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Back matter |
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Analyst,
Volume 121,
Issue 4,
1996,
Page 012-014
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摘要:
International Conference on Analytical ChemistryJune 15-21, 1997Moscow University, Moscow, RussiaThe objective of the conference is to highlight the most recent developments in the field of analytical science, specifically in thesessions. It is hoped that the poster sessions will be used to encourage scientists of different generations to exchange ideas and~= subject areas identified below. Presentations will be given in the form of plenary and contributed lectures as well as posteri share experiences in their respective fields.SCOPE, The following major topics will be discussed at the conference:I , Analytical chemistry: Philosophical aspectPreconcentration (including solid phase extraction)ChemometricsChromatography (GC, HPLC, TLC, IC etc.)and related techniques (CE)Molecular spectroscopy (IR, Raman)Nuclear methodsKinetic methodsBioanalytical chemistryAnalysis of new materials(including high-purity materials)Sampling and sample treatmentOrganic analytical reagentsQua1 ity assurance/qual i ty controlAtomic spectroscopy (absorption emission,Mass spectrometryElectroanalytical methodsExpress test methodsAnalysis of raw materialsAnalysis of food and agricultural productsClinical analysisfluorescence, XRF, lasers)ORGANISING COMMITTEEChairperson, Yu A.ZolofovVice-chairmen , B . F. Myasoedova , V .A. Davankov and V . G . KoloshnikovGeneral secretary, L.N. KolomietsYu A. Karpov, I.N. Kiseleva, P.N. Nesterenko, G.I. Ramendik, O.A. Shpigun, S.I. Sinkov, 1.1. Smirenkina,B.Ya. Spivakov, M.M.ZaletinaINTERNATIONAL SCENT IFIC CO MMITTEEChairman, Yu A. ZolotovF. Adams, BelgiumR. Barnes, USAM. Novotny, USAH. Englehardt, GermanyT. Fujinaga, JapanM. Grasserbauer, AustriaB. Welz, GermanyA. Hulanicki , PolandB. Welz, GermanyE. Mentasti, ItalyB . F. Myasoedov , RussiaV .A. Davankov , RussiaH. Frieser, USAE. Pungor, HungaryI. Havesov , BulgariaJ.F.K. Huber, AustriaT Yotsuyanagi, JapanM . I. Karayannis , GreeceCONFERENCE SECRETARIATFor further information please contact :H. Akaiwa, JapanC. Boutron, FranceH. Pardue, USAK. Niemax, GermanyP.G. Zambonin, ItalyI.Kuselman, IsraelS . Tsuge, JapanV.G. Koloshnikov, RussiaG. Werner, GermanyJ.G.H. du Preez, South AfricaJ .A. Perez-Bustamente, SpainL. Sommer, Czech RepublicW. Lindner, AustriaF. Macasek, SlovakiaM. Valiente, SpainH.M. (Skip) Kingston, USAM. Widmer , SwitzerlandYu. A. Karpov, RussiaDr L. N. Kolomiets,Scientific Council on Chromatography RAS, Leninsky Prospect 31, 117915 Moscow, Russia.E-mail : Iarionov@lmm.phyche.msk.suTel: 7 (095) 952 0065; 7 (095) 955 4685 Fax: 7 (095) 952 0065; 7 (095) 952 530
ISSN:0003-2654
DOI:10.1039/AN99621BP012
出版商:RSC
年代:1996
数据来源: RSC
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Front cover |
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Analyst,
Volume 121,
Issue 4,
1996,
Page 013-014
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"AnalystThe Analytical Journal Of The Royal Society Of ChemistryAssociate Scientific Editors*Chairman: Professor James N. Miller(Department of Chemistry, Loughborough University of Technology, UK)Dr Yngvar Thomassen (Arbeidsmiljo lnstituffet,Oslo, Norway)Professor Colin S. Creaser (Department ofChemistry and Physics, Noffingham TrentUniversity, UK)Professor Pankaj Vadgama (Department ofMedicine, University of Manchester, UK)Professor Malcolm R. Smyth (Department ofChemical Sciences, Dublin City University, Eire)'All ASEs are also members of the Analytical Editorial Board.US ASSOCIATE EDITOR, Julian F. TysonDepartment of Chemistry, University of Massachusetts, Box 3451 0 Amherst, MA 01 003-451 0, USATelephone: +1 413 545 0195; Fax: +1 413 545 4846; E-mail: TYSON@CHEM.UMASS.EDUAnalytical Editorial BoardChairman: Professor J.N. Miller (Loughborough, UK)M. Cooke (Sheffield, UK)A. G. Davies (London, UK)A. G. Fogg (Loughborough, UK)G. M. Greenway (Hull, UK)S. J. Hill (Plymouth, UK)R. M. Miller (Gouda, The Netherlands)H. S. Minhas (Cambridge, UK)B. L. Sharp (Loughborough, UK)Advisory BoardN. W. Barnett (Victoria, Australia)K. D. Bartle (Leeds, UK)A. M. Bond (Victoria, Australia)R. G. Brereton (Bristol, UK)U. A. Th. Brinkman (Amsterdam, The Netherlands)A. C. Calokerinos (Athens, Greece)P. Camilleri (Harlow, UK)P. R. Coulet (Lyon, France)D. Diamond (Dublin, Eire)L. Ebdon (Plymouth, UK)H. Emons (Julich, Germany)J. P. Foley (Villanova, PA, USA)M. F. Gine (Sao Paulo, Brazil)J.D. Glennon (Cork, Eire)L. Gorton (Lund, Sweden)S. J. Haswell (Hull, UK)A. Hulanicki (Warsaw, Poland)S. Lunte (Lawrence, KS, USA)F. Palmisano ( Palermo, Italy)J. Pawliszyn (Ontario, Canada)T. B. Pierce (Harwell, UK)J. Rititka (Seaffle, WA, USA)I. L. Shuttler (Uberlingen, Germany)K. Stulik (Prague, Czech Republic)J. D. R. Thomas (Wrexham, UK)K. C. Thompson (Rotherham, UK)M. Thompson (Toronto, Canada)M. ValcArcel (Cordoba, Spain)C. M. G. van den Berg (Liverpool, UK)J. Wang (Las Cruces, NM, USA)I. D. Wilson (Macclesfield, UK)Publishing Division, AnalyticalManaging Editor, Harpal S. MinhasDeputy Editor, Sarah J. R. Williams Editorial Secretaries: Claire Harris; Frances ThomsonTelephone: +44(0)1223 420066; Fax: +44(0)1223 420247; E-mail: ANALYST@RSC.ORGProduction Division, AnalyticalProduction Manager, Janice M.GordonProduction Editor, Caroline Seeley Technical Editors: Yasmin Khan, Ziva Whitelock, Roger A. YoungSecretary: Lesley TurneyTelephone: +44(0) 1223 420066; Fax: +44(0) 1223 423429; E-mail: ANALPROD@RSC.ORGFor enquiries relating to manuscripts from receipt to acceptance, contact the Publishing Division, andfor enquiries relating to manuscripts post-acceptance contact the Production Division, Royal Society ofchemistry, Thomas Graham House, Science Park, Milton Road, Cambridge, UK CB4 4WFAdvertisements: Advertisement Department, The Royal Society of Chemistry, Burlington House,Piccadilly, London, UK W1 V OBN. Telephone +44(0)171-287 3091.Fax +44(0)171-494 11 34.Information for AuthorsFull details of how to submit material for publicationin The Analyst are given in the Instructions toAuthors in the January issue. Separate copies areavailable on request.The Analyst publishes original research papers,critical reviews, tutorial reviews, perspectives,news articles, book reviews and a conferencediary.Original research papers. The Analystpublishes full papers on all aspects of the theoryand practice of analytical chemistry, fundamentaland applied, inorganic and organic, includingchemical, physical, biochemical, clinical,pharmaceutical, biological, environmental,automatic and computer-based methods. Paperson new approaches to existing methods, newtechniques and instrumentation, detectors andsensors, and new areas of application with dueattention to overcoming limitations and tounderlying principles are all equally welcome.Full critical reviews. These must be a criticalevaluation of the existing state of knowledge on aparticular facet of analytical chemistry.Tutorial reviews.These should be informallywritten although they should still be a criticalevaluation of a specific topic area. Some historyand possible future developments should be given.Potential authors should contact the Editor beforewriting reviews.Perspectives. These articles should provideeither a personal view or a philosophical look at atopic relevant to analytical science. Alternatively,they may be relevant historical articles.Perspectives are included at the discretion of theEditor.Particular attention should be paid to the use ofstandard methods of literature citation, includingthe journal abbreviations defined in ChemicalAbstracts Service Source Index.Whereverpossible, the nomenclature employed should followIUPAC recommendations, and units and symbolsshould be those associated with SI.Every paper will be submitted to at least tworeferees, by whose advice the Editorial Board ofThe Analyst will be guided as to its acceptance orrejection. Papers that are accepted must not bepublished elsewhere except by permission.Submission of a manuscript will be regarded as anundertaking that the same material is not beingconsidered for publication by another journal.Associate Scientific Editors.For the benefit ofall potential contributors wishing to discuss thescientific content of their paper@) a Group ofAssociate Scientific Editors exists. Requests forhelp or advice on scientific matters can be directedto the appropriate member of the Group (accordingto discipline). Currently serving Associate ScientificEditors are listed in each issue of The Analyst (andAnalytical Communications).Manuscripts (four copies typed in double spacing)should be addressed to:H. S. Minhas, Managing Editor, orJ. F. Tyson, US Associate EditorAll queries relating to the presentation andsubmission of papers, should be addressed to thePublishing Division and any correspondenceregarding accepted papers and proofs, should bedirected to the Production Division for The Analyst.Members of the Analytical Editorial Board (whomay be contacted directly or via the Editorial Office)would also welcome comments, suggestions andadvice on general policy matters concerning TheAnalyst.There is no page charge.Fifty reprints are supplied free of charge.The Analyst (ISSN 0003-2654) is published monthly by The Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge,UK CB4 4WF.All orders, accompanied with payment by cheque in sterling, payable on a UK clearing bank or in US dollars payable on a US clearing bank, shouldbe sent directly to The Royal Society of Chemistry, Turpin Distribution Services Ltd., Blackhorse Road, Letchworth, Herts, UK SG6 1 HN.Turpin Distribution ServicesLtd., is wholly owned by the Royal Society of Chemistry. 1996 Annual subscription rate EC f487.00, USA $923.00, Rest of World f499.00. Purchased with AnalyticalAbstracts EC f951 .OO, USA $1 804.00, Rest of World f975.00. Purchased with Analytical Abstracts plus Analytical Communications EC f 11 23.00, USA $21 29.00,Rest of World f 11 51 .OO. Purchased with Analytical Communications EC f610.00, USA $1 156.00, Rest of World f625.00. Air freight and mailing in the USA byPublications Expediting Inc., 200 Meacham Avenue, Elmont, NY 11 003.USA Postmaster: Send address changes to: The Analyst, Publications Expediting Inc., 200 Meacham Avenue, Elmont, NY 1 1003. Second class postage paid atJamaica, NY 11431. All other despatches outside the UK by Bulk Airmail within Europe, Accelerated Surface Post outside Europe. PRINTED IN THE UK.0 The Royal Society of Chemistry, 1996. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form,or by any means, electronic, mechanical, photographic, recording, or otherwise, without the prior permission of the publishers
