13 Radiochemistry By D. S. URCH Chemistry Department Queen Mary College London El 4NS 1 Introduction Radiochemical techniques and procedures are used in most branches of chemistry; a review of recent progress in radiochemistry must therefore be selective if it is not to cover too wide an area and to repeat consideration of topics covered on other sections of Annual Reports. The topics that will form the main sections of this review are those where radioactivity would seem to be of prime importance (i) the production of specific radioactive isotopes (ii) the synthesis of labelled molecules and (iii) chemical reactions initiated by nuclear transformations (but excluding radiation chemistry). The safety aspects of radiochemistry will also be considered. But the inorganic chemistry as opposed to the radiochemistry of the heavy radioac- tive elements is more conveniently considered elsewhere in this Report.Perhaps however some recent reviews should be noted on the chemistry of polonium’ and of and the appearance of four Gmelin supplements for uranium (solvent e~traction,~ compounds with Group V elements and germanium,’ ion exchange and chromatography,6 and the analytical chemistry of uranium7) and two general articles on the transuranium Other reviews of transuranium chemistry have considered lower lo and higher’ oxidation states the solution chemistry of the actinides,I2 and the prod~ction’~ and chemistryI4 of the trans-plutonium elements. ’ K. W. Bagnall Radiochim. Acta 1983 32 153. ’ L. Stein Radiochim.Acta. 1983 32 163. V. V. Avrorin R. N. Krasikova V. D. Nefedov and M. A. Toropova Vsp. Khim. 1982 51 23. 2. Kolarik ‘Uranium Supplement D2’ Gmelin Handbook of Inorganic Chemistry Springer Berlin 1982. D. Brown P. E. Potter and H. Wedemeyer ‘Uranium Supplement C14’ Gmelin Handbook of Inorganic Chemistry Springer Berlin 1982. H.0. Haug J. Schoen Y.Marcus and S. Specht ‘Uranium Supplement D4’ Grnelin Handbook of Inorganic Chemistry Springer Berlin 1983. ’ E. Gantner E. Mainka H. Ruf H. Wertenbach H. Schieferdecker and A. Seidel. ‘Uranium Supplement A7’ Gmelin Handbook of Inorganic Chemistry Springer Berlin 1982. ’G. T. Seaborg Am. Sci. 1980 68 279. G. T. Seaborg Sci. Quesr 1980 53,7. lo N.B. Mikheev Radiochim Acta. 1983 32 69. ‘I V.I. Spitsyn Izv. Akad. Nauk SSSR Ser. Khim. 1982 731. ’’G. R. Choppin Radiochim. Acta 1983 32 43. l3 ‘Review of the accomplishments and promise of US transplutonium research 1940-8 l’ (DGE/ER/ 10984- 7) ed. 0. L. Keller R. G. Wymer Nat. Academy of Sciences Washington U.S.A 1982. l4 E. K. Hulet Radiochim Acta 1983 32 7. 325 326 D. S. Urch A major multi-author treatise on radiochemistry has appeared in CzechlSa and also in a German’5b3‘ translation which covers all aspects of nuclear chemistry. At a more practical level is the ‘Radiochemical Laboratory Course’ in which basic radiochemical techniques are described.I6 The more sophisticated separation methods that are required for low-level radioactive measurements and environmental analysis” have also been reviewed.The recently published ‘Radiation Data Base’ is a mine of useful information” on half-lives decay schemes etc. but is in Japanese a less ambitious listing has also appeared in Portuguese.” Reactor Chemistry and Reactor Engineering20,2’ are subjects of a recent report and book respectively. The radiochemistry associated with nuclear explosions the formation of heavy isotopes local hot-atom reactors production of radioactive liquids and gases etc. has been considered in some Finally a new and rather exciting development in radiochemistry is the use of the radiation from naturally occurring trace isotopes to pin-point specific mineral grains in complex mineralogical phases or specific sites in full cell elements and on catalyst surfaces the so called ‘nuclear mi~roprobe.~~ 2 Radioisotopes In this section methods for the production of specific radioisotopes will be reviewed.Tritium 3H.-Tritium is easily produced by the thermal neutron irradiation of lithium [6Li(n a)3H]; if this reaction is carried out in lithium-doped aluminium on silica the tritium is captured presumably as -03H. The tritium can be released either by strong heating (>300”C) or it has been found,24 by an exchange reaction with ethylene. Much concern has recently been shown in methods to separate tritium from hydrogen gas (an anticipated problem in fusion systems) and from water (in swimming pool reactors). For hydrogen gas the methods investigated have included thermal diff u~ion,~~,~~ the use of zeolites (NaX-3 M)27or molecular sieves,28 occlusion by lamellar potassium graphite,29i30 and diffusion through metal films (palladium3’ and uranium32).The catalytic oxidation of tritium as a way of removing it from Is (a) V. Majer J. Cabicar V. Cernik V. Kacena J. Stary K. Svoboda and A. Zeman ‘Foundations of Nuclear Chemistry-Zaklady jaderne chemie’ Prague Czechoslovakia 1981 ;(b) ibid. German translation J. A. Barth Leipzig 1982 (c) ibid, German translation Hauser Munich 1982. l6 R. Schwanker ‘Einfuehrung in das kern- und radio-chemische Grundpraktikum’ Schoeningh Paderborn BDR 1980. W. S. Lyons Radiochem. Radioanal. Lett. 1982 53 259. ” ‘Radiation Data Book’ ed. Y. Murakami A. Danno M. Kobayashi Chijin Shokan Tokyo Japan 1982. l9 C. H. Collins J. C. de Andrade and K.E. Collins Quim. Nou. 1981 4 57. 20 E. Akatsu ‘Fundamentals of Reactor Chemistry’ (JAERI-M-9827) Jap. Atomic Energ. Res. Inst. Tokyo Japan 1981. 21 M. Benedict H. Levi and T. Pigford Nucl. Sci. Eng. 1982 82 476. 22 A. S. Krivokhatskij Radiokhimiya 1982 24 277. 23 C. J. Maggiore T. M.Benjamin D. S. Burnett P. J. Hyde P. S. Z. Rogers S. Srinivasan T. Tesmer and D. S. Woolum IEEE Trans. Nucl. Sci. 1983 30 1224. 24 M. Matsuyama and T. Takeuchi J. Nucl. Sci. Technol. (Tokyo) 1981 18 15. 25 A. Kitamoto K. Hisajima and Y. Takashima in ‘Symposium on the separation of deuterium and tritium’ ed. M. Shimizu and S. Isomura Gakkai Shuppan Senta Tokyo Japan 1982 p. 67. 26 0. Takayasu I. Makino S. Yamagami and T. Takeuchi Bull. Chern. SOC.Jpn.1982 55 1238. 27 A. S. Polevoj and I. P. Yudin Zh. Fiz. Khim. 1982 56 2015. 28 F. Ono Y. Takahashi and M. Nakazawa re$ 25 p. 121. 29 T. Terai and Y. Takahashi Nucl. Sci. Technol. (Tokyo) 1981 18 643. 30 Y. Takahashi T. Terai and M. Kanno re$ 25 p. 131. 31 H. Fujita K. Fujita H. Sakamoto and K. Higashi re$ 25 p. 157. 32 S. Imoto T. Tanabe K. Utsunomiya reJ 25 p. 151. Radiochemistry 327 helium has proved ~uccessfu1,~~ although the development of suitable techniques to facilitate exchange between hydrogen gas and water proved more difficult.34 Molecular sieve 4A gave good results35 in isotopic separation of various isotopic water molecules (as steam) e.g. 'H3H0 and 3H20. Such approaches will be helped by the measurement of vapour pressures of a range of small molecules (H2 H20 NH3)36of different isotopic composition.Laser techniques have also been employed to separated tritium-labelled molecules ; C3HF3 proved a suitable 'Be.-Although this isotope is normally produced by proton or deutron bombardment of lithium-6 or boron-10 respectively it is possible to make small amounts of 'Be by the thermal neutron irradiation of lithium utilizing the secondary nuclear reactions brought about by the recoil trition~~~ thus:- 6Li(n a)3H 6Li(3H 2n)7Be. 32Si.-A method for the production of 32Si by bombarding lithium sulphate with 51 MeV protons [34S(p 3~)~~Sil has been described.39 First Row Transition Elements.-Both 52Fe and 52Mn are produced by the bombard- ment of nickel targets with 800 MeV protons:40 separation is effected with an ion exchange resin; techniques for the preparation of high purity "Fe have also been rep~rted.~' 6SZn can be separated efficiently and cleanly from tin and bismuth by amalgam formation and electr~lysis.~~ 63Zn (T,,~= 38.1 minj a positron emitter can now be easily produced43 on small cyclotrons using the 63Cu(p-15 MeV n)63Zn reaction.Ga.-Problems associated with the preparation of this isotope from zinc targets enriched in 68Zn have been con~idered.~~ The production of 68Ga from tin oxide has been Br.-Bromine-75 which would appear to be the most suitable bromine isotope for use in nuclear medicine46 can be prepared from krypton-78 by b~mbardment~~ with quite low-energy protons [78Kr(p-l 5MeV a j75Br].Methods for the purification of 33 T. Abe K. Tsukumo M. Fukuhara T. Suzuki and S. Okazaki FAPlC (Tokyo) 1981 97 24. 34 Y. Asakura H. Yusa and H. Yamashita re$ 25 p. 31. 35 S. Tanaka and R. Kiyose ref 25 p. I I 1. 