo B.K. 242 Teo S.-B. 51 Teoh. S.-G. 51 Teplukhina. L.V. 108 Terada. M.. 361 Ter-Akopian. G.M.. 243 Teraoka. H.. 400 Terlouw J.K.. 35 62 Terner J. 500 Terry M.R.. 357 Terzis A, 204. 207 269 291 Tesh K.F..45 Teske C.L. 255 Testa A.M. 442 Teuben. H.H.. 466 Teuben. J.H. I 15. 116 351 Teunissen. H.T.. 67 Tewson. T.J.. 462 Author Zndex Teze A, 129 Tfouni E. 221 318 Thackeray M.M. 413 Thakur A.N.. 443 Thakur. M.L. 466 Thami T. 269 Thangaraji. A, 115 Theopold K.H.. 131 378 Theurig. M. 101 Thewalt. U. 373 Theys R.D. 360 Thiel F.A.. 37 405.406 Thiele B. 16 Thiele. G. 170 236 Thilgen C. 34 38 Third K. 248 Thoden J.B.. 385 Thole B.T. 447 Thomas A.H. 425 Thomas. B. 29 Thomas. F.D.. 466 Thomas J.A. 277 Thomas M.F. 444 Thompsett A.R.. 8 Thompson C. 58 Thompson D.J.,210 Thompson D.T. 210 Thompson G.R. 443 Thompson J.A. 182 199 Thompson J.D.,39 449 Thompson J.S.,269 292 Thompson L.K. 204 284 305 329 341 345. 448. 449 Thompson M.A.. 182 Thompson M.E.. 114 Thompson R. 3 Thompson R.C. 306 Thompson R.M. 69 165 166 Thomsen D.S. 160 288 Thomson S.K. 234 Thorburn I.S. 215 Thorell. J.-0.. 461 462 Thorn D.L. 39 Thornback J.R. 250. 306 466 Thornton D.A.. 201 Thornton E.R. 160 288 Thornton G.. 397 Thornton P.. 203 275. 277 278 Thornton-Pett M.8 12 Thorp. H.H.. 160 192. 269 329 495. 496 Thouvenot R. 129 Thurston T.R.. 440 Thyer. A.M. 163 Tian Z.G.. 25 Tiefenauer. L. 468 Tiekink E.R.T. 153 174 228. 346. 389 51 1 Tietza-Jaensch H. 438 Tilley R.J.D. 420 Tilley T.D. 97 216 235. 260 Tillmanns B.. 46 Tilset. M. 354 Timar T. 90 Timinski. P.A. 253 Timm M.J. 23 Timmer-Bosscha H.. 210 Timmermans. J.H. 114 Timms D.N. 428 Timperman A.T. 489 Timura K.. 94 Tindall. D.A.. 425 Tindall P.J. 38 Ting. G. 465 Tinker N.J.. 468 Tippin D.B. 202 Tipton A.R. 182 498 Tirelli S. 463 Tiripicchio A. 217. 269 379 380. 386 Tiripicchio Camellin M. 217. 379 Tisato F.. 163 Tjaden. E.B.. 365 Tkachev. V.V.. 108 Tobe M.L. 485 Tobe T.323 Tobe Y. 185 Tobin. K.. 181 Tocher D.A. 174 196 249 274 280 283 285. 295. 298 Toda. M. 337 Todd L.J. 10 Tohji K. 172 Tokhomirova G.S.,265 Tokii T. 161. 175. 203. 255. 295. 296 297 329 448. 497 Tokitoh N.. 49 50 Tokunioto M. 404 451 Tokura. S.. 42 Tokuyama. K. 344 Toledano P. 113 Tollin G. 474 Tolman. W.B.. 162 171. 195 273. 507 Tolstaya. T.P.. 89 Tomanek D. 404 Tomas F.. 232 Tomimoto K. 402 Tominaga K.. 475 Tomita I.. 102. 114 Tomita M. 270 Tomita Y.. 255 Tomkinson. N.P. 78 314. 474. 503 Tomlinson. A.A.G.. 114 Tommes. P.. 62 Tong. W. I1 I 289 Tong W.-F.,218. 287 476 Tong-Hu. L. 245 Tonkovic M. 28 Tonon. C.. 78 Toplikar E.G.. 104 Tor. Y. 191 Torardi C.C. 200 Toreki.R. 358 Torigoe K.. 241 561 Torii. Y. 464 Torikachvili. M.S.. 425 Toriumi K.. 183 204 273. 508 Tornai M. 454 Tornieporth-Oetting I.C. 16 53 82 89 238 Toronto. D.V. 387 Torres-Martinez L.M.. 410 Toscano. P.J. 121. 126. 197 300 Tosik. A.. 448 Toth A.L.. 87 Touchard D. 360 Toupadakis A, 389 Toupet L. 359 Tour J.M.. 34 Tourillon. G.. 182 498 Tourneaux M. 416. 