ISSN:0003-2654
DOI:10.1039/AN99621FX013
出版商:RSC
年代:1996
数据来源: RSC
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Contents pages |
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Analyst,
Volume 121,
Issue 4,
1996,
Page 015-016
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摘要:
ANALAO 121(4) 33R-44R, 379-572, 41N-55N (1996) APRIL 1996II I II'"An a I y s tI I1The analytical journal of The Royal Society of ChemistryCONTENTSREVIEWS33R Organic Microheterogeneous Systems in Kinetic Analysis. Self-assembled Systems-A Review-MariaLopez Carreto, Soledad Rubio, Dolores Perez-BenditoThe Fifth International Symposium on Kinetics in Analytical ChemistryCONFERENCE PAPERSFOREWORD 379GUEST EDITOR 379 Professor Horacio A. MottolaBACKGROUND 380 The Road to MoscowPERSPECTIVE 381 From Erlangen to Moscow: Minor Redirections-Horacio A. MottolaPLENARY 385PLENARY 391395Unified View of Kinetic-based Analytical Methods With Emphasis on Ruggedness-A Review-Harry L.PardueAutocatalytic Decomposition of Cobalt Complexes as an Indicator System for the Determination of TraceAmounts of Cobalt and Effectors-Masatoshi Endo, Masahito Ishihara, Takao YotsuyanagiArtificial Neural Networks and Partial Least Squares Regression for Pseudo-first-order With Respect to theReagent Multicomponent Kinetic-spectrophotometric Determinations-Marcel0 Blanco, Jordi Coello,Hortensia Iturriaga, Santiago Maspoch, Miguel Redbn, Nuria VillegasExpert System for Catalytic Titrimetry-Part 1 .Determination of Organic Acids-Bibana F. AbramoviC,Borislav K. AbramoviC, Danilo M. ObradoviC, Ferenc F. GaalSimultaneous Kinetic Spectrophotometric Determination of 0-, m- and pAminophenol Using Partial LeastSquares Calibration-Guillermo Lopez-Cueto, Santiago Maspoch, Jose F. Rodriguez-Medina, CarlosUbideIndicator Reaction for Sensitive Kinetic Micro-determination of Cysteine and Cystine in a Mixture WithoutPrior Separation-A.Giannousios, C. PapadopoulosThermal Lens Determination of Vanadium(v) and its Activators by Oxidation of Aniline by BromateIons-Mikhail A. Proskurnin, Nataliya V. Osipova, Vera V. Kuznetsova, Elena K. Ivanova, Andrei G.AbroskinAutomation of a System for Titrimetric Measurements. Catalytic Thermometric Titrations of OrganicBases-Biljana F. Abramovic, Sanja D. Tepaveevic, Borislav K. AbramoviC, Ferenc F. GaalEnzymic Method for the Determination of Ethanol and Methanol with Spectrophotometric Detection of theRate of the Process-Ulyana M. Mizgunova, Galina A. Zolotova, lnga F. DolmanovaAmperometric Determination of L-Malic Acid in a Flow Injection Analysis Manifold Using Packed-bedEnzyme Reactors-Mamas I.Prodromidis, Stella M. Tzouwara-Karayanni, Miltiades I. Karayannis, PankajVadgama, Andrew Maines40140741 3419425431435CHEMOMETRlCSlSTATISTICS441 Resolution of Multicomponent Mixture Spectra in Mid-infrared Spectroscopy Using Spherical ProjectionFactor Analysis: Application to Real Data Including a Six-component Mixture Set-Stephen. P. Gurden,Richard G. Brereton, John A. GrovesInverse Scattering Theory of Fourier Transform Infrared Photoacoustic Spectroscopy-J. F. PowerComparative Study of the Ratio Spectra Derivative and Partial Least Squares Methods Applied to theSimultaneous Determination of Atrazine and Ametryn in Ground Waters-R. Corbella Tena,M. A. Rodriguez Delgado, Ma. J.Sanchez, F. Garci MontelongoInfluence of Pesticide-Soil Interactions on the Recovery of Pesticides Using Supercritical FluidExtraction-John R. Dean, Ian J. Barnabas, Susan P. Owen451459SAMPLE HANDLING465Continued on inside back cover-THE ROYALCHEMISTRYInformationServices Cambridge, EnglandTypeset and printed by Black Bear Press Limited,0003-2654C199614:l-ATOMIC SPECTROSCOPY/SPECTROMETRYMOLECULARSPECTROSCOPY/SPECTROMETRYSEPARATION SCIENCESENSORSELECTROANALYTICALSURFACE ANALYSISCLASSICAL METHODSOTHER METHODS46947748348949550 150551 152 152753 153554 1547553559563567571Conditions for Solid-phase Extraction of Agricultural Chemicals in Waters by Using n-Octanol-WaterPartition Coefficients-Motoshi Nakamura, Masatoshi Nakamura, Shinkichi YamadaFlow injection Spectrofluorimetric Determination of Fluoride or Phosphate Based on Their Inhibitory Effecton the Photo-oxidation of Acridine Catalysed by Iron( iii)-Tomas Perez-Ruiz, Carmen Martinez-Lozano,Virginia Tomas, Antonio SanzSlurry Preparation by High-pressure Homogenization for Cadmium, Copper and Lead Determination inCervine Liver and Kidney by Electrothermal Atomic Absorption Spectrometry-Yanxi Tan, William D.Marshall, Jean-Simon BlaisExtraction-Atomic Absorption Spectrometric Method for the Determination of the Platinum Group Elementsand Gold in Copper-Nickel Ores Using an Autoclave Sample Decomposition Technique-V. G.Torgov,M. G. Demidova, T. M.Korda, N. K. Kalish, R. S. ShulmanDetermination of Gas-phase Sidestream Cigarette Smoke Components Using Fourier Transform InfraredSpectrometry-S. Keith Cole, Patricia MartinLucigenin Immobilized on Silicon Oxides as a Solid-phase Chemiluminescent Reagent-0. A.Zaporozhets, V. V. Sukhan, N. A. LipkovskaDual-detector System for the Shipboard Analysis of Halocarbons in Sea-water and Air for OceanographicTracer Studies-Stephen M. Boswell, Denise Smythe-WrightRetention Properties of a Spacer-bonded Propanediol Sorbent for Reversed-phase Liquid Chromatographyand Solid-phase Extraction-Donna S. Seibert, Colin F. Poole, Michael H. AbrahamPoly(viny1 chloride), Polysulfone and Sulfonated Polyether-ether Sulfone Composite Membranes forGlucose and Hydrogen Peroxide Perm-selectivity in Amperometric Biosensors-Yazid Benmakroha, IanChristie, Mohamed Desai, Pankaj VadgamaFilled Fluorosilicone as Matrix Material for Ion-Selective Membranes-C.Dumschat, S. Alazard, S. Adam,M. Knoll, K. CammannPotassium Ion-selective Optodes Based on the Calix[G]arene Hexaester and Application in Human SerumAssay-Wing Hong Chan, Albert W. M. Lee, Daniel W. J. Kwong, Wing Leong Tam, Ke-Min WangThin Plastic Film Colorimetric Sensors for Carbon Dioxide: Effect of Plasticizer on Response-AndrewMills, Lela MonafElectrochemical Decomposition of Cyanides on Tin Dioxide Electrodes in Alkaline Media-C. S. Fugivara,P. T. A. Sumodjo, A. A. Cardoso, A. V. BenedettiPolarographic Behaviour of Sulfadiazine, Sulfamerazine, Sulfamethazine and Their Mixtures.Use of PartialLeast Squares in the Resolution of the Non-additive Signals of These Compounds-T. Galeano Diaz,A. Guiberteau Cabanillas, M. I. Acedo Valenzuela, F. SalinasMediaeval Stained Glasses of Pisa Cathedral (Italy): Their Composition and Alteration Products-AndreaOrlando, Filippo Olmi, Gloria Vaggelli, Mauro BacciParaformaldehyde as an End-point Indicator in Hydrolytic Thermometric Titration of Metal Ions andIodine-Julio Cesar B. Fernandes, Luiz M. Aleixo, Graciliano de Oliveira Neto, Oswaldo E. S. GodinhoDetermination of Trace Amounts of Reduced Glutathione by a Chemical Oscillating Reaction-RafaelJimenez-Prieto, Manuel Silva, Dolores Perez-BenditoProton Nuclear Magnetic Resonance Determination of Hexamethylenetetramine in the Presence ofFormaldehyde and Urine-Gary L. Madsen, David S. Crumrine, Bruno JaselskisCUMULATIVE AUTHOR INDEXNEWS AND VIEWS 41N Book Reviews47N Conference Diary52N Courses53N54N Papers in Future Issues55N Technical Abbreviations and AcronymsConference Report4. D. R. ThomasCover picture: St. Basil’s Cathedral in Red Square, Moscow, Russia
ISSN:0003-2654
DOI:10.1039/AN99621BX015
出版商:RSC
年代:1996
数据来源: RSC
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Organic microheterogeneous systems in kinetic analysis. Self-assembled systems. A review |
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Analyst,
Volume 121,
Issue 4,
1996,
Page 33-44
María López Carreto,
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摘要:
Analyst, April 1996, Vol. 121 (33R44R) 33R Organic Microheterogeneous Systems in Kinetic Analysis. Self-assembled Systems A Review Maria Lopez Carreto, Soledad Rubio and Dolores Perez-Bendito* Department of Analytical Chemistry, Faculty of Sciences, University of Cbrdoba, Cbrdoba, Spain Summary of Contents Introduction Physico-chemical Features of Self-assembled Systems Catalysis by Surfactant Aggregates: Physico-chemical Studies and Analytical Applications General Kinetic Treatments Micellar Catalysis Single-component kinetic determinations Multicomponent kinetic determinations Catalysis by Premicellar Aggregates Catalysis by Reverse Micelles Catalysis by Microemulsions Catalysis by Functional Micelles Alteration of Reaction Paths Alteration of Stereochemistry Synkinetic Approach for Modelling Reactivity Conclusions References Keywords: Surfactant aggregate; micellar catalysis; kinetic analysis; nzicroemulsion; synkinesis; review Introduction Supramolecular chemistry is a growing research area, as is evident from the abundance of new journals and monographs with this name. Membrane mimetic agents are of central importance in supramolecular chemistry; increasing numbers of scientists from very different disciplines (e.g., synthetic, physical, colloid, polymer and biological chemists; physicists, biophysicists; pharmacologists; and engineers) are interested in the practical exploitation of membrane-mediated processes in relatively simple chemical systems.In the last two decades, a large number of organic systems have been identified which mimic the organizational ability of membranes and enzymes by bringing reactants together in highly structured specific micro- environments .