36 S. M. Dave S. K. Ghosh and H. K. Sadhukhan (BARC-I 168) Report Bhabha Atomic Research Centre Bombay India 1982. 37 Y. Makide S. Hagiwara 0.Kurihara K. Takeuchi and Y. Ishikawa reJ 25 p. 179. 38 K. Sakai Tokai Daigaku Kiyo Koga Kuba 1981 39. 39 L. Linder and P. Polak Radiochim. Acta 1982 31 23. 40 H. A. O'Brien jun. P. M. Grant G. E. Bentley J. W. Barnes and H. M. Zacharis J. Labelled Comp. Radiopharm. 1982 19 1366 4' A. 1. Egorov B. A. Morozov A. F. Ivanchenko G. I. Karazhanova and A. V. Safonov Radiokhimiya 1982 24 262." R. Gok and E. Edguer Turk. J. Nucl. Sci. 1982 9 108. 43 R. E. Bigler J. R. Dahl L. S. Rothman and P. B. Zanzonico J. Labelled Comp. Radiopharm. 1982 19 1429. 44 R. D. Fin J. P. Dwyer K. K. Koh A. Rodon Y. Sheh J. S. Sinnreich and P.M. Smith J. Labelled Comp. Radiopharm. 1982 19 1340. 45 Y. Yano and T. F. Budinger J. Labelled Comp. Radiopharm. 1982 19 1441 46 A. M. J. Paans T. Wiegman W. Hoeve and W. Vaalburg Nucl. Geneeskd. Bull. 1982 4 130. 47 A. M. Friedman 0.J. De Jesus P. Harper and C. Armstrong J. Labelled Comp. Radiopharm. 1982 19 1427. 328 D. S. Urch bromine-77 (from the selenium target where it is made by proton bombardment) have been described.48 Kr.-77Kr can be prepared by 3He bombardment of a selenium target.49 82Rb.-This positron emitter can be eluted from a column containing adsorbed 82Sr.45 Second Row Transition Elements.-Technetium continues to command most attention in this area from methods to purify the molybdenum from which it will be made5' to optimizing the condition for its separation from m~lybdenum.~' Protons (1 5 MeV) [92M0(p n)92Te] can be used to produce lighter technetium isotopes.52 But much higher proton energies (67.5 MeV) have to be used to get 97R~ The from 101Rh.53 extraction of "'Ag from hydrochloric acid can be effected54 with di-n-pentyl or di-n-octyl sulphoxide.115m In.-This isotope can be prepared when required by elution from an ion-exchange resin carrying ' ''Cd.55 1.-The production of the favoured 1231isotope by the following reactions has been described '24Te(p 2n)'231,56 12'Sb(a2n)'231,57 123Xe decays8 and the possibility of initiating 124Xe( 'y n)'23Xe(EC/3)'231 by means of 25 MeV bremsstrahlung has been ~onsidered.~~ An 1221 generator utilizing '22Xe decay has also been described.45 lBCs.-This isotope can be made in a 'generator' as well,45960 from the decay of 128Ba which had been produced by 132Cs(p 6n)128Ba.172 Lu.-This isotope can be separated from its long-lived parent '72Hf by solvent extraction.61 178 W.-Chromatography was the preferred technique for separating 17*Wfrom the parent 178Ta.62 19'Ir.-40 MeV ?-Irradiation of platinum (198) gave rise to two isomeric forms of I9'Ir with half-lives of 6.1 and 8.9 minutes.63 48 Z.B. Alfassi J. Radioanal Chern. 1983,76 325. 49 G. Blessing K. Suzuki H. Youfeng S. M. Qaim and G. Stocklin J. Labelled Cornp. Radiopharrn. 1982 19 1431. S. A. Ali and H. J. Ache J. Labelled Cornp. Radiopharrn. 1982 19 1439. 5' M. Molter D. Puetter and A. G. Hoechst German (BRD) Patent 2906439/A 1980. 52 R. M. Lambrecht and S. M. Montner J. Labelled Comp. Radiopharrn. 1982 19 1434. 53 M. C. Lagunas-Solar M. J. Avila N. J. Navarro and P. C. Johnson J. Labelled Cornp. Radiopharrn. 1982 19 1436. 54 A. S. Reddy M. L. Reddy and B. R. Reddy Radiochern. Radioanal. Lett. 1983 55 227. s5 G. J. Ehrhardt W. Volkert W. F. Goeckeler and D. N. Kapsch J. Nucl. Med. 1983 24 349. 56 G. Goin J. Vernois C. Cimetiere and J. Leger in 'International Conference on cyclotrons and their applications' Les Editions de la Physique Les Ulis France 1982 p.697. 57 L. Yongjian S. Qixun S. Degun et a/. J. Labelled Cornp. Radiopharrn. 1982 19 1358. 58 J. W. Barnes M. A. Ott K. E. Thomas P. M. Wanek G. E. Bentley F. J. Steinkruger and H. A. O'Brien jun. J. Labelled Cornp. Radiopharrn. 1982 19 1432. 59 A. B. Malinin V. T. Kharlamov N. V. Kurenkov and V. B. Popovitch J. Labelled Cornp. Radiopharrn. 1982 19 1360. 60 M. C. Lagunas-Solar F. E. Little and H. A. Moore J. Labelled Cornp. Radiopharrn. 1982 19 1450. 61 P. M. Grant R. J. Daniels W. J. Daniels G. E. Bentley and H. A. O'Brien jun. J. Radioanal. Chern. 1983 76 319. 62 R. D. Neirinckx A. Le Blanc M. Vogel J. Trumper J. L. Lacy and P.C. Johnson J. Labelled Cornp. Radiopharrn. 1982 19 1447. 63 D. W. Anderson H. Issaian and R. F. Petry Med. Phvs. 1982 9 340. Radiochemistry 329 3n) produces 195Hg Au.-Proton bombardment of gold 197A~(p 64 which can be used as a convenient source of 195A~ for nuclear medicine. The quality control of 198Au has also been con~idered.~’ T1.-The chemistry of thallium relevant to the production of 203Tl has been described;66 this isotope is of interest as precursor of 201T1.Another way of producing this isotope is by the decay of 201Pb67 (produced by 24 MeV proton bombardment of natural thallium). The lead and thallium can be separated by ion exchange. Heavy Radioactive Elements.-Ion exchange methods for separating 210Pb,68*69 210gi68,69 and 210p068,70 have been described whereas a liquid-liquid two-phase extraction7’ process was used to purify 228Ac.Solvent extraction was also used to purify 227Ac.72 Techniques for the production of gram amounts of protoactinium metal have been described.73 Chr~matography,~~ and the liquid-liquid e~traction,~~ formation of crown-ether complexes76 have all been used in the purification of uranium. The optimum conditions for separating 239Np from 243Am77 and for the recovery of americium78 using chromatographic methods have been described. 3 Labelled Compounds One of the most important and fastest growing areas for the production of labelled compounds and for the development of new techniques for producing them continues to be that of radiopharmaceuticals for use in nuclear medicine -both diagnostic and therapeutic.This field of activity has been reviewed considering the especial problems of producing compounds labelled with short-lived isotope~~~-~l and the relationship between structure and activity in radioactive compounds.8z It has also been the subject of many international conference^^^-^^ as well as a dominant 64 R. Bett J. G. Cuninghame H. E. Sims and W. H. Willis J. Labelled Comp. Radiopharm. 1982 19 1444. 65 H. El-Asrag S. El-Bayoumy and E. Hallaba Arab J. Nucl Sci. AppL 1981 14 253. 66 H. H. Caudill H. R. Gwinn and L. E. McBride Nucl. Instrum. Methods Phys. Res. 1982 200 145. 67 A. M. S. Braghirolli MSc Thesis University of Rio de Janeiro Brazil 1981 Atomindex INIS-BR-07.68 R. A. Pacer J. Radioanal. Chem. 1983 77 19. 69 D. K. Bhattacharya and A. De J. Radioanal. Chem. 1983 76 109. 70 V. R. Casella C. T. Bishop A. A. Glosby M. H. Hiatt N. F. Mathews L. A. Bunce and P. B. Hahn Radiochem. Radioanal. Lett. 1983 55 279. 7’ J. R. Noyce J. M. R. Hutchinson and W. A. Kolb J. Radioanal. Chem. 1983 79,5. 72 A. I. Mikhajlichenko E. G. Goryacheva N. M. Aksenova and A F. Denisov Radiokhimiya 1982,24 207. 73 J. C. Spirlet E. Bednarczyk and W. Mueller J. Less-Common Metals 1983 92 L27. 74 Y. Sakuma M. Okamoto H. Kakihana J. Nucl. Sci. Technol. (Tokyo) 1981 18 793. 75 B. V. Stamicarbon Netherlands Patent No. 8000832/A 1980. 76 A. M. Rosen Z. I. Nikolotova N. A. Kartasheva A. G. Luk’yanenko and A. V. Bogatskij Dokl.Akad. Nauk SSSR 1982 263 1165. 77 P. D. Wilson J. Less-common Metals 1983 91 L13. 78 W. I. Yamada L. L. Martella J. D. Navratil J. Less-common Metals 1982 86 21 I. 79 S. Tazawa and Y. Nishihara Sumitomo Jukikai Giho 1982 30 76. no G. J. Uhlenhut H. Koch P. Kopecky and K. Svoboda Report of the Central Institute for Isotope and Radiation Research Leipzig Akad der Wissenschaften der DDR Leipzig DDR 1982 p. 37. ” J. S. Fowler and A. P. Wolf Report BNL-31222 Brookham Nat. Lab. Upton N.Y. U.S.A. 1981. 82 ‘Radiopharmaceuticals Structure-Acitivity Relationship’ ed. R. P. Spencer Grune and Strutton New York U.S.A. 1981. 83 ‘Radiopharmaceuticals 11 Proc. 2nd Int. Syrnp. Radiopharm.’ Society for Nuclear Medicine ed. V. J. Sodd D. R. Allen D.R. Hoogland and R. D. Ice New York U.S.A. 1980. 134 S. S. Zoghbi M. L. Thakur A. Gottschalk S. Pande S. C. Srivastava and P. Richards Report BNL-31282 Brookham Nat. Lab. Upton N.Y. U.S.A. 1982. 85 Proceedings of the 4th International Symposium on Radiopharmaceutical Chemistry J. Labelled Comp. Radiopharm. 1982 19 (issues 11 and 12). 330 D. S. Urch feature of many laboratory report^.'^-'^ The problems of radiochemical purity especially associated with autoinduced radiation damage have been considered in general'' and in particular for 34C,92 81Kr,93and ""'TC.'