418 Townsen. P.T.. 74. 219 Toyama H. 454 Toyokuni. T. 461 Toyota. E.. 174 Toyota. K. 63 65. 147 Trace. R.L.. 360 Trachevskii. V.V.. 348 Trahanovsky. W.S.. 363 Traill P.R.. 153 511 Trainor. R.W. 72 Trautmann. N. 455 Trautwein A.X. 137 180 186. 289. 3 15 448 499. 500 Traverso 0..224 Traylor T.G. 493 499 Treffry A,. 502 Tregloan.P.A. 485 Treindl. L.. 48 1. 482 Tremel. W. 57 123 345 Tremmel J.. 26 Trepanier. S.J. 279. 448 Tresoldi ti.,269 Tressaud. A, 200. 422. 423. 434. 439 Treutmann. W. 438 444 Trevor P.L. 37; 406 Trikha A.K. 248 Triki. S.. 77 Tripathi. A.B.R..459 Tripathi. U.N. 196. 253 Troemal. W.. 109 Trotimenko S. 176. 369. 272 273 Trogler. W.C.. 228 363. 387. 480 Troitzsch C. 55 Trojan K.L. 255 Trombe J.-C..207 Trost B.M. 226 Trotter. J. 354 Troyanchuk. 1.0..442 Troyanov S.I. 108. 115. 201 Trut. L.. 423 Tsai. C.N. 25 Tsai H.-L. 159 162. 187. 497 Tsai J.S. 37 405 Tsangaris J.M.. 269 Tschabunin H. 59 Tsipis C.A. 204 448 Tsipursky S.J. 33 Tsubornura T. 340 Tsubota K.. 255 Tsuboyarna.K. 321 Tsuboyarna S. 321 501 Tsuchida S. 197 Tsuchirnoto M. 183 Tsuchiya S. 499 Tsuda Y . 488 Tsuge K.. 138 Tsuji S. 466 Tsuji Y. 257 Tsukada N. 336 Tsukerblatt B.S. 125 Tsukihara T. 100 Tsukube H. 332 337 342 Tsutsurni M. 329 Tsutsurnida J.. 313 Tuck D.G. 25 Tucker J.H.R. 347 Tuczek. F. 74 Tudela D. 51 Tuerler A. 457 Tuinman A.A. 39 Tun Z. 431. 437 Tung H.-C. 171 Tuntulani T. 292 Turk B. 445 Turler A, 265 Turnbull M.M. 152 Turner J.J. 145 371 492 Turner S.C.. 288 Turner T.S. 397 Turney T.W. 362 Turos E. 38 Turowsky L. 74 81 Turpeinen U. 292 506 Turro C. 475 Turro. N.J. 213 Turta K.I. 285 Turton D.R. 460 463 Twardowski A, 441 445 Tweddell I. 397 Twigg M.V.210,445 Tyagi S. 442 Tycko R. 405 Tyeklar Z. 197 300 Tykwinski R. 88 Tyldesley S. 464 Tyler. A.N. 24 Tyler D.R. 104 127. 369 493 Tyrra W. 87 Tzalrnona A. 481 Tzeng. S.Y. 26 Uchibori Y. 85 Uchida T.. 203 Uchida Y. 270 Uchirnaru Y. 100 Udovenko A.A. 108 Ueda H. 451 Ueda S. 462 Ueda. Y. 29 Uehara A. 185 306 317 448 Uehara M. 402 Uekusa H. 203 448 Uemura S. 61 Uernura Y. 435 Uemura Y.J. 436 Ueng C.-H. 146. 147 Uenishi J. 342 Ueno K. 470 Ueyarna N. 153 179 190 502 Uggeri F. 250 319 Ugo R.. 223 Ugozzoli F. 202 379 386 Uhl W. 24 43 50 Uhlmann P.. 38 Uhlrich D.L. 180 Uhrrnacher M. 443 Ujairni. A.R. 185 Uji S.. 451 Ujiie S. 94 Ujirnoto. K. 342 Umeno M. 85 Underiner T.L.358 Unfried G. 88 235 366 Unfried P.. 246 Unni P.R. 456 Unoura K. 300 508 Upasani R.B. 38 451 Upton T.H. 187 432 501 Urbano A.M. 250 Urieze. K. 280 Urland W.. 247 Urtiaga M.K. 202 276 277 Ushijirna H. 45 1 Uson R. 212 Utsuno S. 270 Utting H.L. 74 170 291 Uzawa. J. 31 Vaalburg W. 466 Vacca A. 177 294 Vagg R.S. 285 Vahrenkarnp. H. 273 509 510 Vaidya N.D. 456 Vaimakis T.C. 199 Vaisserrnann J.. 129 200 Vajda E. 10 Valdez C. 152 Vale M.G. 69 Valene A, 108 Valentine J.S. 507 508 Valentine K.G. I14 Valentini M.T.G. 469 Valero C. 7 218 Valigura D. 201 Valkonen J. 207 Vallarino L.M. 175 244 Valle G. 200 Vallw B.L.. 510 Vallet M. 439 440 Valois J.M. 462 Valtancoli B. 347 van Asselt.A. 68 Author Zndex Van Beausichern N. 232 Van Bekkum H. 28 Van Billoen H. 466 Vance D. 453 Vancso G.J. 98 van de Grarnpel J.C. 84 van den Broek A.C.M. 389 van den Winkel Y.. 43 Vander Borght T. 462 van der Donk W.A. 13 220 Vanderheyden J .L. E . 