-3 Membrane mimetic agents can conveniently be divided into self-assembled systems (normal and reversed micelles, micro- emulsions, vesicles, liquid crystals, etc), supramolecular hosts (macrocyclic polyethers such as crown ethers, coronands, cryptands and podands, cyclodextrins, etc.) and amphiphilic polymers (polyelectrolytes). These are broadly known as microheterogeneous systems, because of their colloidal dimen- sions, in spite of the large number of molecules they contain. Alteration of reaction rates, reaction pathways and stereo- chemistry in the environments provided by these organic microheterogeneous systems has been recognized for a long time4 and very diverse applications in different areas based on * To whom correspondence should be addressed.the reactivity control exerted by these systems have been Kinetic behaviour in microheterogeneous systems has been mostly investigated by physical chemists. Owing to their peculiar organization and mobility characteristics, most of the laws describing diffusional kinetics of homogeneous solutions are not valid in these microheterogeneous media. Considerable effort is being expended on the theoretical side to provide adequate models that can satisfactorily account for various kinetic features of the reactions in these aggregated sys- tems.13J4 Conclusions derived from the large number of physical chemical studies on the kinetic behaviour in micro- heterogeneous systems provide the basis for their rational use in different areas of application.Use of organic microheterogeneous systems in analytical chemistry for developing new kinetic-based determinations or improving previously established kinetic methods has been developed recently and although the results obtained have been extremely promising,15 their potential has hardly been explored. This review will attempt to evaluate the real potential of a type of organic microheterogeneous system, self-assembled systems, in kinetic analysis. The purpose of the present review is three- fold. The first is to analyse the main conclusions derived from physico-chemical studies on the effect of self-assembled systems on chemical reactions.The goal is to provide an up-to- date background, sufficient to guide further investigations in this area by selecting the more promising topics. We will concentrate on three topics. Firstly catalysis: alteration of reaction paths and alteration of stereochemistry. Secondly, to show some of the kinetic methods developed to date based on reactions occurring in self-assembled systems. No attempt will be made to catalogue the literature with respect to kinetic methods based on reactions occurring in these microheteroge- neous systems. Rather, the goal is to illustrate their utility through discussion of examples from the literature. In our selection we will concentrate, to some extent, on some topics which have been the subject of our own investigations during the last few years.Thirdly, to discuss new approaches that could be promising for kinetic analysis. To summarize, we will comment briefly on the synkinetic approach, through which molecules that produce self-assembled systems with a defined structure and/or function are synthesized. Since the rational use of self-assembled systems requires a sufficient understanding of their physical chemical properties, first we will compare briefly some of these properties, with special attention paid to the microenvironments provided by them and the solubilization and organization of substrates in these systems. Physico-chemical Features of Self-assembled Systems Amphiphilic molecules such as surfactants and lipids have several fascinating features because of their tendency to associate spontaneously in water and/or apolar solvents.The34R Analyst, April 1996, Vol. 121 structure of the molecule aggregates formed is determined by the structure of the constituent molecules, along with the solvent or other surrounding medium. In this paper, we will concentrate on those surfactant aggregates which are more promising in kinetic analysis, namely, aqueous and reverse micelles and microemulsions. Table 1 provides a comparison of some of their properties.lJ6 Important points to bear in mind with respect to these aggregates are the dynamic nature of their aggregation, the presence of distinct hydrophobic and hydrophilic microphases and associated interphases and their ability to solubilize substrates of very different nature. Micelles are transient in nature with the lifetime of a single monomer within a micelle being of the order of microseconds, while micelles exist on the millisecond time scale before they dissolve and reform.17 The behaviour of microemulsions is quite analogous.Surfactant aggregates provide regions of different polarities, acidities and viscosities. Traditionally, aqueous micelles are considered to contain a hydrophobic ‘liquid-like’ core and a polar surface. Thus, the environment changes as we move radially toward the centre of a micelle and while the detailed structure of the various zones is disputed, there is no doubt that this gradient of polarity exists. Surfactants aggregate in non-polar solvents predominantly by dipole-dipole and ion-pair interactions. 1,18,19 The properties of these aggregates, and indeed the terminology used to describe them,20 depend on the amount of co-solubilized water, on the presence or absence of co-surfactants and on the concentration of components.18 These systems can be considered to be surfactant-entrapped water pools floating in the hydrocarbon.The chemist can view them as mobile, tailored-to-size micro- reactors, where guest molecules can be induced to react.2l Although there are a wide variety of definitions of the term water-in-oil (w/o) microemulsion (water droplets dispersed in an oil-rich phase), there is fairly compelling experimental and theoretical evidence for the following picture. Up to a water-to- surfactant molar ratio ( R ) equal to the surfactant’s hydration requirements (about 4-10 molecules per surfactant molecule Table 1 Comparison of different aggregates Aqueous Characteristic micelles Constituents Surfactants Average molecular mass 20006000 Diameter/%l 30-60 Stability Weeks, months Kinetic stability (leaving rate of monomer)/s = 10-5 solubilizates per aggregate Few binding constants/ 1 mol-I Solubilizate residence Number of Substrate Up to about 106 timeis 10-3-10-5 Available Surface, solubilization stem layer sites vicinity of head-groups characteristics of some surfactant Reverse micelles Microemulsions Surfactants Surfactants and apolar and apolar solvents solvents 2000-6000 105-106 40-80 50-100 Few Large 10-3-10-5 > 1 Aqueous pool, Inner pool, inner surface inner surface surfac tant surfactant tail tail depending on the nature of the latter), one is dealing with reverse micelles.In these aggregates all water molecules are tightly bound to the surfactant head-groups and have high viscosities, low mobilities, polarities which are similar to hydrocarbons, and altered pH levels. Surfactant-bound water in reverse micelles resembles the polar pockets in enzymes and are responsible for many of the useful applications of these systems. Once the R value modestly exceeds the hydration requirement and free water starts to appear in the water p001*2,23 with essentially bulk properties at the centre of the droplet, the system is called a ‘water-in-oil microemulsion’. Therefore, the aqueous cavities of these aggregates are inhomogeneous in their physico-chemical properties and are characterized by different local polarities, viscosities, etc., at different points.24.25 When the water-apolar solvent-surfactant ternary system consists of equivalent amounts of water and apolar solvent the dominant microstructure is a bicontinuous microemulsion.We can imagine that the bicontinuous structures are comprised of interconnected fluctuating conduits filled with water. The oil/ water interfacial area will then be fixed by the surfactant concentration, and the conduit volume will be determined by the amount of water and counterion in the system. The diameter of the conduit is determined by the balance between oil penetration and electrostatic interactions. The extent of oil penetration will depend on both chain length and the surfactant-to-oil ratio, The evidence obtained to date supports the formation of a highly interconnected, chaotic network which can be described in terms of a dynamic, porous medium.26 Addition of enough apolar solvent leads to the formation of oil droplets dispersed in a water-rich phase (o/w microemulsion).For a particular surfactant, the progression of phase system from w/o-bicontin- uous-o/w microemulsions may be obtained by progressively changing a system variable such as the electrolyte concentra- tion, temperature, co-surfactant concentration, the nature of the oil component (e.g., chain length of n-alkane type oils) or some other.27 Substrates are dynamically solubilized in surfactant aggre- gates. The residence times of a variety of substrates within normal and reverse micelles and microemulsions range in the microsecond time scale and, therefore, the location and microenvironment of the molecule of interest are constantly in a state of flux between the aqueous phase and the micellar phase.Solubilization introduces two new situations that can influence the reaction rates; alteration in the local distribution of the solute (reactants) and surface/interface effects. There have been speculations and conjectures on the relative importance of these two factors. Numerous parameters influence the magnitude and distri- bution of solubilizates in the different systems. In ‘normal’ micelles the location of solutes will depend on its hydro- phobicity and concentration, as well as on the nature of the surfactant. Ionic species oppositely charged from the head- groups of the micelle may bind tightly to those functionalities via coulombic attraction.Non-polar species possessing polariz- able electrons (e.g., aromatics) have been found to reside near the polar head-groups rather than deep within the core of the micelle. Only very apolar molecules enter the micellar core because its volume is small, as compared with that of the micelle, and a guest in that region disrupts the packing of the apolar residues of the surfactant. Substrates having amphiphilic character may exhibit a special interaction with micelles and align themselves with the more polar end of the molecule directed outwards towards the head-groups of the micelle and the tail directed inward towards the core of the micelle.28 In general, surfactant aggregates in non-polar solvents will entrap polar molecules in the aqueous interiors, charged species will electrostatically bind to surfaces and hydrophobic sub- strates will be interspersed among the alkyl chains of surfactant tai 1s .29-32Analyst, April 1996, Vol.121 35R Catalysis by Surfactant Aggregates: Physico-chemical