~~~ It is not however the purpose of this section of the report to consider this particular field in any depth nor to list every new synthesis of a labelled compound but rather to attempt just an overview of recent developments in labelling methods.3H-Tritium.-The chemistry of tritium is the subject of a recent Japanese and more specifically methods for making poly-tritiated molecules have been reviewed." A popular method for the production of tritium-labelled compounds continues to be by exposure to tritium gas but usually in the presence of a catalyst such as PdO {r3H]rnethyl-5-hydroxyyluracil and -thymine,98 [7,8,19,20-3H]naloxone,99 gonadotropin,"' and steroids'"} although it has been reported that side effects can be reduced by using a low pressure of tritium gas;'02 attempts at 'normal' Wilzbach labelling of insulin gave negative result^."^ A micro-wave dis- charge can also be used to induce tritium labelling;lo4 the presence of a methine site is found to be advantageous.Another popular method of labelling is catalytic halogen-tritium exchange (e.g. rnianse~in,'~'porcine dynorphin (1-17),Io6 [1,7,8-3H]dihydromorphine,'07 [5-3H]uraci1,'08 [6-3H]uraci1,'09 tamoxifen'" etc.). Other methods include exchange with labelled water"' ([ 15-3H]gibberellin-A3) and the 86 D. Comar in '9th Int. Conf. on cyclotrons and their application'-ed. G. Gendreau Les Editions de la Physique Les Ulis France 1982 p. 645. n7 E. I. Mikerin At. Ehnerg. 1982 (August) 89. an 'Radiochemistry Division annual report 1980' (BARC-I 160) ed. N. C. Jayadevan and S. B. Manohar Bhabba Atomic Research Centre Bombay India 1982. 89 A. G. de Silva 0. F. Lemos J. L. 0.de Britto J. A. Osso M. A. V. Bastos A.M. S. Braghirolli D. F. S. Chamma G. W. A. Newton and R. Weinreich Atomindex 1982 INIS-mf-7885. 90 (a) G. W. Kabalka 'Report on Nuclear Medicine' 1980-1982' (DOE/EV/ 10363-4) University of Ten- nessee Knoxville U.S.A. 1983; (b) G. W. Kabalka 'Progress Report on Nuclear Medicine 1982-1983' (DOEIEVJ 1063-3) University of Tennessee Knoxville U.S.A. 1983. 91 W. J. Welsh 'Guidelines for radiopharmaceutical quality control in hospitals' (EHD-8 1 -77) Department of National Health and Welfare Ottawa Canada 1982. 92 B. F. H. Drenth and R. A. de Zeeuw Inr. J. App. Radiar. Isor. 1982 33 681. Y3 M. Comet J. Croize M. Gautley J. P. Mathieu C. Pernin F. Dubois A. Verain J. Godart and J. Boutet J. Eiophys. Med. Nucl. 1982 6 121. 94 S. Vallabhajosula S.J. Goldsmith and H. Lipszyl J. Labelled Comp. Radiopharm. 1982 19 1565. 9s A. Yokoyama and K. Horiuchi in 'Proc. 3rd Int. Radiopharmaceutical Dosimetry Symposium' (FDA-8 1-8166) ed. E. E. Watson A. T. Schlafke-Stelson J. L. Coffey and R. J. Cloutier Bureau of Radiological Health Rockville Md. U.S.A. 1981. 96 'Chemistry of Tritium from Basics to Application' Atomic Energy Society of Japan Tokyo Japan 1982. 97 F. Cacace M. Speranza A. P. Wolf and R. Ehrenkaufer J. Labelled Comp. Radiopharm. 1982 19,905. 9n J. Filip and L. Bohacek Czechoslovak Patent 192238/B 1981. 99 G. Toth F. Sirokman M. Kramer A. Borsodi and A. Ronai J. Labelled Comp. Radiopharm. 1982 19 1021. loo E. Klauschenz M. Bienert H. Egler U. Pleiss H. Niedrich and K. Nikolics Peptides (Fayetteville N.Y.) 1981 2 445.101 J. Protiva E. Klinotova J. Filip and R. Hampl Radiochem. Radioanal. Lett. 1982 53 277. 102 H. Pluciennik and J. Hrebenda Radiochem. Radioanal. Lett. 1983 56 25. Io3 J. Uschkoreit D.Sc. Dissertation Tech. Hoschschule Aachen 1979 Atomindex INIS-mf-8266. 104 B. E. Gordon W. R. Erwin R. M. Lemmon and G. T. Peng fnt. J. Appl. Radiat. fsot. 1982 33 715. 105 J. S. Favier J. Wallaart and F. M. Kaspersen J. Labelled Comp. Radiopharrn. 1982 19 1125. lo' R. A. Houghton Life Sci. 1982 31 1805. I07 G. Toth M. Szuecs S. Benyhe F. Sirokman and M. Kramer Radiochem. Radioanal. Lett. 1983,56,209. I on J. Filip and L. Bohacek Czechoslovak Patent 192239/B 1981. 109 J. Filip and L. Bohacek Czechoslovak Patent 1971 18/B 1982.110 D. W. Robertson and J. A. Katzenellenbogen J. Org. Chem. 1982,47 2387. M. Lischewski and G. Adam J. Labelled Compd. Radiopharm. 1982 19 1231. Radiochemistry 33 1 use of tritium labelled borohydride as a reducing agent.'12 The location of tritium in compounds produced by a variety of the above techniques has been studied using tritium N.M.R.' l3 C.-Most current interest in the production of carbon-labelled compounds centres upon "C rather than I4C; the short half-life of "C often necessitates inovative chemistry to produce the desired product. Methods for optimizing the direct forma- tion of useful materials such as "CO '14 or nitrogen-containing "C c~mpounds"~ have been described. Reactions involving recoil "C atoms as a way of augmenting the number of carbon atoms in a molecular have been proposed,'16 although care must be taken in purifying the products because a mixture of labelled compounds usually results.Chromatography is of course useful for this purpose and h.p.1.c. has proved especially valuable for radiopharmaceutical production;' l7 the use of a capillary column has even allowed the isolation of ["Clmethane.' l8 Remote-control (e.g. for handling "CO "C02 and H'1CN)1'9 and automatic methods for the preparation of ''C-labelled compounds'20 are being rapidly developed in many laboratories e.g. 2-deoxy-~-glucose,'~' glucose,123 anti- 3-[I 'C]methyl-~-glucose,'~~ methyl iodide,'25 L-[S-methyl-''C]methi~nine.'~~ ~yrine,'~~ Most routes to "C-labelled molecules start from simple compounds such as ["Clcarbon dioxide from which labelled butanol,'26 pr~pandiol,'~' pal mi ti^'^^^'^^ and other carboxylic acids,'29 acetate anion,'30 and glucose'23 can then be produced.Methods to maximize the initial "C02 prod~ction'~~ as well as a study of its reaction in a micro-wave discharge'32 and its reactions with metallo-aldimines to make imino acids'33 (and so to ["C]ketoacids) have been described. I I2 B. Steiner K. J. Clemetson and E. F. Luescher Thromb. Res. 1983 29 43. 113 Y. S. Tang Ph.D Thesis University of Surrey Guildford U.K. 1982. I14 S. C. Jones G. D. Robinson A. Alavi E. Mclntyre and M. Reivich ref:85 p. 1352. 'I5 K. Roessler B. Lattke C. Mathias L. M.Al-Shukri and M. Vogt ref. 85 p. 1618. I16 G. Gundlach E.L. Sattler U. Wagenbach and K. Wittig ref 85 p. 1371. I I7 G. Berget M. Maziire J. M. Godot J. Sastre C. Prenant and D. Comar 'Preparation of "C-Labelled radiopharmaceuticals by the use of HPLC method' (CEA-CONF-66 18) Centre &Etudes Nucleaires de Saclay. 91 Gif-sur-Yvette France 1982. I18 G. Berger C. Prenant J. Sastre and D. Comar ref 85 p. 1486. I19 G.-J. Meyer T. Harms and H. Hundeshagen reJ 85 p. 1362. 120 M. J. Welch C. S. Dence and M. R. Kilbourn ref:85 p-1382. I21 S. A. Stone-Elander E. Ehrin and J. L.G. Nilsson ref 85 p. 1372. I22 P. Laufer and G. Kloster Int. J. App. Radiat. Isot. 1982 33 775. 123 K. Ishiwata M. Monma R. Iwata and T. Ido ref:85 p. 1347. I24 (a) D. van Haven P. de Clerq T. Vandewalle and C. Vandecasteeie Int.1. AppL Radiat. Isot. 1982 33 751; (6) D. van Haven P. de Clerq T. Vandewalle and C. Vandecasteele in 'AOC 3rd World Congress of Nuclear Medicine and Biology' ed. C. Raynaud Pergamon 1982 Volume 1 p. 1108. 12' J. Davis Y. Yano J. Cahoon and T. F. Budinger Int. J. AppL Radiat. Isot. 1982 33 363. lZ6 (a) F. Oberdorfer F. Helus W. Maier-Borst and D. J. Silvester Radiochem Radioanal. Lett. 1982 53 237; (b) F. Helus W. Maier-Borst F. Oberdorfer and D. J. Silvester ref. 85 p. 1501. 127 G. Berger M. Maziire C. Prenant J. Sastre A. Syrota D. Comar J. Radioanal. Chem 1982 74 301. 128 H. C. Padgett G. D. Robinson and J. R. Bamo Int. J. AppL Radiation Isot. 1982 33 1471. 129 B. Schmall P. S. Conti B. Sundoro-Wu J. R. Dahl J. K. Jacobsen and R. Lee 1.Labelled Comp. Radiopharm. 1982 19 1278. I30 V. W. Pike M. N. Eakins R. M. Allan and A. P.Selwyn Znt. J. Appl. Radiat. Isot. 1982 33 505. 131 T. Vandewalle and C. Vandecasteele ref:85 p. 1376. I32 K. Niisawa J. Saito K. Taki T. Karasawa and T. Nozaki re$ 85 p. 1616. 'I' (a) M. R. Kilbourn and M. J. Welch Int. J. Appl. Radiat. Isot. 1982 33 359; (b) M. R. Kilbourn and M. J. Welch ref 85 p. 1273. 332 D. S. Urch ["CIMethyl iodide'25 is a particularly useful reagent for introducing the "C-label at a known and usual stable site in a e.g. methiodide quinuclidinyl ben~ilate,'~' L-methionine 13' N-alkyl derivatives of 2-amino-6,7-dihydroxy- 1,2,3,4- tetrahydr~napthalene,'~'and anti~yrine.'