457 Van der Kelen G.P. 315 316 van der Lee A, 84 van der Linden J.G.M. 78 370 van der Made A.W. 101 Van der Sluys L.S. 140 Van der Sluys W.G. 244 262 VanDerveer D.G. 337 van der Zeijden A.A.H. 140 Van de Vondel D. 315 van Diernen J.H. 269 283 Van Dijk N.H. 425 Van Doorn A.R. 261 314 van Dorsselaer A, 301 Van Dover R.B. 400 407 Vanduyne G.D. 145 Vanduyneveldt. A.J. 446 Van Dyke B.R. 474 van Eldik R. 321 322 474 473 476 478 479 480 482 483,484 486,490 492 Van Gastel F.213 Vanhecke M. 326 Vankai. V.A. 274 van Koningsbruggen. P.J. 204 van Koten G. 198 227 233 27 I 280 van Leeuwen P.W.N.M. 101 365 van Leijen. M.. 216 van Lier J.E. 467 van Loon L.R. 469 Van Nerom C. 466 Vanquickenborne L.G. 65 144 3 26 van Roon M.. 280 van Rooyen P.H. 379 Van Seggen D.M. 79. 240 Vansweevelt H. 65 Van Tendeloo G.. 395 van Vliet J.P.M. 198 271 Van Voorst J.D.W. 109 Van Wart H.E. 478 Varagny K.. 273 285 Vareka W.A. 403 404 Varga V. 115 Vargas M.D. 225 Vargas R.M. 360 Varma R.N. 455 Varnagy K. 321 Varret F. 192 Varshney. A, 309 Vasallo A.M. 33 Vasanthacharya. N.Y. 414 Author Index Vasella A, 38 Vasharosh. L. 459 Vasiliev A.D.401 Vasquez. R.P.. 397 Vassallo A.M. 34 35 Vaughan G.B.M.. 404 Vaughan O.J. 172 304 Vaughey. J.T. 399 Vaughn C. 491 Veal B.W. 397 Veber. M. 200 Vedrine J.C. 199 Veillard. A. 127 Velasco J.M.P. 269 Veleshko I.E. 256 Veltheer J.E. 69. 390 Vemulapalli. K. 246 Venanzi L.M. 272 Vencato. 1.. 301 496 Venema F.R. 28 Venkatasubramanian K. 74 213 329 Vennos D.A.. 118 420 Venter P.J. 262 Venturini E.L. 396 Vera A.. 207 Verbaere A. 416 Verbist A, 468 Verboorn. W. 261. 314 Verbruggen A.. 466 Verbruggen R.. 459 463 Verdaguer M. 182 201 303 436 498 Verin. I.A. 248 Verkade. J.G. 69 122 287. 288 Verrneulen D.. 459 Vermeulen L.A.. 114 Verne H.P. 61 Verpeaux. J.-N. 165 Verstelle J.C. 446 Verweiji P.D.297 Veszprerni. T. 69 Vettier C. 436 441 Veyre. A,. 465 Vezzosi I.M. 54 Vicente M.G.H. 182 Vicente R.,207 303 308 313 Vieira A.L. 278 Vierling P. 267 Viezzoli M.S. 495 507 510 Vigato P.A. 330 340 Vigdorchik A.G. 248 Vigner D. 162 261 497 Vigner J. 264 265 Vigneron. J.-P.. 196 Vijayaraghavan R. 30 Vila A.J. 318 509 Vilas-Boas L. 278 Villa M. 226 Villaeys A, 269 Villanueva L.A.. 366 Villarred. N.Z.. 358 Villegas. C.A. 323 Villeneuve G.. 433 Villers G.. 443 Villiers C. 264 Vincent J.B. 162 497 501 Vincentini G. 244 245 248 Vincze L. 318 Violi F. 501 Virovels A.V. 175 Viscardi G.. 213 Visciglio V.M. 117 Visscher. K.B.. 97 Visser D. 435 441 Vistin L.L. 247 Viswanathan R.202 291 Vitagliano A. 366 Vitale M. 198 Vitrano E. 498 Vittal J.J. 42 222 229 379 Vivanco M.. 357 Vizza F. 365 Vlceck A. Jr. 491 Vogelzang J. 115 351 Vogler A. 198 Vogler C. 196 233 Vogler S. 84 Vogt o.,447 Volatron F.G. 245 Volden. H.V.. 26 61 112 120. 