Studies and Analytical Applications General Kinetic Treatments For several decades, many workers have explored the varied and often pronounced effects of micelles, microemulsions, etc., on a wide variety of ground- and excited-state reactions and equilibria. Kinetic models were developed concurrently and provide good qualitative, and often quantitative, descriptions of many seemingly disparate obervations. Kinetic treatments have been developed most extensively for reactions in the presence of aqueous micelles.In the pseudophase kinetic model, largely developed by a Russian school of scientists,33,34 the kinetics of an nth order reaction are analysed by considering the partition- ing of the reactants between the two pseudophases (bulk water and the micelles). Surfactant monomer, organic molecules, and ions associate with micelles at nearly diffusion-controlled rates, and they exit at a rate, governed by the strength of binding, that is generally much faster than those of most thermal reactions. Thus, micellized surfactant is at thermal equilibrium with solutes throughout the reaction, and observed rates can be treated as the sum of rates of concurrent reactions in each pseudophase. Assuming that the concentration of reactants are sufficiently small that the structure of the micelles is not seriously affected, it may be shown that the observed second- order rate constant, kexp, for a reaction between A and B can be expressed as where the subscripts M, w, A and B denote quantities related to the micellar phase, aqueous phase and reactants, respectively; PA and PB are the partition coefficients of the reactants (i.e., PA = [A],/[A],); c is the surfactant concentration (molarity) minus the critical micelle concentration; V is the molar volume of the surfactant; the factors CV and (1 - cv) are the volume fractions of the micellar and aqueous phase, respectively; and K A and KB are the binding constants of the reactants, viz., KA = (PA - l)V and KB = (PB - 1)V.The rate constants kM and k, denote the rate constants of the reactions taking place in the micellar and aqueous phase, respectively; kIM the rate constant of the reaction resulting from collisions between reactant A in the micellar phase and reactant B in the aqueous phase; and k”M the reaction between reactant B in the micellar phase and reactant A in the aqueous phase.In this model no distinction is made between the various regions of the micelles, although reactions generally occur in the Stern layer, at the micelle/water interface, rather in the hydrocarbon-like core of the micelle.35 Therefore, it might be more reasonable to estimate second-order rate constants in the micelle in terms of reactant concentrations in the Stern layer. However, for many ionic micelles the volume of the Stern layer is approximately 30-50% of the volume of the micelle so that choice of the volume does not have a large effect on the conclusions of the treatment.In quantitative investigations of micellar catalysis and interactions it is desirable to determine the binding or association constant for the formation of the substrate-micelle complex and, if feasible, to elucidate the nature of the environment of the substrate in the molecular aggregate. Quantitative knowledge of these binding constants is a prerequisite for understanding the efficiency of micellar catalysis. Although binding constants can, in principle, be obtained from kinetic analysis,36 it is often desirable to measure these quantities separately via solubility measurements, NMR, electron spin resonance (ESR) and UV spectroscopic methods, gel filtration, ultrafiltration and chrornatography.377.3x The pseudophase model in its various guises explains many features of micellar rate effects and it can be applied, at least qualitatively, to reactions in a variety of colloidal assemblies as microemulsion droplets39.40 and reverse micelles.1,4,4143 How- ever, eqn.(l) is inadequate for treating ionic reactions in the presence of charged micelles and for accounting for electrolyte effects on the rates of micelle-catalysed reactions. Ionic reactants lacking hydrophobic groups are concentrated on the surface of oppositely charged surfactant aggregates. The greatest catalytic effect is expected between reactants of the same charge, localized on oppositely charged surfaces.Thus, rate constants for the Hg2+ induced hydration of Co(NH&Cl2+, are enhanced by factors of 140 000 in aqueous anionic micellar sodium dodecylsulfate (SDS).44 The major problem in analys- ing the effect of microheterogeneous systems on these reactions is modelling interfacial concentrations and distributions of ionic reactants, although in favourable cases they can be measured dire~tly.35,45,~6 Ion distributions have been modelled in two ways.14 In the pseudophase ion exchange (PIE) model, micellar surfaces are treated as selective ion exchangers saturated with ~ounterions.353~547 The key parameter in the PIE model is the ion-exchange constant, K3.48 Ionic competition at the micellar surface is governed by differences in the specific interactions of two counterions, and coulombic effects are assumed to cancel.Values of K g for a variety of counterions are similar to those of loosely cross-linked ion-exchange resins and generally follow a Hofmeister series, i.e., large, weakly hydrated, polarizable anions displace hydrophilic anions. Values of K,# have been estimated from rate and equilibrium data, spectrally, by ultrafiltration, and electro~hemically.35~~* In the Poisson-Boltzmann equation (PBE) m0de1,~9-~ reactions are assumed to occur in a surface region of defined thickness and solution of the PBE gives the concentration of ions in this region. Interfacial ionic concentrations depend on total concentrations of ions and surfactant, micellar radius and aggregation number, and a specific binding parameter, which is large for low charge density, polarizable ions, but is small or has zero value for hydrophilic ions such as OH- and F-.Estimated values of kM for different types of reactions are generally close to or somewhat smaller than k,, consistent with reaction at a water-rich micellar surface, and show that catalysis by non-covalent polymeric assemblies is often due largely to the increased reagent concentrations in the micelles as compared with bulk solvent.47 However, this generalization may reflect the types of bimolecular reactions chosen for study, e.g., those which are not very sensitive to solvent polarity. Some unimolecular reactions, the reaction rates of which depend strongly on solvent polarity, have very different rate constants in micelles and water.13 Micellar Catalysis Ever since the first studies of kinetic micellar effects, micellar catalysis has been the goal of intensive current research. 1,2,4 Micelles have been considered as simple model systems for aspects of enzymic catalysis, both from a kinetic viewpoint and in terms of stereochemical and substrate selectivity.In micellar catalysis the observed non-covalent substrate binding, satura- tion type kinetics, and competitive inhibition in non-functional model systems are similar to the behaviour of enzymes. However, there are two major differences between the two systems. Firstly, the effectiveness of micelles in enhancing the rates of reactions is generally less than that of enzymes; for micelles the effect rarely exceeds 1 00-fold.Secondly, micellar catalysts are less specific than enzymes. The reason for the relatively poor catalytic power and specificity of aqueous micelles is related primarily to the dynamic equilibrium that exists between the monomeric and micellar surfactant species. Unlike enzymes, which generally maintain their native confi- guration prior to and subsequent to binding substrates at the active sites, micelles are continuously being formed and36R Analyst, April 1996, Vol. 121 reformed. There is another crucial difference between micellar and enzymic catalysis. In enzyme-catalysed reactions the substrate concentration is usually several orders of magnitude larger than the enzyme concentration. By contrast, in micellar solutions the concentration of at least one of the reactants is maintained at levels rather similar to that of the micelles.For second and higher order reactions, this may then lead to a large change in the relative concentrations of the reactants in both pseudophases if at least one of the reactants is strongly bound to the micelles. As a result, this difference leads to different concentration effects which directly affect the catalytic mech- anisms involved. Thus, today, ample evidence is being accumulated which renders aqueous micelles to be relatively poor models for complex bioorganic interactions. Rate profiles for a wide variety of bimolecular reactions show characteristic patterns which depend upon substrate charge and hydrophobicity, surfactant head-group charge and chain length, and counterion concentration and type. Likewise, added salts have marked effects on the rates of bimolecular reactions in micellar solutions, well beyond typical salt effects in water.1.234 Variations in the substrate have a profound influence, in many cases, on the magnitude of micellar catalysis.The general rule seems to be that the more hydrophobic the substrate the more pronounced the micellar catalysis, since incorporation of reactants into the micelle increases with increasing reactant hydrophobicity. It appears that reactant structure influences not only distribution of reactants between solvent and micelles, but also the relative free energies of reactants and transition state in the micelles, i.e., the specific reaction rate in the micelles. For charged substrates and reactants which are not expected to penetrate the micellar core, but remain fixed at the surface, the micellar rate constants should be independent of substrate hydrophobicity.35 The surfactant head-group charge influences the catalytic power of the micelles.Thus, catalysis of some nucleophilic aromatic substitution reactions and particularly of the reaction of fluoride ion with p-nitrophenyldiphenyl phosphate is more pronounced by dicationic micellar surfactants than by cationic micellar hexadecyltrimethylammonium bromide.52 Likewise, the catalytic power of the micelle also depends on head-group bulk. Micelles with bulky head-groups [i.e.,(n-Bu)3N+J can exclude water from their surfaces and probably the extent of solvation of the initial and transitions states will be affected.A decrease in hydration owing to exclusion of water from the micellar surface should therefore assist the reaction. The observation that rate constants at micellar surfaces depend on head-group bulk means that the generalization kM/k, =: 1 is only a first approximation, especially for surfactants that have bulky head-groups. 