~~ Other starting materials have included [''Cjphosgene { 1,3-bis(2-chloroethyl)nitrosourea,138 [2-''C]-5,5-dimethylox-a~olidine-2,4-dionel~~*'~} and [''Clformaldehyde (erthromycin A'41).Recent advances in l4C-labe1ling have included a rapid and efficient synthesis of [1,2-'4C]acetic the production of a series of 3-substituted in dole^,'^^ the use of an enzyme to make ['4C]ATP'44 and the description of a method for labelling bacteria with [14C]palmitic Nu~leotides'~'and a series of uridine deriva- tive~~~~ have also been labelled with 14C. 13N,'50.-A method for the synthesis of 13NH3 from 13C enriched targets using micro-wave radiation has been described.'48 13NH3 [from l60(p a)13N] has been used for the production of ~-['~N]glutamate,'~~ nitrous oxide can be made labelled either with 13N15* (pyrolysis of ammonium [13N]nitrate) or with H2150 has also been made."4 '*F.-Trying to produce 18F in a conventional thermal neutron reactor is rather like trying to run up a scree slope-you have to run hard and you don't get very far.Even so it has been tried'52 using the reactions 'Li (~,LY)~H followed by 160(3H,n)'8F in lithium hydroxide. The overall yields of 18F were about 40mCi. Considerable effort has recently been expended in attempting to design suitable mixtures in which nuclear reactions that produce "F can take place so that subsequent chemical reaction will deliver 18F in a convenient chemical form. If the deutron-neutron reaction takes place in a copper or tungsten vessel the 18F that adheres to the walls can be removed by heating in a hydrogen-helium mixture to give anhydrous Hl8F.lS3 Inconel-600 has also been studied as a container material,'54 but using neon-134 H.Svaerd K.Naagren P. Malmborg D. Sohn S. Sjoeberg and B. Laangstroem ref 85 p. 1519. 135 M. Maziire G.Berger J.-M. Godot C. Prenant J. Sastre and D. Comar J. Radioanal. Chem. 1983 76 305. 136 G.-J. Meyer A. Osterholz and H. Hundeshagen ref:85 p. 1286. 137 J. F. van der Werf H. D. Beerling-Van der Molen A. M. J. Paans T. Wiegman J. Korf and W. Vaalburg ref 85 p. 1296. 138 M. Diksic S. Farrokhzad S. Yamamoto and W. Feindel J. Nucl. Med. 1982 23 895. I39 J. Z. Ginos R. S.Tilbury M. T. Haber and D. A. Rottenberg J. Nucl. Med. 1982 23 255. 140 M. Berridge D. Comar D. Roeda and A. Syrota Int.J. Appl. Radiat. Isot. 1982 33 647. l4I A. J. Palmer V. W. Pike P. L. Horlock L. A. Perun L. A. Frieberg D. A. Dunnigan and R. Liss ref 85 p. 1275. 142 T. Elbert and J. Filip Radiochem. Radioanal Lett. 1983 57 21 1. 143 J. Schallenberg and E. Meyer 2.Naturforsch. Teil B 1983 38 108. 144 Z. Nejedly H. Tauchmanova J. Filip and J. Kolina Radiochem Radioanal. Lett. 1982 53 329. 145 S. Abaas FEMS Microbial. Lett. 1983 18 283. I46 V. Svoboda I. Kleinmann and J. Kolina Radioisotopy 1982 23 301. 147 J. L. Ruth S. K. White and D. E.Bergstrom J. Labelled Comp. Radiopharm. 1982 19 861. 148 R. A. Ferrieri D. J. Schlyer A. P. Wolf and B. Wieland ref 85 p. 1614. I49 K.Suzuki K.Tamate T. Nakayama T. Yamazaki Y.Kasida K.Fukushi Y. Muruyama H. Maekawa and H.Nakaoka ref 85 p. 1374. Is' G. Del Fiore J. M. Peters L. Quaglia N. Bougharouat D. Lamotte and T. Niethammer J. Biophys. Med. Nucl. 1982 6 163. 151 C. Crouzel and J. C. Baron ref 85 p. 1612. I s2 S. J. Gatley and W. J. Shaughnessy 1nt. J. Appl. Radiat. Isot. 1982 33 1325. I53 J. R. Dahl R. Lee R. E. Bigler B. Schmall and J. E. Aber Int. J. Appl. Radiat. Isot. 1983 34 693. J. C. Clark and F.Obderdorfer ref 85 p. 1337. Radiochemistry 333 hydrogen mixtures as the target gas. H18F can be used to make 18F-difluorine gas,155 to fluorinate aromatic system^"^ (via triazeno method) and to prepare 2-[18F]-2-deoxy-~-glucose'~~ (this compound can also be prepared starting with 18F. F'58 see ref 114). If the mixture CF,,H2 Ne is irradiated with deutrons a very reproducible yield of H18F is produced.159 The methods all produce F2 or HF in an anhydrous and carrier-free form.Water can however act as a useful target material if an 3He ion beam is available 160(3He,p)'8F. This reaction has been the basis of a series of successful radiopharmaceutical syntheses by the Julich group e.g. fluoroacetyl urokinase,160 6-['8F]-nicotininic acid dieth~lamide'~'-'~~ and 3-[IBF]-3-deoxy-~- glucose.'64 If the nuclear reaction takes place in a solution of ammonium acetate then acetyl [18F]hypofluorate is produced which can be used to make 5-[18F]-5-de~xyuridine'~~ This latter compound has also and 2-[18F]-2-deoxy-~-glucose.'66 using xenon [18]difl~oride169 been produ~ed'~~*'~~ to introduce the radioactive fluorine atom.Silver ['8F]fluoride continues to be used to produce labelled organic molecules e.g. alkyl fluorides,'70 6- or 2-['8F]-9-benzylpurine'71and 6-fluoromethyl- 19-norcholesterol.'72 Attempts to improve the fluoro-labelling of have included the use of crown ether fluoride reagent^."^ 35S,36C1.-Methods 17'35S-labelled thiosemicarbazone offor the preparation 2,4-dithiobi~ret,'~~ and also 36C1-labelled hypo- and an anticoagulant p~lyelectrolyte,'~~ chlorous acid and C102179 have been described. 67 Ga.-Desferrioxamine forms a stable complex with gallium (67Ga)180-'82 which can couple with human serum albumen thus providing a label. Other labelled gallium 155 M. G. Straatmann D. J. Schlyer and J. Chasko ref. 85 p. 1373. IS6 M.R. Kilbourn H. Saji and M. J. Welch ref. 124(b) p. 1101. I57 S. Levy D. R. Elmaleh and E. Livni 1. Nucl. Med. 1982 23 918. R. Iwata T. Takahashi M. Shinohara and T. Ido ref 85 p. 1350. I59 R. A. Ferrieri R. R. MacGregor S. Rosenthal D. J. Schlyer J. S. Fowler and A. P. Wolf ref:85 p. 1620. 160 C. N. Mueller-Platz G. Kloster G. Stoecklin and G. Legler re$ 85 p. 1645. 161 E. J. Knust H.-J Machulla and M. Molls ref. 85 p. 1643. I62 E. J. Knust C. Mueller-Platz and M. Schueller J. Radioanal. Chem. 1982 74 283. I63 E. J. Knust H.-J. Machulla and Ch. Astfalk Radiochem. Radioanal. Lett. 1983 55 249. E. J. Knust H.-J. Machulla and K. Dutschka Radiochem. Radioanal. Lett. 1982 55 21. I65 C.-Y. Shiue A. R.Wolf and M. Friedkin. ref 85. p. 1395.I66 C.-Y. Shiue P. A. Salvadori A. P. Wolf J. S. Fowler and R. R. MacGregor J. Nucl. Med. 1982,23 899. I67 S. Sood G. Firnau and E. S. Garnett Int. J. Appl. Radiat. Isot. 1983 34 743. I68 J. S. Fowler C. Y. Shiue A. P. Wolf P. A. Salvadori and R. R. MacGregor ref. 85 p. 1634. 169 G. Firnau R. Chirakal G. Schrobilgen and E. S. Garnett re$ 85 p. 1342. 170 M. Yagi Y.Murano and G. Izawa Int. E Appl. Radiar. Isot. 1982 33 1335. 171 T. Irie K. Fukushi 0. Inoue T. Yamasaki T. Ido and T. Nozaki Int. J. Appl. Radiat. Isot. 1982 33 633. I72 T. Kobayashi M. Maeda and M. Kojima ref 85 p. 1507. 173 L. A. Spitznagle C. A. Marino and S. Kasina ref 156 p. 636. 174 J. S. Ng J. A. Katzenellenbogen and M. R. Kilbourn J. Org. Chem. 1981,46 2520.175 T. Irie K. Fukushi T. Ido Y.Kasida and T. Nozaki hr. J. Appl. Radiat. hot. 1982 33 1449. 176 H. Renault Ann. Pharm. Fr. 1982,40 377. 177 W. R. Porter K. D. Williams and R. E. Peterson J. Labelled Compd. Radiopharm. 1982 19 881. 178 L. C. Sederel L. Van der Does A. Bantjes and Z. Kolar J. Labelled Comp. Radiopharm. 1982.19 1251. 179 H. A. Ghanbari W. B. Wheeler and J. R. Kirk in 'Proc. 4th Conf. on Water Chlorination; environmental impact and health effects' ed. R. L. Jolley W. A. Brungs J. A. Cotruvo R. B. Cummings J. S. Mattice and V. A. Jacobs Ann Arbor Sci. Pubs. Ann Arbor Mich U.S.A. 1983 volume 4 p. 543. I80 G. A. Janoki J. F. Harwig and W. Wolf ref. 85 p. 1405. I81 Y. Yokoyama Y. Ohmomo K. Horiuchi H. Saji H. Tanaka K. Yamamoto Y.Ishii and K. Torizuka J. Nucl. Med. 1982 23 909. I** A. G. Janoki J. F. Harwig and W. Wolf ref. 156 p. 689. 334 D. S. Urch compounds that have been prepared recently include the tri~atecholamide'~~ and the tetrasulphothalocyanine complex.'84 75 As,75Se.-The use of [76As]dimethylchloroarsineas an intermediate in the produc- tion of radiopharmaceuticals such as dimethylarsinopenicillamine has been de~cribed.'~~ Sodium hydrogen selenide (NaH7%e) which can be made by reducing [75Se]selenious acid with sodium borohydride can similarly be used as an inter- mediate to introduce selenium radioactivity into molecules such as fatty acids steroids etc.186*187 Br.-A variety of different techniques has been described (and the limitations reviewed188) for inducing s~dium[~~Br]bromide to react with organic molecules (i) with an alcohol in acetonitride solution with chl~rotrimethylsilane,'~~ (ii) with an alcohol carbon tetrachloride and triphenylpho~phine,'~' (iii) with estrone diol diacetate hydrogen peroxide and acetic acid.19' Organoboranes also react with sodium bromide (in the presence of chloramine-T) to produce the corresponding alkyl or aryl bromide (this work was done with 82Br).192 Labelled dibromine itself can be used in chloroform as in the formation of [6-82Br]cholestrol from 6-chloromer- cury chole~trol.'