166 Volkert W.A. 466 Volkov. V.E. 401 Voloshin Y.Z. 348 Vondrak T. 1 15 von Gudenberg D.W. 165 von Philipsborn. W. 492 von Schnering H.-G. 26. 57 34 42. 46 196 420 von Zelewsky A. 272 Vos. J.G. 212 269. 283 Vosejpka P.C. 358 Voth. G.A.. 36 Vrabel. V. 180 Vrieze K. 21 I 216 365 Vrtis M. 149 Vukovich Zh.. 469 Vuorinen. R.T. 426 Wachter. J.. 20. 123 Wada H. 407 420 Wada S. 268 3 19 439 Wada. T. 398 400 Waddling C. 98 Wade P.W..322 465 Wadepohl H.. 382 Waegell B. 509 Warnmark K. 273 Wagener D. 395 Wagenknecht. P.S. 217 Wagner. H.N. Jr. 462 Wagner. M.J. 34 200 256. 279 448 Wagner R.. 463 Wahlgren U. 200 Wahren. M. 163 Wainwright K.P. 196 292 Waizumi K. 170 200 Wakabayashi T. 34 Wakatsuki Y. 361 Wakita. K. 462 Walda K.N. 192 299. 493 Walder. L. 491 Walder P.. 491 Waldrnan. T.E. 352 Waldo G.S. 497 Waldraff C.A.A. 38 Walker C. 319 Walker F.A. 181 182. 498 Walker G.C. 475 Walker. J.M. 181 Walker. J.V. 174 294 295 Walker M.C. 474 Walker N.M. 352. 353 Wallbridge M.G.H. 27 113 Wallis S.C. 31 1 Walsh. P.J. 351 Walther B. 372 Walther P. 56 147 Walton D.J. 194 Walton D.R.M. 34 35 36 38 39 Walton.G. 294 Walton R.A. 165 167. 357 Waltz W.L. 318 Walz L.. 16 Walzer J.F.. 97 Wambeke D.M. 315 316 Wan. H. 131. 378 Wan. M.X. 451 Wan. Z.. 38 Wan-Chuan X. 258 Wang B. 259 Wang C. 358 Wang C.-C. 202 Wang C.-P. 504 Wang C.Y.. 307 Wang. G. 204 477 Wang G.-L. 207 289 448 Wang H.. 204 390 Wang H.H. 451 Wang H.L.. 451 Wang I.-H. 492 Wang. J.. 38 499 Wang J.R.,248 Wang L. 363 Wang P. 491 Wang R. 256 269. 283 475 Wang R.-J.. 173 279. 318 Wang R.T. 480 Wang S. 115 162 200 204 205 247. 256. 261. 279 448 449.497 500 Wang S.-L. 199 356 416. 417 43 3 Wang S.P. 148 Wang W.. 383 387 Wang W.Y. 294 Wang. X.. 185 250 251. 289 Wang X.Z. 397 Wang Y.. 76 166 181 236 367 448,456 Wang.Y.-P. 166 285 Wange 2..463 Wannowius K.J. 479 Warczewski J. 442 Ward D.L. 153 Ward M.D. 154 203 267. 275. 277 278 Ward R.C.C. 447 Ward S. 212 489 Ware. M.J. 171 Warncke K. 474 Warne N. 462 Warren. A.C. 48 Warren D.S. 57 Warren R.M.L. 475 Wasa K. 394 Wasfi S.H. 129 Wasgestian F. 31 1 318 Wasielewski K. 207 Wasserburger A, 3 11 Wasserman E.. 37 39 Wassermann W. 24 Watanabe I. 300 508 Watanabe K. 158 Watanabe M. 410 Watanabe Y. 180 200 465 478. 500 Waterhouse R.N. 467 Waters J.M. 280 Waters S.L. 460 463 Watkin D.J. 314 Watkin. J.G.. 244 252 263 Watkins. G.M. 201 Watkins W.C. 371. 492 Watkins W.N. 234 Watkinson M. 161 289 Watson C.T. 181 498 Watson P.G. 79 89 Waygood S.J.480 Weakley T.J.R. 341 Weatherburn D.C. 321 448 Weaver J.H. 36 39. 246. 261. 405 406 Weaver K.K. 469 Weaver. M.J. 474 Weaving R.. 477 Webb K.J. 79 Webb. R.J. 162 189. 306 448 501 Weber. A. 457 Weber E. 334 Weber K. 463 Weber L. 65 Weber W.P. 101 Webster. M.L. 159. 