13 Micellar catalysis tends to be more pronounced for surfac- tants that have longer alkyl chains, i.e., for those which are more hydrophobic. Such an effect can be rationalized by postulating an increase in the charge density of the ions of the surface of the micelle with increasing carbon chain length which, in turn, would increase the electric field of the reaction site.4 The effects of added salts on micelle-modified reactions can be quite varied, ranging from inhibition, the most commonly observed phenomenon, to activation, which is observed in certain cases.53 Such effects have been shown to be strongly dependent on the nature of the detergent head-group, the initial counterion present, and the total ionic content of the system.In unbuffered solutions of cationic or anionic surfactants, the effectiveness of a series of counterions in inhibiting the reaction follows a Hofmeister series, i.e., increase with the size of the ion. For organic ions, the more hydrophobic the ion, the more effectively it inhibits reactions. Enhancement of the micellar- catalysed reaction rate by electrolytes has been suggested to be owing to changes in micellar structure by the salts. Several lines of evidence strongly suggest that most reactions occur on the surface of the micelle, at or near the highly charged double layer which surrounds the hydrocarbon core and not whithin the hydrocarbon core itself. Typically for reactions between non-ionic reactants, second-order rate constants in the micellar pseudophase are lower than in water, because the micellar surface appears to be less polar than in water, and these reactions are inhibited by a decrease in the polarity of the reaction medium.Reactions between very hydrophobic sub- strates and hydrophilic anions also seem to have lower second- order rate constants in the micellar pseudophase than in water, probably because the anions are located in the Stern layer at the micelle/water interface whereas the substrate may be, on average, more deeply in the micelle.Substantial ‘true’ micellar catalysis has been found for different nucleophilic aromatic substitutions. An example is the catalysis of cetyltrimethylammonium bromide in the attack of azide ion on 2,4-dinitro~hIoronaphthalene,5~ with a kM/k, of about 400. Nucleophilic aromatic substitution most frequently involves a two-step bimolecular mechanism in which either the formation of an intermediate or its decomposition can be rate determining. These type of reactions often involve the forma- tion or the destruction of charged species, and the changes in the magnitude and the distribution of the charges between the initial state and the transition state have been correlated with the effects of the medium on the rate of nucleophilic reactions in a wide variety of cases.35 Consequently, the numerous charge changes theoretically possible for nucleophilic substitutions should serve as fertile ground for studying the effects of micelles on the rates of these reactions.Single-component kinetic determinations The use of micellar catalysis in kinetic-based determinations has been studied recently and although the results obtained are very promising this is still a fairly unexplored field. To date, kinetic determinations involving both catalysed and uncataly- sed reactions have been developed.15 A special effort has been made to determine the intrinsic reactivity of the substrates implied in the studied systems. In general, the results obtained agree with the established theory according to which estimated values of k M are close to or somewhat smaller than k,.To our knowledge, the only exception to this behaviour is that found for the oxidation reaction between CrV1 and Pyrogallol Red (PR).55+56 When this reaction occurs in the presence of micelles of dodecyl trimethylammonium bromide (DTAB), the calcu- lated ‘true’ second-order rate constant in the micellar pseudo- phase (kM) exceeds that in aqueous solutions by a factor of approximately 55. Determining the real origin of the reactivity change induced by DTAB on the PR-CrVI system is an interesting challenge in order to find other similar systems and study their analytical potential. The enhanced sensitivity of kinetic-based determinations in micellar media arises mainly from the concentration of reactants in the micellar pseudophase.Often, the concentration effect implies a simultaneous alteration of various physico-chemical properties of substrates and/or intermediates and products, and the corresponding analytical procedures would benefit from some of the effects produced. Thus, concentration of the monitored species within the micelle gives rise to enhanced analytical signals and as a result an increased reaction rate is produced, i.e., DTAB micelles substantially increase the absorbances at 292 and 360 nm in the spectra of the triiodide ion; this effect has been used for the kinetic determination of arsenite ion based on its accelerating effect on the reaction between iodide and bromate, catalysed by Osvr11.57 Inasmuch as the variation of the absorbance of triiodide ion with time wasAnalyst, April 1996, Vol.121 37R ~~ used to monitor the reaction development, an increase in the molar absorptivity of this species resulted in a proportional increase in the reaction rate. To date, most of the micellar kinetic determinations based on uncatalysed reactions have involved aromatic nucleophilic substitutions. Typical examples are the reactions between 1 -fluoro-2,4-dinitrobenzene (FDNB) and primary and secon- dary amines,sg,sg phenolic compounds60 and thiok6 These reactions are considerably accelerated by cationic micelles and have been used for the determination of different analytes, even in turbid and coloured samples, by using a fluoride ion-selective electrode. Micellar media can also enhance the sensitivity of kinetic methods based on catalysed reactions provided that the catalyst concentrates at the micellar surface.Our experience in this area indicates that a direct association between a catalyst and the micelles is often hindered by exclusion phenomena arising from substrates present in the reaction medium, the concentrations of which often exceed that of the catalyst by a few orders of magnitude.62>63 As a result, different strategies have been approached to increase the sensitivity of catalytic kinetic methods in micellar media.15 Probably the more promising alternative is the formation of stable or transient catalyst- substrate complexes that concentrate on the micellar surface. Stable complexes have been used for the determination of Pb1164 and SbIII;65 in both methods using a micellar medium results in substantially increased sensitivity and selectivity for the determined ions.Transient catalyst-substrate complexes are formed in many redox reactions where the catalyst reacts with a substrate to yield the product and its own activated form. When the substrate is an organic compound, interaction between this and the catalyst generally entails the prior formation of a charge- transfer complex between both species, which in turn requires that the catalyst be temporarily concentrated at the micellar surface if the substrate is concentrated by a group other than that via which the catalyst forms the complex. Since this step will be the rate-determining step, the resulting local concentration of the catalyst can result in a more sensitive determination.This approach has been used for the determination of iron(m), with substantially improved sensitivity, based on the reaction of oxidation of sulfanilic acid by potassium periodate, activated by 1 , 10-phenanthroline.66 Concentration of this catalyst on pos- itively charged hexadecylpyridinium chloride (CPC) sub- micellar units occurs by formation of a transient phenanthro- line-FeIII-sulfanilic acid ternary complex, which probably concentrates in the surfactant aggregates through the sulfonic group of the sulfanilic acid. Although comparatives studies on the selectivity of kinetic determinations in micellar and aqueous media have been performed in some of the developed methods, no clear conclusions can be drawn from results obtained when concen- tration of reactants is the only effect of the micellar medium.Substantial improvement in selectivity has been obtained for some of the studied kinetic rnethods,64,65 however this is not a general rule. To date, clear selectivity improvements of kinetic methods by using micellar media have only been obtained when the concentration of reactant in the micelle produces an alteration of physico-chemical properties of substrates and/or reaction products. For example, selectivity of analytical kinetic methods can be enhanced on the basis of micelle-induced changes in pK,. To this end, at least one of the reactants must possess acid-base properties and one of the forms involved in the equilibrium must concentrate preferentially at the micellar surface.Thus, anionic SDS micelles, which catalyse the reaction between hex- acyanoferrate(I1) and 1 , 10-phenanthroline, accelerated by Hg", allow the ferroin complex to be formed at a lower pH. This effect results in an appreciably higher selectivity in the kinetic determination of HgIJ relative to the reaction in a purely aqueous medium.67 Micelle-induced spectral shifts of the monitored species can also increase the selectivity of kinetic methods. Thus, CPC cationic micelles induce a bathochromic shift for triiodide ions from 350 to 500 nm and this effect has been widely used to enhance the selectivity of kinetic methods involving the I*/I- system .6*-7 Besides improved sensitivity and selectivity, kinetic methods can take advantage of other micellar effects.In particular, micelles can be used to promote processes that are strongly reversible in water. Thus, the reaction between sulfite and 1 ,3,5-trinitrobenzene7 which yields the coloured Meisenheimer complex, is incomplete in an aqueous medium and lies toward the reactant