~~ The radiobromination of aromatic systems has been studied in the absence of and a range of other bromine-labelled molecules has been prepared triflu~robromomethane,'~~'~~ 4-bromomisonidazole,198 bromo-D-glucose ana-logue~,~~~ bromobenzodiazepine,200 bromo-estrogens201 etc.Tc.-The chemistry of technetium has been the subject of a general review,202 some v,'" electrochemi~try,~~~ particular reviews (valencies I-Iv,~'~ X-ray photoelectron I83 S. M. Moerlein D. D. Dischino K. Raymond F. L. Weitl and M. J. Welch re5 85 p. 1421. 184 J. E. van Lier and J. Rousseau ref 85 p. 1467. Ins F. Hosain A. Emran R. P. Spencer and K. S. Clampitt Int. J. Appl. Radiat. Isot. 1982 33 1477. I86 S. A. Sadek G. P. Basmadjian and R. D. Ice NucL Med. Commun. 1982 3 247. G. P. Basmadjian S. Sadek and R. D. Ice ref 85 p. 1482. inn K. D. McElvany M. J. Welch J. A. Katzenellenbogen S. G. Senderoff. G. E. Bentley and P. M. Grant Int.1.AppL Radiation Isot. 1981 32 41 1. 189 M. R. Kilbourn K. D. McElvany and M. J. Welch Int. J. Appl. Radiation Isot. 1982 33 391. 190 M. R. Kilbourn and M.J. Welch Int. J. Appl. Radiation hot. 1982 33 1479. 191 S. G. Senderoff K. E. Carlson D. F. Heiman J. A. Katzenellenbogen K. D. McElvany and M. J. Welch Int. J. Appl. Radiation Isot. 1982 33 545. 192 G. W. Kabalka K. A. R. Sastry and P. G. Pagni J. Radioanal. Chem. 1982 74 315. I93 L. Bo-Li J. Yu-Tai P.Zhong-Yun and M. Kojima J. Labelled Compd. Radiopharm. 1982 19 1089. I94 R. S. Coleman R. H. Seevers and A. M. Friedman 1.Chem. SOC.,Chem Commun. 1982 1276. 19s G. S. Petzold Dissertation Institute for Nuclear Chemistry Cologne University Cologne BRD 1982. 1% D. de Jong and B.W. van Haltern Int. J. AppL Radiat. Isot. 1982 33 387. I97 A. G. Rodriguez T. P. Estrada and G. V.Perez 4th Symposium on Nuclear- Radio- and Radiation- Chemistry Universidad Nacional Autonoma de Mexico (Centro de Extudios Nucleares) Mexico City Mexico 1982. I98 J. S. Rasey S. Freauff and K. A. Krohn J. Radiat. Res. 1982 91 542. I99 G. Kloster P. Laufer W. Wutz and G. Stoecklin reJ 85 p. 1626. 200 H.Scholl P. Laufer G. Kloster G. Stoeckiin ref 85 p. 1294. 20I S. W. Landvatter M. K. Mao J. A. Katzenellenbogen M. D. McElvany and M. J. Welch ref:85,p. 1292. 202 K. Schwochau Radiochem. Acta 1983 32 139. 203 A. G. Jones and A. Davison Int. J. AppL Radiat. Isotop. 1982 33 867. 204 A. Davison and A. G. Jones Int. J. Appl. Radiat. Isotop.1982 33 875. 2os C. D. Russell Int. J. Appl. Radiat. Isotop. 1982 33 883. Radiochemistry 335 spectroscopy,206 n.m.r.207) and of two new Gmelin supplement^.^^^*^^^ Recent pro- gress in the field of 99mTc-radiopharmaceuticalshas also been briefly reviewed?l0 as has the relationship between structure and2I1 activity for these compounds. The development of suitable 99mT~ 'generators' from which the isotope can be eluted as and when required continues to be of interest,212 as does the radiochemical purity of what actually comes off the The quality and stability2'" of technetium complexes has also been considered. Whilst the number of 'labelled complexes' of technetium is large and continues to expand rapidly it has to be admitted that quite often the exact chemical nature of what is formed is not well characterized -either as to structure composition or even valence state of the technetium.This is because most preparations start with Tc04-(VII) which is reduced in situ with Sn2+. A detailed study of products formed in citric acid however revealed217 oxo(bis-citrato)technatecomplexes with TcV or Tc'" (as hydroxo-etc.) depending upon the extent of reduction. Similarly reduction in the presence of aminopolycarboxylic acids gave complexes of Tc'" or Tc"' depending upon the PH.~'' The problem has been considered more generally for a range of ligands such as mercaptoethylamine pyr~phosphate,~~~ etc. The role of solvent and possible proton sources have also been investigated.220 A detailed study of iminodiacetate-technetium complexes revealed that many pharmaceutical prepar- ations are in fact mixtures.221 Other technetium compounds and complexes (mix- tures?) that have been reported recently have ligands such as cyclamen,222 ethylen- diamine,223 tr~polone,~~~ nitrogen heterocycles,225 substituted iminodiacetic acids,226 dithiocarbamate~,~~' and penicillamine.228 Univalent technetium can apparently be stabilized by r-acceptor ligands such as i~ocyanide.~~~ 206 V.N. Gerasimov S. V. Kryuchkov A. F. Kuzina V. M. Kulakov S. V. Pirozhkov and V. I. Spitsyn Dokl. Akad. Nauk SSR 1982 266 148. 207 K. J. Franklin C. J. Lock B. G. Sayer and G. J. Schrobilgen J. Am. Chem. Soc. 1982 104 5303. '208 'Technetium. Suppl. Vol. 1 General Properties Isotopes Production Biology' ed.H. K. Kupler and C. Keller Gmelin Handbook of Inorganic Chemistry Springer Berlin BRD 1982. 209 'Technetium. Suppl. Vol. 2 Metal-Alloys-Compounds-Chemistry in Solution' ed. G. de Alleluia J. Burgess R. D. Peacock C. Keller S. Moebius S. Ruprecht and K. Schwochau Gmelin Handbook of Inorganic Chemistry Springer Berlin BRD 1982. 210 B. A. Johannsen and B. Johannsen Drsch. Gesundheitsw. 1982 37 1753. 21 I R. Muenze re$ 85 p. 1453. 212 S. M.Milenkovic J. L. Vucina L. M.Jacimovic E. S. Karanfilov and T. V. Memedovic Isotopenpraxis 1983 19 85. 213 P. Naesman and T. Vaeyrynen Eur. J. Nucl. Med, 1983 8 26. 214 J. Cifka Int. J. Appl. Radiat. isot. 1982 33 849. 215 V. Jananovic T. Maksin and J. Bzenic Eur. 1.Nucl.Med. 1983 8 179. 216 R. Berger Int. J. Appl. Radiat. Isot. 1982 33 1341. 217 R. Muenze I. Hoffmann R. Dreyer and I. Dreyer J. Radioanal. Chem. 1982 74 63. 218 S. Seifert B. NOH and R. Muenze Int. J. Appl. Radiat. Isot. 1982 33 1393. 219 M. A. Gracheva 0. N. Ilyushchenko G. E. Kodina and V. I. Levin ref 85 p. 1535. 220 J. B. Slater J. F. Harwig and W. Wolf re$ 85 p. 1605. 22 1 C. D. Russell and A. G. Speiser Int. J. Appl. Radiat. Isot. 1982 33 903. 222 D. E. Troutner W. A. Volkert C. Reid T. Hoffman and R. A. Holmes ref 85 p. 1600. 223 W. A. Volkert D. E. Troutner and R. A. Holmes Int. J. Appl. Radiat. Isot. 1982 33 891. 224 L. A. Spitznagle C. A. Marino and S. Kasina J. Radioanal. Chem 1982 74 307. 225 S. Seifert R. Muenze and B.Johannsen Radiochem. Radioanal. Lett. 1982 54 153. 226 A. E. A. Mitta C. Archiprete and E. G. Gros J. Labelled Cornp. Radiopharm 1982 19 1602. 227 J. Baldas and P. M. Pojer in 'Annual Review Research Projects 1981' ed. D. W.Keam (ARL/TR-050) Australian Radiation Laboratory Melbourne Australia 1983 p. 77. 228 A. Yokoyama and K. Horiuchi Int. J. Appl. Radiat. Isot. 1982 33 929. 229 A. G. Jones A. Davison M. J. Abrams et al. ref 85 p. 1594. 336 D. S. Urch Pd In.-The preparation has been described of 109Pd-8-hydroxyquinidine as well as 109Pd-labelled porphyrin~.~~' In-tetraphenylp~rphyrin~~' has also been made and the relative efficiency of all those compounds for labelling lymphocytes and platelets compared. The only other recently reported work with indium concerns the 'labelling' of high molecular weight proteins using either 12' In-~xine~~~ or I 13"In bound to tran~ferrin~~~ in the presence of chelating groups based on iminodiacetic or nitrilotriacetic acids.Te.-The synthesis of 34123mTe]nonadecanoic and 18-methyl- 17-['23Te]nonadec-9-enoic acids for use as heart imaging agents has been described.234 Carrier-free ItsmTe in the tetravalent state in brine forms a 1.-Most recent work concerning the preparation of compounds labelled with radioactive iodine has centred upon the incorporation of 1231 or I2'I although some materials with I3'I have been reported. A lot of activity has upon a-substituted long chain fatty acids where the end of the chain substituent is either iodine or an iodine-containing group.Exchange reactions between 16-iodohexadec- 9-enoic or 17-bromoheptadecanoic and radioactive sodium iodide in acetone (or a higher ketone) procede at temperatures of about 100°C and are facilitated by ultrasonic irradiation. The preparation of 15( p-iodopheny1)pen- tadecanoic acid was brought about using an organic thallium intermediate,240 but the same product can be made by a simple exchange reaction.241 Similar acids but with a methyl side chain e.g. 14- or 15-(p-[1231]iodophenyl),2-or 3-(R,S)-methyl (tetra- or penta)-decanoic acid have also been labelled242 with radioactive iodine. Tellurated substituted fatty acids 15-( p-['251]iodophenyl)-6-tellurapentadecanoic acid have been made as well.243*244 The rather more complex [1231]iodohistamine- labelled A3-tetrahydrocannabinol-1 1 -oic acid has been prepared.245 A very wide range of other compounds usually with biochemical tracer potential has also been made; 1,2-diphenyl-3,3-dichlorocyclopropane246 (radioactive iodine is found to replace chlorine most effectively when the thallium 'iodine carrier' or triazine hydrolysis methods are used) iodinated I-substituted 4-~henylpiperazines,~~~ 230 S.C. Srivastava R. A. Fawaz T. R.T. Wang T. Prach P. Richards and P. 0.Alderson ref:85 p. 1392. 