309 Wedd. A.G.. 153 195 51 1 Wedler M. 45 254 262 Wedlich R.C.. 195 Wegener D. 12 Wehman-Ooyevaar I.C.M..233 Wehrli S. 164. 292 Wei P. 250 Wei. S. 41. 107 Wei W. 425 Weidenbruch. M.. 42 Weihe H. 143 144. 316 Weiler M. 464 Weill F.. 415 Weiller. B.H. 492 Weiner. J. 482 Weinfurter H. 437 Weinstein B.A. 169 Weiske. T. 35 36 Weiss. E.. 197 Weiss J.. 110 31 1. 315 510 Weiss R. 111 124 180. 182 254 45 I 499 500 Weissgraber S.179 Welch A.J. 8 Welch. M.J.. 454. 455 464 467 Weller F. 119. 120 Weller M.T.. 396. 398 Wellman G.F. 431 Wells A.P.. 226 Wells M.R.. 446. 447 Wells R.L. 23 Wells. S.A. Jr. 467 Welp U.. 397 451 Welz D.. 428 435 Wemmer D.E.. 460 Wen K.. 248 Wendt. H.G.. 109 Weng L.. 160 Wengqi C. 260 Wenschuh E. 77 178 Wenzel T. 443 Wermer. P.H. 492 Werner H. 7 218 221 365 391. 492 Wertheim G.K. 37 406 Weselucha-Birczynska. A, 180 Weser U.. 506 West A.R.. 410 415 West B.O.. 296 West J.T. 181 West. R. 43 47 57. 93 98 West W.J. 222 Westbrook. J.G. 215 Westcott S.A. 13 220 Westerberg G. 461 Westerhausen M.. 45. 50 71 Weston. R.A. 431 Weston S.C.. 32 341 Westre T.E.. 500 Wettling T..63 Wever. K.. 495 Weyhermiiller. T. 110. 312 Whang. D. 11 1 173 Whangbo. M.-H. 57. 396 Wheeler. A.E.. 35 Wheeler D.R.. 137 Wheeler J.W. 239 283 342 Wheeler W.J. 460 Whelan J.. 116 220 Wherland. S.. 480 Author Index Whetten. R.L. 33 34. 36 38 246 Whidden T.K.,81. 86 Whinnery L. 68 Whitcombe T.W.. 172 White. A.H.. 159 195. 197. 206 248 252 258. 269. 274. 321. 322 384 484 White A.J.P.. 121. 165 White C. 221 365 White. D.J.,314 Whitc G.S. 364 White J.L. 97 White J.P. 258 White P. 141 White P.S. 53 58 81 82. 83 84. 86 182 356. 370 White. R.L..426 White R.P. 140. 171 177 449 White. W.H.. 239 Whitehead. J.P. 187 191 Whitehead. R.J. 83 414 444 Whitmire. K.H. 72 174 371 Whittaker.C.. 375 Whitten D.G. 488 Whittle B. 355 Whittlesey M.K. 215 Whu. S.-J.. 115 Wiarda D.,443 Wickramasinghe W.A. 362 Widen L. 461 462. 463 Widenhoefer R.A. 378 Widoloev. A,. 182 Wieber M.. 54 71 Wiegers. G.A. 407 421 Wieghardt. K.. 110. 137. 189. 311 312. 315 448 510 Wiehe. H. 276 Wieland B. 463 Wieschollek. R. 374 Wiesendanger R. 427 Wiesinger K.J. 134. 135 Wigley D.E. 119 353 Wilbur. D.S.. 468 Wild S.B. 272 334 Wildner. K.. 419 Wiley J.B. 39 Wilisch W.C.A.. 162. 290 448 Wilk. A. 197 Wilkes B. 88 Wilkes E.N. 321 Wilkins C.J. 170 173 Wilkins R.G. 187 501 Wilkinson A.P. 215 Wilkinson. G.. 118. 150 Wilkinson M.P.. 71 Will G.. 446 Willett R.D. 200 207 437 448 Willey. G.R.. 54 74. 110 245 317.331. 332 342 Willey. K.F.. 240 Williams A.F.. 196. 275. 284. 299 Williams A.J. 77 490 Author lndex Williams. D.J. 73. 74. 75. 76. 84. 90. 111. 121 165. 219. 236. 239. 307 341 347 Williams. G.. 428 Williams G.A. 164 Williams. I.D.. 118. 200 Willianis. J.. 207 Williams. J.M.. 451 Williams. N.A.L.. 56 Williams P.A. 285 Williams. P.G. 460 471 Williams. R.E.. 3. 4 Williams. R.J.P.. 495 Williams. R S . 