side. However, the position of the nucleophilic equilibrium reaction can be quantitatively shifted to the desired product side -\.?a the use of a cationic cetyltrimethylammonium bromide (CTAB) micellar system and this effect has been used for the determination of sulfite ion? Likewise, condensation reactions such as formation of hydrazones, oximes or Schiff bases from carbonyl compounds which are strongly reversible in water can be promoted by micelles. Taking advantage of this micellar effect, Yatsimirsky et a1.73 have recently developed a kinetic method for the determination of hydrazine and phenyl- hydrazine based on their condensation with p-(dimethylamino)- benzaldehyde in anionic SDS micellar solutions.Micelles also allow co-solubilization of compounds of very different hydrophobic and hydrophilic character and as a result chemical reactions can be developed which otherwise would proceed only with difficulty.74 An example is the formation of o-phthalaldehyde adducts from water-insoluble amines of high molecular mass.75 Use of micellar catalysis in dynamic systems such flow injection systems has also been investigated. In general, the greater viscosity of the micellar phase increases dispersion for non-reacting systems, but when monitoring a reaction product the increased reaction rate can counteract this and the micellar carrier can show less over-all dispersion than the aqueous carrier, lowering the limits of detection.76-78 Multicomponent kinetic determinations Perhaps one of the most promising areas of application of micellar catalysis in kinetic analysis is the implementation of new differential reaction-rate methods.Micelles can alter the apparent rate constant ratio of two or more species that interact with a common reagent by both altering their intrinsic reactivity and, more generally, binding in a different extension to analytes. According to eqn.( 1 ), observed second-order rate constants, kexp, of bimolecular reactions in micellar media depend on partition coefficients of analytes binding to the micelle.So, if two analytes show different partition coefficients, different kexp ratios can be established when kexp values are obtained as a function of surfactant concentration. As a result, micellar aggregates might be of use for resolving mixtures of species with insufficiently different apparent rate constants in aqueous or organic media by applying differential reaction-rate methods, or in those cases where a given component takes too long to react so that it precludes analytical measurements. Simultaneous kinetic determination of nickel(I1) and cobalt(II), based on the complex-formation reaction between these ions and 5-octyloxymethyl-8-quinolinol in the non-ionic micellar medium provided by Triton X-100, has been pro- posed? This surfactant decreases the rate of formation of both complexes compared with an aqueous medium, so permitting their monitoring by conventional spectrophotometry.Since the formation of the Co" complex is forty-four times faster than Ni" in the micellar medium, it is possible to determine, simultane-3 8R Analyst, April 1996, Vol. 121 ously, both ions in the concentration range (0.2-5.0) x 10-5 moll- by using the logarithmic extrapolation method. The influence of the cationic surfactant CTAB on the apparent rate constants of the reactions of cyanide, sulfide and sulfite with 5,5’-dithiobis-(2-nitrobenzoic acid) (DTNB) has also been investigated.80 The anion mixture can not be resolved by conventional differential kinetic analysis in an aqueous medium because of the similar reactivity of sulfide and sulfite ions and the slowness of the reaction between cyanide and DTNB (which takes about 100 min to complete).The dependencies obtained by plotting the observed rate constants, kexp, of the reactions between the three ions and DTNB as a function of the CTAB concentration show that by selecting an appropriate concentration of surfactant, adequate differences between the rate constants are obtained and binary mixtures of the anions at micromolar concentrations can be resolved by using a multiple linear regression method. Although to date only aqueous micelles have been used for the implementation of new differential reaction-rate methods, extension of this topic to non-aqueous solvents by using reverse micelles or microemulsions could lead to new possibilities for the differentiated determination of water-insoluble com- pounds.Catalysis by Prernicellar Aggregates In some cases substantial rate enhancements have been observed in aqueous surfactant solutions at concentration orders of magnitude lower than the c.m.c. Submicellar aggregates are particularly evident in aqueous solutions of cationic surfactants such as tetraalkylammonium halides. 1 Rate enhancements provided by premicellar aggregates can readily be rationalized in terms of the kinetic treatments derived for second-order reactions in aqueous micelles.8l.82 Based on such treatments, the reaction rate is determined by the reactant concentrations in the aggregates. Since small premicellar aggregates contain more reactant molecules per aggregate than micelles at the same reagent concentrations, a more efficient reagent concentration in the smaller aggregates often results in higher second-order rate constants for reactions in premicellar aggregates than for those observed in micelles. To our knowledge the only application of catalysis by premicellar aggregates in kinetic analysis is the determination of iron(m) based on its catalytic effect on the oxidation of sulfanilic acid by potassium periodate, in the presence of 1 , 10-phenanthroline as activator.66 Premicellar aggregates of the cationic surfactant CPC enhance the rate of the catalysed reaction and have no effect on the uncatalysed reaction.The kinetic study carried out shows that the effects of this surfactant on the iron(m)-catalysed reaction can be entirely attributed to increased reactant concentrations in the surfactant micelle subunits. The detection limit found for iron(m) is seven times lower than that of the method using an aqueous medium.Applicability of the micellar kinetic method to the determina- tion of iron(I1r) in blood serum samples has been proved. Premicellar aggregates thus broadens the scope of application of surfactants in kinetic analysis. Catalysis by Reverse Micelles The catalytic effects and substrate specificity in reverse micelles are far in excess of those encountered in aqueous micelles. Water molecules included in the core of reverse micelles form water pools, which are extensively used as ‘tailored-to-size microreactors’ for chemical, photochemical, biological, elec- tron-transfer reactions, Many kinetic studies have been undertaken in order to increase our knowledge of the way in which the velocity constants in such microreactors vary.The acceleration of reactions in reverse micellar systems is caused, apart from the trivial effect arising because the reactants are concentrated as a result of being bound to the micelles and the effects of the micromedium in the inner cavity (namely a reduced polarity, a high microviscosity, and a high concentra- tion of functional groups), by the rigid fixation of the reactant molecules to the inner cavity of the micelles, as occurs in enzyme catalysis.33.87 Effects associated with specificity in relation to the sizes8 and configuration89 of the reactant molecules, characteristic of enzyme catalysis, can also be observed in catalysis by reverse micelles.The nature of the cavity can be altered to investigate effects of its size, polarity, structure of the polar functional groups and water contents on both substrate interactions and catalysis.4 For reactions catalysed by reverse micelles, reaction rates often decrease as water is added. Generally, a decrease in substrate binding will be the cause of this decrease. However, when large decreases are observed, deactivation of surfactant head-groups (by hydration) which act as nucleophiles in the reactions involved, such as ester hydrolysis, will be the major contribut- ing factor.”) It is important to mention that, as a rule, the rates of chemical reactions involving water increase sharply on passing from an aqueous solution to a system of hydrated reverse micelles and the acceleration effect can reach a factor of lo6 and rnore.87,91392 The acceleration effect is largely due to the high reactivity of the water solubilized in the inner cavities of the reverse micelles where the reaction takes place.For example, the nucleophilic activity of the water solubilized by inverted AOT micelles is at least lo3 times higher than that of the bulk-phase water. The water which is either involved in the hydration of the polar groups in the surfactant molecule or appears directly after the completion of the hydration shows the highest reactivity. Further addition of water leads to the formation of hydrogen bonds between the water molecules themselves which results in a decrease of their reactivity.The high reactivity of the water molecules involved in the initial hydration of the surfactant can be caused by the high mobility and/or the change in their acid- base characteristics.93 In some cases bimolecular reactions show high substrate selectivity in reverse micelles. Thus, hydration of the tris(oxa- late)chromate(m) anion is up to 5.4 million-fold faster in octadecyltrimethylammonium tetradecanoate solubilized water pools in benzene than it is in water.94 Furthermore, small changes in the substrate, such as replacing the chromium metal by cobalt or replacing the oxalate by azido ligand, results in a drastic decrease of the rate enhacements (100-1000 fold) in the same reversed micellar system. The kinetic behaviour of enzymes solubilized in the water pool of reverse micelles deserves special mention.Because of their practical importance a large number of studies have been carried out to elucidate the effect of different variables on the catalytic activity of enzymes incorporated in these tailored-to- size microreac tors. 87395396 It has been demonstrated that the catalytic activity of enzymes is dependent on the degree of surfactant hydration, expressed as the ratio of molar concentrations of water and surfactant, R , which determines the size of inner polar cavities of hydrated reverse micelles. For micelles with a defined size this dependence is bell-shaped, i.e., there