23 I C. Cloutour J.-C. Pommier D. Ducassou and L. Vuillemin fnt. J. Radiat. hot. 1982 33 1311. 232 B. J. Weiblen A. J. Melarango N. Catsimpoolas and C. R.Valeri J. Immunol. Methods 1983 58 73. 23.3 A. Rokos B. Angelis and J.Cifia Radioisotopy 1981 22,649. 234 G. P. Basmadjian R. D. Ice and S. L. Mills Nucl. Med. Commun. 1982 3 150. 235 Y. Maruyama and Y. Nagaoka Radiochem. Radioanal. Lett. 1983 56 23 1. G. El-Shaboury and M. El-Garhy ref 85 p. 1529. 236 237 F. Riche M. Vidal J. P. Mathieu G. Busquet M. Comet S. Coornaert A. Bardy and J. Godart ref 85 p. 1321. 238 F. Riche M. Vidal J. P. Mathieu M. Comet S. Coornaert and M. L. Conti Radiochem. Radioanal. Lett. 1982 53,225. 239 W. Vanryckeghem A. Bossuyt R. van den Driessche J. Mertens and P. van den Winkel J. Biophys. Med. Nucl. 1982 6 159. 240 P. V. Kulkarni and R. W. Parkey ref 85 p. 1319. 24' M. Eisenhut Int. J. Appl. Radiat. Isot. 1982 33,499. 242 M. M. Goodman G. Kirsch and F. F.Knapp ref:85 p. 1316. 243 M. M.Goodman F. F. Knapp A. P.Callahan and L. A. Ferren J. Nuel. Med. 1982 23,904. 244 F.F.Knapp M. M. Goodman and A. P.Callahan ref 85 p. 1323. 245 B. Law P. A. Mason A. C. Moffat and L. J. King J. Labelled Comp. Radiopharm. 1982 19 915. 246 G. P. Basmadjian D. L. Gilliland R. A. Magarian R. D. Ice and A. P. Marchand ref 85 p. 1484 247 (a) R. N. Hanson ref 85 p. 1303; (b) R.N. Hanson fnt. 1.Appl. Radiat. Isot. 1982 33,629. Radiochemistry 337 Jiod~estradiol,~~~ ['231]iodoamphetamine,248 16~u-['~~I 3,3',5 tri-['251]iodo-thyr~nine,~~~.~~' as substituted guanidines,2s2 ~ytidines,~'~ as well ~racils,~~~ and even humic Toluidine Rose Be~~gal,~~~ ~radines,~~~ a derivative of vitamin B1 (cyanocobalamin-d -['2sI]iodohistamide),2s9 and an insulin frag- ment260 have also been labelled with radioactive iodine.ortho-Iodohippuric acid has been prepared in a variety of ways either by exchange with Na'3'126' or by exchange with 1231produced by the irradiation of 124Te02 with protons or '22Te02 with deutrons.262 The relative merits of various radio-iodination procedures for aromatic compounds have been considered.263 Heavier Elements.-Ytterbium- 169 has been incorporated into a phytate complex264 for use in nuclear medicine. Osmium-191 ('910sC14 in HC1) can be exchanged for the iron in ferrocene in 45% yield to give radioactive osmocene.26s Radioactive versions of platinum-containing anti-cancer drugs containing '9smPt have been pre~ared~~~,~~' At.-Studies of the chemistry of astatine have permitted the boiling points of At1 and elemental astatine to be estimated268 (486 and 503 K respectively).Complex ions of the type AtX2- (X = C1 Br I,269 SCN or CN270) have also been investigated. It has been found that astatine in hot dilute acid solution undergoes a substitution reaction with benzene to form a~tatobenzene.~~' The only other aspect of astatine chemistry to be reported recently is the synthesis of the anti-tumour drug 6-[" Atlastato-2-methyl-1,4 naphthoquinol as the bis-diphosphate salt.272 248 R. M. Baldwin T. H. Lin and J. L. Wu ref 85 p. 1305. 249 F. Therain J. Gros and A. Souchu J. Biophys. Med. Nucl. 1982 6 155. 250 M. B. Espejel and C. J. Lezama ref 197 p. 23. 25 I R. Somack S. K. Nordeen J.W. Apriletti J. D. Baxter and N. L. Eberhardt Endocrinology 1982 111 1758. 252 P. Angleberger M.Wagner-Loeffler and R. Hruby ref 85 p. 1479. 253 U. Linz J. Labelled Comp. Radiopharm. 1982 19 1151. 254 J. R. Mercer L. I. Wiebe E. E. Knaus W. Maier-Borst and F. Helius ref 85 p. 1398. 255 A. Freud D. Solenchek E. Ben-Hur and 2.Teitelbaum in 'Research Laboratories Annual Report-1981' (1 A- 1379 Israel Atomic Energy Commission Tel Aviv Israel 1982 188. 256 J. C. Lobartini N. R. Curvetto and G. A. Orioli Int. J. Appl. Radiat. Isot. 1982 33 1331. 257 S. Soenarjo Majafah BATAN 1981 14 1. 258 E. G. Alekseev and V. M.Zaitsev J. RadioanaL Chem. 1983 78 53. 259 T. M. Hoults Clin. Chim. Acta. 1982 126 315. 260 Y. M. Megahed M. F. Abdel-Wahab M.A. Zewall and A. M. Shalaby Isotopenpraxis 1983 19 274. 26 I K. Kopicka P. Hradilek and L.Kronrad Jad. Energ. 1982 28 369. 262 G. J. Beyer G. Pimental L. Kronrad and P. Hradilek ref 85 p. 1488. 263 H. Youfeng H. H. Coenen G. Petzold and G. Stoecklin J. Labelled Comp. Radiopharm. 1982 19,807. 264 N. H. Agha A. M. Al-Hilli H. A. Hassen M. H. S. Al-Hissoni and K. M.Miran Int. J. Appl. Radiat. Isot. 1982 33,673. 265 G. Schachschneider and M. Wenzel J. Labelled Comp. Radiopharrn. 1982 19 1071. 266 W. Cole J. Wiza B. Odenheirner. W. Wolf J. D. Hoeschele T. A. Butler and R. D. Srnyth ref:85 p. 1400. 267 J. D. Hoeschele T. A. Butler J. A. Roberts and C. E. Guyer Radiochim. Acra. 1982 31 27. 268 K. Otozai and N. Takahashi Radiochim.Acta 1982 31 201. 269 R. Dreyer I. Dreyer F. Roesch and G.-J. Beyer Radiochern. Radioanal. Letf. 1982 54 165. 270 R. Dreyer I. Dreyer M. Pfeiffer and F. Roesch Radiochern. Radioanal. Lett. 1983 55,207. 27 1 (a) L.Vaslros Yu. V. Norseyev and V. A. Khalkin Dokl. Akad. Nauk SSSR 1982 266 120; (b) L. Vaslros Yu. V. Norseyev D. D. Nhan and V. A. Khalkin Radiochem. Radioanal. Lett. 1982 54 239. 272 (a) I. Brown Radiochern. Radioanal. Lett. 1982 53,343; (b) I. Brown ref 85 p. 1389. 338 D. S. Urch 4 Chemicals Effects of Nuclear Transformations Chemical reactions intitated by nuclear reactions and also nuclear decay processes but excluding radiation chemistry will be considered in this section of the report. All aspects of this subject are discussed in depth in the book ‘Modern Hot Atom Chemistry and its Applications’.273 The topic is discussed in Volume 3 of Majer’s ‘Foundations of Nuclear Chemistry’,’’ and recent progress was discussed at the eleventh hot atom chemistry symposium274 which was eventually held at Davis University in 1982.Szilard-Chalmers type reactions have been studied in to determine the effects the passage of high energy recoil particles have upon the exchange of ions between different sites as a function of energy. Tritium.-Detailed trajectory calculations have been reported for the system hot 3H + CH4;277 calculations for the hot 3H + CH3NH2 system have suggested278 the possibility of NH2 replacement by 3H via a Walden inversion route. Experimental studies with ethyl and 1,2-difl~oroethylene~~~ at various pressures have revealed the importance of vibrational excitation following the 3H for H labelling reaction.Such excitation was found to be even more important in the reactions of recoil tritium atoms with monogermane where neither H3H nor GeH33H yields were affected by the addition of scavanger or the amounts of added moderator.281 In the liquid phase reactions with chloromethanes282 and chl~roethylenes~~~ have been studied. Very low yields of H3H were found; indeed in carbon tetrachloride 99% of the recoil atoms did not react (to form a stable bond) whilst translationally excited. Not surprisingly labelled polymers were the major yield from the unsaturated molecules. In the solid state the reactions of recoil tritium atoms with ethane adsorbed on a zeolites have been investigated.284 Whilst the mass spectrum of propane shows C3H5+ to be the commonest ion the major products formed by the decay of a tritium atom in multi-tritiated propane in the presence of benzene or toluene were labelled n- and iso-propyl arene~.~~’ This result may be rationalized by assuming that whilst the initial ionization of propane yields C3H7+ the reaction C3H7+-* C3H5+ + H2 has a low activation energy and can proceed rapidly enough in a mass spectrometer for the ally1 ion to be formed extensively.11 C,I3N,”0.-The reactions of recoil 13N with methanol and [2H4]methanol have been studied286 and showed neither temperature nor isotope effects. “C and I3N 273 T. Tominaga and E.Tachikawa ‘Modern hot-atom chemistry and its applications’ Springer Berlin BRD 1981. 274 ‘Eleventh International Hot Atom Chemistry Symposium’ Abstracts ed. J. Root University of California at Davis California U.S.A. 1982. 275 P. A. Newell and L. V. C. Rees Zeolites 1983 3 28. 276 A. Dyer Q. Guan-Lin and L. V. C. Rees Zeolites 1983 3 108. 277 T. Valencich J. Chem. Phys. 1983 79 671. 278 R. S. Asatryan I. A. Abronin and A. N. Nesmeyanov Izv. Akad. Nauk SSR Ser. Khim. 1982 1958. 