226 Williamson. D.J.. 28 Williamson S.M.. 20 Williard. P.G.. 45 Willis A.C. 334 Willner. H.. 158 Willner I.. 269 Wilmarth W.R.. 244 Wilson A, 36 Wilson. A.A.. 462 Wilson A.M.. 352 Wilson. C. 355 Wilson. C.C. 425. 427 Wilson. D.L.. 181 Wilson J.C.. 297 Wilson. K.S. 502 Wilson.M.. 480 Wilson. M.A.. 33 34 Wilson. S.R.. 7 153 375. 384 Wilson W.W. 53 Wimmer H.. 470 Wmcott P.L. 397 Windawi H.. 209 Wing. R.M. 232. 485 Wingert. B.. 47 Winkhofer. N. 48 166 Winkler. H. 180. 186. 289. 448 Winkler J.R.. 474. 495 Winkler U.. 47 Winpenny. R.E. 195 Win-Qi C. 258 Winter. C.H.. 109 Winter J. 404 Winter. M.. 448 Winter M.J.. 354 Winter. R. 56 Wirbser J. 273 Wirringa U.. 48. 167 Wischert W. 399 Wishart J.F. 474 495 Wisian-Neilson. P.. 95 Withnall R.. 222 Witt. B. 172 Wittmann F. 102 Wocadlo S.. 67 Woerman. H.R.. 341 Woggon W.D. 499 Woitha. C.. 120. 513 Wojclcki. A. 372 Wojnowski W.. 16 196 Wojlczak W.A.. 109 Wolczanski P.T.. 48. 113. 145 Wolf. A.P.. 454 456 464 465.467 Wolf J.G. 71 Wolf. R.. 63. 226 Wolf. T.. 406 41 1 Wolf W.. 468 Wok. K. 20 Wolfus Y. 446 Wollermann. (3.. 154 Wollert R.. 82. 83 Wolrnershaeuser. G.. 56. 147 Wolriy J.A.. 289 291. 425 Wolowiek. S.. 176. 272 Wolynec. P.P. 157 Wong. C.Y.. 74. 1 I1 Wong E.H.. 152 Wong. K.-Y.. 166. 218. 285 287. 318. 477 Wong. M.. 432 Wong. T.. 35. 62 Wong Y.J. 432 Wong Chi Man. M.. 51 Woo. D.. 512 Woo H.-G. 97 Woo. L.K.. 477 Wood. G.L.. 19. 71 Woodall D.R.. 35 Woodhouse M.G.. 79 Woodruff W.H. 134. 475 Woodrum M.K. 19 Woods. C.. 86. 196. 202 283 Woodward S. 387 Woolcock. J.C.. 232. 485 Woollam. S.F.. 381 Woollins J.D.. 73 74. 75. 76. 81. 84 111. 121 236 307 Woon. T.C.. 233 487 Worden.D. 195 Workman J.M. 326 Workman M. 414 Workman R.K. 34 Worsley D.. 215 Woska D.C.. 480 Wosnitza H.V.. 446 Woulfe. K.W.. 382 Wrackmeyer R.. 63 Wright. A.H.. 382 Wright. D.S.. 44 45 Wright. L.J. 183. 217 Wright. M.E.. 104 Wright. P.E. 510 Wrobel. G.. 109 Wu C.Q.. 80 Wu. C.T.. 210 Wu. 11.. 127. 160 WU. F.Y.-H.. 510 Wu. G.. 259 416 wu G.-Z..493 wu. Id. 338 Wu. J.. 133 240 wu. K. 395 Wu. L.P.. 204 Wu. P.. 421 Wu. R.Q.. 426 wu w. 182 210 237 382. 386 Wu W.D.. 436 Wu. X. 133. 155. 240. 397 Wu X.T. 195 wu. z., 259 WU. Z.-Z. 259 wu Z.W.. 301 Wudl. F.. 34. 37. 38. 39. 449 Wiirthwein. E.-U.. 374 WiirtL. A.. 377 Wunderlich H. 186 Wurz. P. 36. 246 Wuyts. B. 396 Wyatt P.B..477 Wylie. R.S.. 489 Wynne K.J. 105 Xanthopoulos. C.E.. 204 Xia. J.-S. 25Y Xia X. 3. 41 Xia. Z.. 109 Xiang X.-D. 403. 404 Xiao. Z.. 51 1 Xiaohua. B.. 195 Xiaoxiang. Z. 465 Xie D.. 457 Xie. Q.. 36 Xie. Z.. 257 Xin. L.. 322 Xin. X.. 174 Xing Shen 467 Xinkan. Y.. 297 Xin-Min G.. 245 Xintao. W.. 81 Xiuhua. S. 457 Xu. G.. 250 251 xu G.-X.. 247 Xu J.. 264. 349 Xu J.C. 446 Xu R.. 29 xu Z.. 259 Xue B. 203 Yabuki. T. 132 Yacoby E.R.. 446 Yaegashi. Y.. 398 Yagasaki A, 129 Yaghi O.M.. 117 Yagi. M.. 471. 490 Yagi T.. 14. 504 Yagyu. T. 462 Yajima. S.. 138 Yakushi. K. 404 449 Yam. V.W.-W. 166 198. 