is a certain optimal value of surfactant hydration at which the catalytic activity of solubilized enzyme is at a maximum.84.87~95~’6 It has been suggested that this maximum corresponds to the geometric complement between entrapped enzyme molecules and aqueous cavities of surfactant aggregates.Under conditions when such a complement is reached, the enzyme molecule experiences a close contact with the surrounding surfactant matrix. In this case the matrix can tightly ‘squeeze’ the enzyme molecule, thereby ‘freezing’ its rotational and vibrational motions, which couldAnalyst, April 1996, Vol. 121 39R lead to the fixation of the most catalytically active conforma- tion.96 For polydisperse micelles, increasing the width of the size distribution decreases the observed catalytic activity of the solubilized enzyme since the fraction of micelles with optimal size is reduced.95 Likewise, the optimum level of catalytic activity shifts towards low degrees of hydration, i.e., lower mean micellar radii.This shift is caused by the asymmetry of the size distribution function. An important consequence of such a shift is that in reversed micellar systems with different size distributions the optimal catalytic activity of the same enzyme can be observed at different values of the mean micellar radius.97 In the case of non-spherical enzymes the highest catalytic activity is generally obtained for reverse micelles with the diameter of the aqueous cavity equal to the longest dimension of the enzyme molecule.95 A change in the concentration of surfactant in reverse micellar systems, carried out at a fixed R, results in the alteration of the concentration of identical micelles without influencing their size and other properties.96.98 Therefore, the catalytic activity of solubilized enzymes that do not exert any influence on micellar parameters should not depend on the surfactant concentration if the value of R is kept constant.The validity of this conclusion was demonstrated for a number of enzymes, such as alpha-~hymotrypsin,99~100 trypsin,lOO and alkaline phosphatase. 101 The situation is different if the entrapped enzyme can in some way affect the properties of the micelle. Thus, molecules of lactase and peroxidase bear carbohydrate chains attached to their surface,102,103 and due to this fact the enzymes can interact with the micellar matrix. The catalytic activity of enzymes of this class strongly depends on the surfactant concentration.96 Enzymes can change specificity as a result of their solubili- zation in reverse micelles.This change can be both true, i.e., associated with a change in the catalytic properties of the enzyme itself, and apparent, i.e., caused by a change in the observed Michaelis constant, which depends on the distribution of the substrate in the inverted micellar ~ystem.8~ A striking example of a change in the substrate specificity of an enzyme owing to the substrate distribution effects is provided by the oxidation of aliphatic alcohols catalysed by horse liver alcohol dehydrogenase in the AOT [sodium bis(2-ethylhexy1)sulfo- succinate; Aerosol OT] inverted micelle system in octane. lW The transition from an aqueous solution to the reverse micellar system is accompanied by a shift of the maximum on the curve describing the dependence of the second-order rate constant for this reaction on the length of the hydrocarbon chain in the molecule of the alcohol substrate n; octanol ( n = 8) is the optimum substrate in water, while butanol (n = 4) is the optimum substrate in a colloidal solution of water in octane.In spite of the large body of physico-chemical studies on the reactivity in reverse micelles, relatively few applications of these aggregates in kinetic analysis have been de~cribed.95,~05 In the last few years, however, excellent progress has been made in enzymic analysis and homogeneous enzyme immunoassay. Reverse micellar systems lead to new possibilities for the employment of enzymes in the detection of water-insoluble compounds0 since solubilization of the enzyme in the inner cavity of a reverse surfactant micelle protects it from the denaturing action of the organic solvent.By manipulating the polarity of the micellar interphase, the partitioning behaviour of substrates can be influenced, resulting in a higher interfacial concentration and consequently a higher enzyme activity and improved sensitivity.l05 It has been shown106 that not only enzyme activity, but also inhibition of enzymes by rather apolar compounds, can be studied in reverse micelles and used as an analytical tool. Reverse micelles have been shown to possess some advan- tages for the enzymic analysis of water-soluble compounds. The concentration effect and the effects involving an increase in the catalytic activity of enzymes in reverse micelles can sig- nificantly increase the sensitivity of analytical systems.87 Thus, it has been shown that, on passing from a traditional aqueous solution to the Brij 96-water-octane system, the sensitivity of the bioluminescence analysis of adenosinetriphosphate (ATP) increases by more than an order of magnitude.Furthermore, the stabilization of the level of the detected signal is observed in the micellar system, which makes it possible to simplify sig- nificantly the entire analytical procedure. lo7 Reverse micelles also facilitate coupled enzymic systems as has been shown for analytical procedures for hydrogen peroxide producing enzymes. 10*-110 This compound, upon reaction with luminol, gives rise to chemiluminescence, a reaction that does not take place in aqueous solutions below pH 9 unless a catalyst or co-oxidant is present.These requirements make the coupling between an enzymic assay and the chemiluminescence in aqueous solution virtually impossible. In the presence of a reverse micellar medium of hexadecyltrimethylammonium chloride (CTAC), the chemiluminescence reaction takes place below pH 9, probably catalysed by the surfactant head-groups, and under these conditions a coupling between the two reactions is possible, as has been shown for glucose oxidase. Fluores- cence detection of enzymically formed hydrogen peroxide in CTAC reverse micelles has also been described.111 The reaction rate was enhanced approximately 30-fold in the micellar medium.Enzyme, glucose or hydrogen peroxide can be determined with improved sensitivity. A different, almost unexplored field with potential for applications is antigen-antibody interactions in reverse mi- celles.IO5 Eremin et al. showed that these interactions are not hampered by enclosure in reverse micelles, a fact that might extend the use of antibodies, for analytical purposes, to organic solvents.112 Thus, reverse micelles have been proposed as a new way in homogeneous enzyme immunoassay using thyroxine as an example.' 13 When thyroxine-specific antibodies are added to a peroxidase-thyroxine conjugate solubilized in reverse mi- celles, the immunocomplex is formed, which significantly differs in size from the initial enzyme-antigen conjugate. Since the catalytic activity of solubilized biocatalysts is influenced by the ratio of sizes of the enzyme molecule and the inner cavity of the reversed micelle, the formation of the immunocomplex leads to an alteration of the enzymic activity.Addition of free thyroxine into the system causes the dissociation of the complex with concomitant restoration of the catalytic activity to an extent dependent on the concentration of added free antigen. The sensitivity of the assay procedure can be regulated by changing the degree of surfactant hydration. Catalysis by Microemulsions Kinetics in microemulsions have been treated quantitatively like those occuring in micelles, and the important factor appears to be the concentration of reagents at appropriate surfaces. Microemulsions offer several advantages over aqueous and reverse micelles in that: 1 14 (a) the hydrophile-lipophile balance is adjustable by a proper choice of the relative amounts of the surfactants and co-surfactants so that a variety of surfactants can be made to aggregate in non-polar media.All classes of surfactant, cationic, anionic and non-ionic, form microemul- sions, and the surfaces of these colloids are not unlike those of the corresponding micelles. (b) The aggregation number of the surfactant in microemulsions and the amount of water solubi- lized inside a w/o microemulsion are larger than those usually encountered in reverse micelles. As a result, microemulsions serve the need well for organizing high concentrations of polar and apolar molecules in each aggregate. Oil-in-water microemulsions sometimes provide the medium for spectacularly efficient reactions which do not function in40R Analyst, April 1996, Vol. 121 other environments.3 One important example is the destruction of the oil-soluble chemical warfare agent mustard.1 15 When 5% aqueous hypochlorite was added to half mustard, EtSCH2CHZC1, which is much less dmgerous than mustard but manifests similar chemical reactions, and then dissolved in 15 ml of microemulsion (82.1% H2O; 3.2% cyclohexane; 4.9% SDS; 9.8% butan- 1 -ol), the sulfide was quantitatively oxidized exclusively to the sulfoxide within 15 s. The exceptional speed of this reaction has been explained through the formation of an alkyl hypochlorite at the oil/water interface (Fig. 1) Interestingly, reactivities in microemulsions can be quite different from those in micelles.'6 Thus, the incorporation rate of cupric ions into protoporphyrin dimethyl ester is some 20000-fold faster in aqueous micellar SDS than in hexadecyl- trimethylammonium bromide.' 