279 Y. Tang E. Wu J. W. Anderton and R. R. Clark J. Chem. Phys. 1983 79 2181. 280 E. E. Siefert D. D. Smith R. E. Tricca P. M. Ayoub and Y. N. Tang J. Am. Chem. SOC. 1983 105,330. 2n I M. Castiglioni and P. Volpe Polyhedron 1983 2 225. 282 J. R. Veenboer and G.A. Brinkman Radiochirn. Acta 1982 31 7. 283 J. R. Veenboer and G. A. Brinkman Radiochirn. Acta 1982 30 1983. 284 (a) T. V. Tsetskhladze N. Ya. Tsibakhashvili Khim. Vvs. Ehnerg. 1983 17 86; (6) V. A. Barnov and T. V. Tsetskhladze Radiokhimiya 1982 24 264. 285 F. Cacace R. Cipollini and P. Giacomello J. Phys. Chem. 1982 86 2062. 286 Y. Sensui K. Tomura and T. Matsuura Radiochem. Radioanal. Lett. 1982 55 39. Radiochemistry 339 reactions in solids have been reviewed287 and the importance of radiation dose in determining the distribution of products labelled with llC 13N,and 150has been emphasized.288 18 F.-The gas-phase chemistry of recoil fluorine has been reviewed289 and the reactions with liquid-phase halogenomethanes studied (CCl, CHC13 CFC13).290 Thermalized 18F atoms (using excess SF as bath gas) have also been investigated with hydrocarbons,291 and alkyl ~tannanes.~~~ "Si.-The reactions of recoil silicon atoms [31 P(n,pP1 Si] in phosphine trimethyl- silane mixtures have been shown to give rise to a range of labelled pr0ducts.2~~ In many cases the proposed reaction mechanisms are quite complex and involve the facile rearrangements of silylene intermediates.35S.-A most useful bibliography of recoil sulphur has a recently appeared,295 from Sofia University. C1.-The formation and reactions of vibrationally excited molecules produced as a result of a substitution reaction involving a recoil 'hot' atom have been discussed both in and in particular for systems such as chloromethyl cyclopropane chlorocyclobutane The interconversion of these two isomers was initiated by 38Cl for C1 substitution.Other recent work involving recoil chlorine has been in condensed phases. 5-Chlorourasil 5-chloro-2'-deoxyuridine,and 5-chlorouridine will all react298 with recoil ,'Cl in aqueous solutions to yield the labelled parent molecules as the major organic product (but in small absolute yield). In liquid CC14 CHC13 and CFCl, the reactions of 34mCl and 38Cl have been compared; cage and radical recombination reactions were identified.290 The reactions of recoil chlorine in liquid mixtures e.g. ethyl chloridezw or n-butyl chloride300 with hydrocarbons alcohols and aniline have been investigated and the results analysed by the theory of Kontis and Ur~h.~" Similar studies have been made with aromatic molecules chlor~toluenes,~~~ and halogenoaniline~.~~ o-dichlor~benzene,~~~ The effect of going to the solid state for such mixtures has also been rep~rted.~~*~~~ 287 K.Roessler M. Vogt A. Izquierdo C. Mathias and L. M. Al-Shukri in 'Keorn- Radio- Strahlenchemie- Grundlagen und Anwendungen' Karlsruhe Gesellschaft Deutscher Chemiker Frankfurt-am-Main BRD 1982. 288 G. A. Brinkman Int. J. Appl. Radiat. Zsot. 1982 33 525. 289 J. W. Root Adu. Chem. Ser. (No. 197) 1981 p. 80. 290 G. A. Brinkman and J. Visser Radiochem Radioanal Lett. 1982,54 331. 29 1 J. W. Root C. A. Mathis R Gurvis K.D. Knierim and S. H. Mo Adu. Chem. Ser. (No.197) 1981 p. 207. 292 M.van der Ley B. W. van Halteren and G. A. Brinkman Radiochem. Radioanal. Len 1983 57 55. 293 M. Kikuchi J. A. Cramer R. S. Iyer J. P. Frank and F. S. Rowland J. Phys. Chem 1982 86 2677. 294 S. H. Mo,J. D. Holten (III) S. Konienny E. C. Ma and P. P. Gaspar J. Am Chem. SOC.,1982,104,1424. 295 D. Todorovski and D. P. Koleva 'Hot Atom Chemistry of Sulphur' Khimicheski Fakultet Sofia University Sofia Bulgaria 1982. 296 L. D. Spicer Adu. Chem Ser. (No. 197) 1981 p. 123. 297 L. J. Ferro PhD. Thesis Utah University Salt Lake City Utah U.S.A. 1982 (Microfilm order No. 82-20 778). 298 L. J. Arsenault A. J. Blotcky M. L. Firouzbakht and E. P. Rack Radiochim. Acta. 1982 31 171. 299 A. S. Agrawal and B. S. M. Rao Radiochim Acta 1982 31 13. 300 S.F. Patil R. N. Bhave and A. R. Galande Radiochern. Radioanal. Lett. 1983 57 151. 301 S. S. Kontis and D. S. Urch. Radiochim. Acta 1973 20 39. 302 R.N. Bhave B. S. M. Rao B. W. van Halteren and G. A. Brinkman Radiochim. Acta 1982 31 185. 303 R. N. Bhave and B. S. M. Rao Radiochim. Actq 1982 30,189. 304 V. D. Dedgaonkar S. Mitra and S. Waghmore Radiochem. Radioanal. Lett. 1983 56 87. 305 S. S. Gigoo A. S. Agrawal R. N. Bhave and B. S. M. Rao Radiochem. Radioanal. Left. 1982,53 195. 340 D. S. Urch First Row Transition Metals.-The reactions of recoil chromium atoms in solid and pentane solutions of chromium hexacarbonyl have been studied.306 In the solid state the thermal annealing of 51Cr1*1-doped ammonium dichromate was found307 to give similar results to the neutron irradiation of ammonium dichromate.Related experi- ments with permanganate [,,Mn(n y)56Mn] investigated308 the effects of isochronal heating on the distribution of manganese valency states. Solid state studies for a variety of cobalt systems have also been reported tri~(acetylacetonato),~~~ tri~(dipyridyl),~" and [Co(H,O),]. [Co EDTAI2. 4H20.3' I Br.-76Kr and 77Krdecay by electron capture (e.c.) and by p' (84%) + e.c. (l6%) respectively giving rise to bromines with low recoil energies and various charge states. The chemistry of these different 76Br and 77Br species in pr~pylene,~'~ perflu~ropropylene,~ethyl and trifluoromethyl halides3I4 has been l2 investigated in some detail. For the most part bromine substitution reactions were shown to have an efficiency of only a few per~ent.~" Neutron irradiation initiated reactions in aqueous solutions of bromo-nucleotide bases give small yields of labelled (80Br) parent molecules.298 Annealing studies of the fate of 80mBr in bromates (potassium316 and calcium317) have been made; the importance of surface states in understanding annealing behaviour has been empha~ized.~'~ In mixed crystals K20sBr,-K2SnC1 the recoil reaction of bromine initiated by both 81Br(n,y)82Br and 79Br(y 2n)77Br have been studied and compared.318 Second Row Transition Metals.-The chemistry of recoil Mo atoms in molybdenum hexacarbonyl has been investigated and labelled Mo(CO) was found when Fe(CO), MoCl mixtures were irradiated with neutrons.306 The disruptive effects within a molecule of p-decay p' decay electron capture and isomeric transition have been studied3I9 for oxymolybdenum phthalocyanine by comparing the effect of p-with that of the p' etc.decay of 90M~(t~ decay 99Mo(to99T~) 90Nb); bond rupture is least for p-decay. The effects of isomeric transition in a chemically bound atom have also been studied320 for 95mTCF62- (as potassium salt) both in the solid state where 90% retention was found and in solution where retentions of as low as 1% were found. Neutron irradiation of ruthenium( 11) A-tris( 1,lO-phenanthroline) per- chlorate solutions gave low yields (1-2%) of the parent molecule but less than 306 T. Muto and H. Ebihara Radiochim. Acta. 1982 31 179. 307 M. I. Stamouli Radiochim.Acta 1982 31 117. 308 V. G. Dedgaonkar S. Mitra and S. A. Kulkarni J. Univ. Poona Sci Technol. 1981 54 27. 309 Y. Sakai H. Nishioji S. Yamauchi and T. Tominaga Radiochem. Radioanal. Lett. 1982 53 215. 3 10 M. I. L. Maretti and'C. H. Collins Cienc. Cult. (Sao Paulo) Suppl. 1982 34 378. 31 I G. Albarran C. Archundia and A. G. Maddock Radiochim. Acta. 1982 30 199. 312 D. de Jong G. A. Brinkman B. W.van Halteren and J. Th. Veenboer Radiochem. Radioanal. Lerr. 1983 55 231. 313 D. de Jong G. A. Brinkman and B. W. van Halteren Radiochem. Radioanal. Let(. 1983 56 165. 3 I4 D. de Jong G. A. Brinkman and B. W. van Halteren Radiochem. Radioanal. Lett. 1982 55 113. 315 D. de Jong 'Proefschrift (Dr.) 'University of Amsterdam Netherlands 1982.3 I6 S. Fernandez-Valverdo M. Jirnenez-Reyes J. Serrano J. de la Torre and A. G. Maddock Radiochim. Acta 1982 31 19. 317 V. G. Dedgaonkar R. S. Lokhande and D. A. Bhagwat J. Univ. Poona Sci. Technol. 1981,54 37. 318 H. Mueller and P. Bekk '4th Symposium on Nuclear Chemistry Radiochemistry and Radiation Chemistry' Centro de Estudios Nucleares Universidad Nacional Autonoma de Mexico Mexico City 1982 p. 47. 319 K. Yoshihara H. Sugasawa and T. Sekine Radiochem. Radioanal. Left. 1983 56 349. 32U E. Ianovici 0.Lerch G. Zahner and A. G. Maddock Radiochim. Acta. 1982 31 79. Radiochemistry 341 of the enantiomeric compound,32' from which it may be concluded that most 'retention' probably results from the central ruthenium atom not being dislodged from the complex by the (n,y) reaction.1.