242 Yamabe. T.. 101 449 451 Yamada K. 439. 440 Yamada. T. 402 Yamada.Y.. 313. 467 Yamafuji. K. 403 Yamagata K.. 438 Yamagishi A.. 436 Yamaguchi. K. 180. 432 478. 500 Yamaguchi S. 182 Yamaguchi T. 151 374 Yamaji Y. 329 Yamamoto A, 228 Yamamoto F.. 465 Yamamoto H. 260 Yamamoto J.. 237 386 Yamarnoto J.H. 219 Yamarnoto. K. 301 394 444 Yamamoto M. 250 470 Yamamoto. T. 272 Yamamoto. Y. 72 158 174 498 Yamarnura T. 179 505 Yamanaka M. 297 Yamanaka T. 100 Yamane H.. 401. 402 Yamasaki H. 394 Yamasaki. K. 241 Yamasaki M.. 132. 133 Yamase. T. 129 Yamashita H. 101 Yamashita. M. 183 Yamashita T. 333 Yamashita Y. 306 Yamatera H. 200 Yamato Y. 161 295. 296 297 448. 497 Yamauchi H. 394 395 398 399 400 407 Yamauchi J. 451 Yamauchi K.. 36 183 246 Yamauchi 0,,297 Yamauchi 0..506 Yamauchi Y.470 Yamazaki. H. 31 361 Yamazaki T. 428 Yan S. 204. 276 Yan S.-P. 207 289 448 Yanagihara N. 246 Yanagisawa K. 402 Yanai K.. 462 Yang D.S. 237 Yang E.S.. 242 Yang J. 360 Yang N.-L.. 101 Yang Q. 250 Yang R.. 203 Yang. S. 390 Yang S.D. 455 Yang S.Y. 248 Yang. X. 91 116 153 Yang Y. 124 Yang Y.S.. 433 Yannoni C.S. 36 245 Yano S. 73 175 230 289 Yano Y. 336 Yanovskii A.I. 264 264 Yao B. 28 Yao X. 204 Yao Y. 196 283 Yaron. U. 446 Yasaku K. 340 Yashiro M.. 248 504 Yassar A, 101 Yasuda H.. 150. 260 Yasuoka H. 29 Yatabe T. 42 Yau s.-L.. 37 Ye B. 174 Ye J.. 429 Ye Z. 261 Yeap. G.-Y. 51 Yee K.A. 247 Yee. V.C. 354 Yeh. A, 487 Yeh C.S..240 Yeh S.J. 460 Yeh W.-Y.. 356 Yellowlees L.J.,8 314 Yen W.M.. 442 Yeretzian C. 33. 36 246 Yeshurun. Y.. 446 Yeung K.-S. 166 285 Yewdall S.J. 502 Yi. C.S.. 358 Yi J.H. 456 Yiagas D.L. 445 Yibei. F.. 457 Yin J. 36 360 Yin P. 45 Yin S. 426 Yin. Y. 390 Ying Z. 275 Yingxiang G.,457 Yip H.K. 197 242 Yip. W.-H. 263 318 Yitai Q. 412 Yoblinski B.J. 283 Yoda K. 288 Yoko. T. 256 Yokoi H. 170 Yokoi S.. 482 Yokoozawa A,. 80 Yokota K. 260 Yokoyama. A.. 465 467 Yokoyama. M.. 333 Yoneda H.. 366 Yonemoto E.H. 475 Yong G.J. 181 Yonghui W.. 456 468 Yoo S.E. 112 Yoon. K. 128 Yoon S.C. 471 Yoon. Y.K. 455 Yordanov N.D. 233 Yoshiara K.. 400 Yoshida. H. 49. 441 Yoshida K..397 Yoshida S.. 394 Yoshida. T. 331 332 Yoshifuji M. 63 65 147 Yoshihara K. 459 Yoshikawa H. 407 Yoshikawa S. 73 175. 270. 498 504 Author Index Yoshimura H.. 65 Yoshimura. M. 112 Yoshinaga. N. 153 Yoshioka H.. 85 Yoshizawa H. 439 439 Yoshizawa. K. 170 449 Yosida T.. 436 You J. 89 You J.F. 191 You X. 259 YOU. Y.-S. 329 Youinou M.-T. 196 283 285 347 Young A.P.. 432 Young. C.G.. 141 511 Young. C.J.. 51 1 Young. G.B.. 234 Young R.J. Jr.. 39 Young T. 398 Young V. 69 Young V.G. Jr.. 62 122 Yousfi. A,. 214 Yu. 9.-B. 191 Yu. D.-W. 467 Yu. J.S. 122 Yu. K. 207 390 508 Yu. N.-T.. 498 Yu P. 434 Yu R.. 297. 506 Yu. s..497 Yu S.-B. 79 162 497 Yu. W.-Y.. 279 285 477 Yu.Y.-P. 203 Yuanfang L. 456 468 Yuasa M.. 462 Yufit D.S. 138 Yujiu L. 244 Yumi A.. 242 Yun S.S.,376 Yuqian. L. 457 YusofT A.R. 134 Yusuff K.K.M. 207 Yuzuri M.. 441 Yvon K. 169 Zacharias. P.S. 207 301 448 Zachvalinskiy V.S. 442 Ziihner. H. 500 Zahab A. 34 Zahurak S.M. 404 Zaitsev D.A. 460 Zaitseva N.G. 457 Zakharov L.N.. 257 258 Zakhidov A.A.. 404 449 Zaleski J.M. 475 Zaliznyak I.A.. 433 436 Zalutsky. M.R. 467 Zaman. M.R. 459 Zarnmattio S.J.. 399 Zammit G.S.A. 12 Zanchini C. 80 191. 435 Zandbergen H.W. 395 400. 407 Zanello P.. 57 176 Author Index Zang V. 492 Zang Y. 187 287 501 Zangrando E. 504 Zanobini. F.. 27 177 178 214 Zanotti. G.. 202 Zanotti V. 147 374 Zanotto L.210 Zarembowitch. J.A. 192 Zarestky J. 440 Zatta P. 27 ZLvada J. 334 Zavodnik V.E.. 285 Zefirov. N.S..87 88 Zehnder M. 273 Zeicher M. 468 Zeigler. J.M. 98 Zeisler S.. 455. 463 Zelazowski A.J. 510 Zeldin M. 95 Zeman A, 456 Zentel R. 94 Zerbetto F. 36 Zettl. A, 403 404 Zhang D.. 37 Zhang. H.. 12 57 181. 242. 261. 395 399,474 Zhang. H.-T.. 370 Zhang. H.-Y. 474 503 Zhang J. 109 187 Zhang J.-P.. 41 1 Zhang K. 510 Zhang S. 370 371 478 492 Zhang W.M. 433 Zhang X. 215 Zhang X.L. 477 Zhang Y. 191 197 457 500 Zhang Y.-X. 90. 481 Zhang Z. 479 Zhang Z.Y _,467 Zhang Fuzhong 244 Zhao J. 58 84 Zhao. J.G..451 Zhao X. 247 Zhao Z.X. 419 Zhaoqing L. 468 Zhdankin V.V. 87 88 89 Zhecheva E.233 436 Zhecheva. G. 183 Zhen Y. 480 Zheng J.-C. 204 205 279. 448 Zheng J.-Z. 259 Zheng L. 174 174 Zheng P. 259 Zheng T. 174 Zheng. Y. 219 Zheng. Y.-J.. 486 Zhon Z.Y.. 197 Zhong. Z.. 366 Zhonglin L 457 Zhong-Sheng J. 258 260 Zhou D.. 457 Zhou D.L..491 Zhou F.. 37 Zhou J. 73 394 Zhou J.S.. 474 Zhou M.Y. 421 Zhou. 0..37 39 404. 406 Zhou. P. 200,437 Zhou. Q. 301 Zhou. S.Q. 101 Zhou. W. 406 421 Zhou. W.K. 101 Zhou. W.Y.. 407 Zhou. X. 259 406 Zhou. X.-G.. 259 Zhou. X.Y. 301 Zhou. Z.-Y. 206 Zhu L.G. 248 Zhu Y.. 133 155. 240 Zhu N.Y. 195 Zhu Q.. 39. 404. 406 Zhu S. 181 Zhu W.J. 419 Zhu X. 395 406 Zhu. Y.. 40 223 Zhuang H.. 127 174. 256 Zhuang J. 174 Zhu L.in 467 Ziaee A.489 Ziebarth R.P. 109 Ziegler. M.L. 20 30. 56 58. 123 Ziegler T. 77 Ziessel R.. 347 Zikmund M. 108 Zilian A, 272 Ziller. J.W.. 16. 24 45 48. 56 68. 119 151 259. 260 360 480 Ziltsov S.F.,258 Zimmerman. J.B. 180 Zimrnermann. H.P. 457 Zimmermann K.H. 364 Zincircioglu O. 309 Zink J.I. 226 Zinner. L.B.. 244 248 Ziolo. R.F. 34 169 Zipper L. 174 285.484 Zippi E. 463 Zirong D.. 172 Zobeley. A, 463 Zocchi M. 248 Zoller P. 399 Zolnai L. 80 Zolotarev. A.P. 24 Zolotarev Yu.A.,460 Zompa L.J. 31 1 Zonghui J. 297 Zoroddu. M.A. 448 Zors J.A.. 170 Zou H.. 395 Zou. X. 491 Zovinka. E.P.. 180 Zsolnai. L. 56 Zuberi S.S.,239 Zubieta J. 117. 121. 125 126. 130. 146 153 163 197.204. 212 300. 306 497 508 Zubieta J.A.. 69 166 Zucchini. G.L. 318 Zukerman-Schpector J. 197 Zukowski E. 428 Zuluaga. J. 476 Zunieta. J.. 127 Zuo Q.. 267 Zuyao. C.. 412 Zvara I. 243 265 Zwanziger J.F. 113 Zweit J. 455 Zwernemann 0..464 Zybill C. 41 144 374
ISSN:0260-1818
DOI:10.1039/IC9928900515
出版商:RSC
年代:1992
数据来源: RSC
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