-The chemistry of recoiling "'I species in iodo-aromatic compounds as solids and in solutions of benzene or methanol have been investigated322i323 to determine the roles of neutral and charged species. Recoil I2'I can give rise to labelled parent molecules when solutions of iodo-nucleotide bases are neutron irradiated.298 Heavier Elements.-The reactions of recoil thallium produced either by a-decay of or by the n,y reaction (to give 204Tl),325 "'Bi (to give 208Tl)324 in T113Tl'11 .C16 have been studied to determine the valence-state distribution of the radioactive thallium atoms. Annealing studies revealed that extensive isotope-exchange reactions take place in the solid state. Recoil astatine can also be produced either by electron capture326 or by radon decay,327 and its reactions with nitrobenzene chloronitroben- zene and chlorobenzene have been the object of detailed study.The chemical effect of a-decay has been studied for 235U bound in various complexes. The 'retention' that is observed depends greatly upon the solution pH which suggests that a-decay does indeed cause the uranium atom to break its chemical bonds and that the complex is reformed by finding free ligands in solution.328 5 Radiochemistry and Nuclear Power Sources of Uranium.-There is considerable research activity to determine ways in which uranium might be extracted from sea water using different possible adsor- bent~~~~ and ion-exchange resins.330 Aluminium phosphate33 * and a variety of materials based on hydrated titanium (e.g.with activated charc~al,~~~,~~~ with activated charcoal or made into granules with polyacrylic acid hydroxide as binder)335 have been shown to be quite efficient. So also was the tetraethyleneglycol dimethacrylate cross-linked poly(acry1amidoxime) resin.336 Nuclear Waste.-A very wide range of radioactive elements is produced by the operation of a nuclear reactor and a thorough knowledge of the chemistry and 32' K Sasaki N. Furukawa and H. Yamatera Radiochirn. Acta. 1982 31 121. "* M. Sharon and R. S. Birajdar J. Univ. Poona Sci. Technol. 1981 54 217. 323 M. Sharon and R. S. Birajdar J. Univ. Poona Sci. Technol. 1981 54 229. 3 24 S. Fernandez-Valverde G. Duplatre and J. M. Paulus Radiochirn.Acta. 1982 31 131. 325 S. Fernandez-Valverde 0.Lira de Vega and A. G. Maddock Radiochim. Radioanal. Lett. 1983,55 183. 326 L. Vasaros Yu. V. Norseyev and K. Berei Radiochim. Acta. 1982 31 75. 321 L. Vasaros Yu. V. Norseyev V. I. Forrninykh and V. A. Khalkin Radiokhirniya 1982 24 95. 328 S. I. I. Naqvi and P.Glentworth Palc J. Sci. fnd. Res. 1980 23 5. 329 Yu. A. Afanas'ev L. T. Azhipa A. I. Ryabinin N. B. Savenok and V. P. Eremin Radiokhirniya 1982 24 258. 330 K. Schwochau L. Astheimer H. J. Schenk and E. G. Witte 2. Naturforsch. Teil. E 1982 37 214. 33 I H. Seki I. Kashiki M. Sakai and A. Suzuki Hokkaido Daigaku Suisangakubu Kenkyu fho 1982,33,166. 332 N. Ogata Nippon Kaisui Gakkai-Shi 1982 35 266. 333 S. Shunsaku K. Sakane T. Hirotsu A.Fujii and T. Kitamura Nippon Kaisui Gakkai-Shi 1981,35 156. 334 S. Kotoh K. Sakane T. Hirotsu A. Fujii and T. Kitamura Shikoku Kogyo Gijutsu Shikenjo Hokuku 1981 13 121. 335 Y. Miyai S. Katoh and K. Sugasaka Nippon Kaisui Gakkai-Shi 1981 35 162. 336 K. Sakane T. Hirotsu N. Takagi S. Katoh K. Sugasaka Y. Umezawa N. Takai and H.Takahashi Nippon Kaisui Gakkai-Shi 1982 36 101. 342 D. S. Urch thermodynamic properties of complexes of these elements is required for the formu- lation of suitable separation and disposal techniques. The recent compilation of such data for the actinides is therefore to be welcomed.337 More specific work has shown that diphenyl(dialky1 carbamoylmethyl) phosphine may be used to extract transplutonium elements from acid solutions and that fission product radio- nuclides can be separated by adsorption on diethyleneglycol ~uccinate.~~~ Other recent work in this field has tended to be more element specific e.g.the use of activated-carbon filters for the removal of iodine iodides,340 c0balt-60,~~' and xenon,342 or a cryogenic process for krypton separation,343 or the use of molecular sieves to collect tritiated water vapour and oxides of or methods to remove I4CO2 from gas streams.344 The removal of ruthenium either by complex formation345or by adsorption346 has also been investigated. Nuclear Waste Disposal.-Nuclear waste may be disposed of either at sea or on land. And whilst in either case it is to be hoped that radioactive isotopes would be contained it is necessary to examine what their behaviour might be were they to escape.For this reason the fate of yttri~m-90~~~~~~~ in sea water and cerium- 144349,350 as well as niobium-95 cobalt-60 and chromium-51,3S' have been studied in detail. On land the current research into the adsorption of transurani~~~~" and fission b,c,d ions by clays and by igneous was reviewed at an International Symposium on 'The migration in the terrestial environment of long-lived radionu- clides from the nuclear fuel cycle'.352 Decontamination.-Reports have appeared describing decontamination procedures for problems as diverse as a hot tritium laboratory353 and a plutonium-contaminated 337 N. Edlestein J. Bucher R. Silva and H. Nitsche Report No. 14325 Lawrence Berkeley Lab.University of California USA. 1983. 338 M. K. Chmutova N. P.Nesterova N. E. Kochetkova 0.Eh. Kojro and B. F. Myasoedov Radiokhimiya 1982 24 31. 339 M. B. Hafez B. M. Abo El-Khair J. Radioanal. Chem. 1983 78 25. 340 J. G. Wilhelm 'Seminar on the testing and operation of off-gas cleaning systems at nuclear facilities' International Atomic Energy Agency (IAEA-SR-72) Vienna Austria 1983 p. 178. 34 1 R. Litman P. Jones and J. Ring Radiochem. Radioanal. Lett. 1982 54 359. 342 H. Ringel ref 340 p. 417. 343 R. von Ammon W. Bumiller E. Hutter G. Knittel C. Mas and G. Neffe ref 340 p. 41 1. 344 C. H. Cheh R. W. Glas and V. S. Chew ref 340 p. 471. 345 J. P. Glatz 'Kationische Ruthenium nitrosyl komplexe in radioaktiven Abfalloesungen' Dissertation (DSc) Saar University Saarbruecken B.R.D.1980. 346 'Control of semivolatile radionuclides in gaseous effluents at nuclear facilities' IAEA Tech. Report-No 220 International Atomic Energy Agency Vienna Austria 1982. 347 A. N. Nesmeyanov and A. A. Volkov Radiokhimiya 1982,24 247. 348 A. A. Volkov V. V. Anikeiv and A. A. Lobanov Radiokhimiya 1982 24 382. 349 A. N. Nesmeyanov L. S. Khova and A. A. Volkov Radiokhimiya 1982 24 386. 350 A. N. Nesmeyanov L. S. Khova A. A. Volkov and Yu. A. Sapozhnikov Radiokhimiya 1982 24 542. 351 L. S. Khova A. A. Volkov E. N. Shumilin and Yu. A. Sapozhnikov Vestn. Mosk. Univ. Ser. 2 Khim. 1982 23 306. 352 'International Symposium on migration in the terrestial environment of long-lived radionuclides from the nuclear fuel cycle' (Knoxville Tenn.U.S.A 1981) International Atomic Energy Agency Vienna Austria. 1982. (a) A. Billon ref 352 p. 167; (6) M. Y. Farah A. S. Abdel-Gawad N. Z. Misak W.E. Abdelmalik E. Mitry and H. B. Maghrawy ref 352 p. 70; (c) A. S. Abdel-Gawad N. 2. Misak N. B. Maghrawy and A. Shafik reJ352 p. 812; (d) L. Carlsen and P. Bo ref 352 p. 97; (e) K. Anderson B. Torstenfelt and B. Allard re$ 352 p. 11 1. 353 J. R. Harper and R. Garde Report LA-9056-MS Los Alamos National Laboratories 1981. Radiochemistry portion of Nevada.354 Rather more down to earth is a description of the use of high pressure freon for cleaning up mildly contaminated equipment355 and the use of painted surfaces to adsorb radionuclides from solutions.356 6 Miscellaneous The half-lives of 253Es (20.31 * 0.16 245Cm (8845 * 200 years),358 and "Rb[5.56 f0.025) x 10" years]359 as well as the decay constant for the spontaneous fission of 238U(6.6x lo-'' years-')360 have been determined recently whilst modest interest continues to be given to the changes in half-life that can be ascribed to chemical effects (51Cr).361 And finally for something quite different the chemistry of the light isotope of hydrogen muconium has been reviewed.362 354 355 356 357 358 359 360 36 I 362 J.A. Orcutt Report DOE/ NV/00410-70 1982 INIS Atomindex Abs. No. 749174 1983. J. T. McVey C. Campuzano and D. E. Fowler Nucf. Chem. Waste Manage. 1981 2 197. A. C. Gray and D. F. C. Morris Radiochim.Acta. 1982 31 153. V. G. Polyukhov G. A. Tirnofeev and A. A. Elesin Radiokhirniya 1982 24,494. V. G. Polyukhov G. A. Timofeev V. V. Kalygin and P. A. Privalova Radiokhimya 1982 24 490. E. Akatsu Radioisotopes (Tokyo) 1982 30,647. Z. N. R. Baptista M. S. M. Mantovani and F. B. Ribeiro An. Acad. Bras. Cienc. 1981 53 437. A. N. Murin S. 1. Bondarevskij and V. V. Eremin Radiokhimiya 1981 23 933. D. C. Walker J. Phys. Chem. 1981 85 3960.