16 The rate acceleration is attrib- utable to micellar solubilization of the porphyrin ester, so that the pyrrole nitrogen atoms are located in the Stem layer in close proximity to the copper(I1) ions, which are electrostatically attracted to the anionic micellar surface.Conversely, in microemulsions copper(I1) ion incorporation in tetraphenylpor- phyrin is more facile in the presence of cationic than in anionic or non-ionic surfactants. This is explicable in terms of the cationic surfactant facilitating the transport of copper(I1) ions from the relatively large water pool across the interface of the microemulsion where the porphyrin resides.Reactivity in microemulsions has been frequently studied using enzymic reactions because it is of practical interest. Many different proteins can be solubilized within the water droplets of w/o microemulsions with retention of their native activ- ity.84,86,11731* 8 The microenvironment of the protein within the droplet remains essentially 'water-like' as the protein does not 'see' the oi1.119 However, since the sizes of the protein and the water droplets are generally comparable, proteins hosted within microemulsion water droplets are neccessarily in close prox- imity to, or may be embedded within, the surfactant monolayer stabilizing the droplet. The extent of protein partitioning between the phases is expected to be determined by the interactions of the protein with the surfactant monolayer coating the droplets.For some enzymes an increase in catalytic activity has been observed as a result of favourable conformations stabilized by interaction with the surfactant.' l'l05 Microemulsions, as well as reverse micelles, lead to new possibilities for the employment of enzymes in the detection of water-insoluble compounds, especially when the reactant implied is too big to be easily accommodated in a micelle. However, this aspect remains to be evaluated in terms of its analytical usefulness in kinetic-based determinations. Recent studies have suggested that microemulsions can be used to control and enhance the rates of electrochemical catalysis.The use of a bicontinuous microemulsion of water, dodecarie, and a double-chain alkylammonium surfactant in catalysed reactions initiated by electrogenerated CO(I) com- plexes has been evaluated.120 Cyclic voltammetry has been used HO Fig. 1 SDS) and a co-surfactant (dodecanol). R2S = EtSCH2CH2Cl. Cyclohexane droplets in water stabilized by a surfactant (CTAB or to compare the bicontinuous microemulsion with homogeneous dimethylformamide for cobalt-mediated S N 2 reactions between vitamin B12 and Co, both of which remained in the water phase, and alkyl bromides, which were sequestered in the oil phase during the reactions. The results indicate that the rates of electrochemically initiated bimolecular reactions can be as fast in the bicontinuous emulsion as in a homogeneous solvent, even though the two reactants reside in different phases and the reaction does not take place at the electrode surface, thus indicating that microemulsions can be used to replace organic solvents. Catalysis by Functional Micelles Although, to our knowledge non-application of catalysis by functional micelles has been described in kinetic analysis, its great potential in this field encourages the introduction of some brief considerations on this topic.Substantial progress in the area of functional micellar catalysis has been led by the interest in refining analogies between surfactant aggregates and en- zymes. Micelles functionalized with groups that model the amino acid side chains responsible for enzyme activity are generally impressive catalysts.'~4~~3,45~53~~2~ A functional surfactant is a surfactant containing a reactive residue, usually at the head-group, that can be micellized or co- micellized typically with a chemically inert, non-functional surfactant. Typically the functional group is a nucleophile (weakly acidic functional groups such as imidazoles, iodoarse- noic acids, oximes and hydroxamic acids) or occasionally a general base (for example amino).The substrates have usually been carboxylic esters, although aryl carbonates and phosphates and activated aryl halides have also been used. In most of these reactions the nucleophilic functional group attacks the reaction centre, giving a covalent intermediate, e.g., an acyl imida- zole. 122 The essential factors responsible for the functional micellar catalysis are hydrophobic (proximity or concentration effects produced by high local anionic nucleophile concentrations generated by strong binding or the organic acids) and electro- static (enhanced deprotonation by high local OH- concentra- tions at cationic micellar surfaces) in character. The pseudo- phase model provides a very simple way of predicting the rate of reaction with a functional micelle because every surfactant head-group carries a reactive residue.The results to date are in accordance with the hypothesis that second-order rate constants are similar in micellar and aqueous pseudophases for reactions of a nucleophilic group incorporated into a functional mi- celle.123 The effect of changing the reaction medium from an aqueous to a micellar phase does not significantly affect the activity of an anionic function: enhancement of its nucleophilic properties owing to desolvation is apparently not relevant, which could perhaps indicate that micellar reactions occur mostly on the surface of the Stern layer without benefit of the lower polarity and of the lower water content of the interior part of the layer.Many functional micelles are stoichiometric reagents, and the products of initial nucleophilic attack are so stable that there is no turnover of the reagent.13 Some very interesting turnover systems have been developed and they are very effective as deacylation or dephosphorylation catalysts. These catalytic micelles have as functional groups iodosobenzoate, 23 or gem- diolate residues,l24 or are copper-amine complexes.125 Functional surfactants generate micelles that have a very high concentration of a reactive group at their surfaces and, as a result, large enhancements are sometimes observed, relative to the rate in water. Indeed, in some systems the micellar rate enhancements are of magnitudes similar to those found in enzymic reactions.53 There are now many examples of nucleophilic addition and substitution reactions in which aAnalyst, April 1996, Vol. 121 41R micelle of a functional surfactant is a very effective reagent and these reactions are, in principle, good candidates to prove the utility of functional surfactants in kinetic analysis. Alteration of Reaction Paths Reagent organization in, and the different microenvironments provided by, self-assembled systems open the possibility of controlling pathways leading to product formation. Aqueous micelles, and at lesser extension reverse micelles, have been used for altering reaction pathways, especially when a particular substrate can undergo two reactions, one of which is micellar catalysed and the other inhibited. A large body of data on altered product distribution by micelles exists. Micellar control of reaction pathways leading to specific products can be of great use in multicomponent kinetic analysis.One representative example of the potential of this micellar effect is the simultaneous determination of Vv, CrV1 and TiIV based on their reaction with PR in the presence of DTAB micel1es.s~~~~ In an aqueous medium, PR is gradually deco- lourized by oxidation with chromium(v1) and vanadium(v), so, the simultaneous resolution of these two ions is rendered impossible by their similar reactivity.Titanium(1v) interferes with the individual determinations of these ions by complex formation with PR. DTAB micelles have the following effects on the process (Fig 2): they catalyse the oxidation of PR by CrVI; they allow the oxidation reaction between Vv and PR to be completely displaced by a complex formation reaction between the two species; and they alter the photometric features of the TiIV-PR complex. These changes allow the simultaneous resolution of the three ions from measurements made at three different wavelengths corresponding to as many reaction products. Alteration of Stereochemistry Most enzyme catalysed reactions are highly stereospecific.Interest in exploiting membrane mimetic systems for promoting stereoselectivities is hardly surprising, therefore. Physico-chemical studies of micellar effects on reaction stereochemistry has been an active area of investigation.’ Much of the work on stereoselectivity in micellar catalysis has employed ester derivatives of amino acids or di- and tripep- tides.126 In general, placing the chiral centres in hydrophobic regions of the micelles rather than in the vicinity of the head- groups leads to more pronounced discrimination. ] There are also several systems in which substrate micellization controls the stereochemical course of reactions. REACTIONS + Most of the results obtained to date show that micelles are not particularly effective at controlling the reactivities of enantio- meric substrates, even when the reactions are effectively catalysed.This behaviour can be explained by the fact that although micelles can enhance bimolecular reaction rates by bringing reactants together in a small volume element at the micelle/water interface and, in addition, functional micelles also introduce new reaction paths, neither of these rate-enhancing factors necessarily depend upon the precise arrangement of atoms and groups that are not directly at the reaction centre. But precise arrangement is of key importance in determining stereochemistry, and micellar structures are so loose and mobile that these aggregates are probably incapable of holding reactants in particular conformations.53 Relatively few studies have been performed on stereoselecti- vities in reverse micellar systems.There has been speculation in the literature43 27 that micelle-solubilizate interactions should be more specific [in the sense of (a) one solubilizate orientation being markedly favoured over others or (b) multiple contact points being possible] in reverse rather than in normal micelles. However, in most cases modest enantioselectivities have also been obtained.I26 An overview of the literature on stereochemistry shows that the real applicability of self-assembled systems to promote stereoselectivities is a subject that remains to be proved. Since maximum stereospecificities are expected for systems that provide relatively rigid and specific binding sites for a given substrate and its reactive transition state, other membrane mimetic agents, such as supramolecular host systems, will fulfil more adequately this requirement.’ Synkinetic Approach for Modelling Reactivity Although the parallels between enzymes and the catalytic activity of self-assembled systems will undoubtedly continue to be profitably explored, it seems that future developments of self-assembled systems acting as catalysts will probably emphasize synthetic ~hemistry.~ Until the 1980s, membrane mimetic agents had been largely studied by physical chemists and biophysicists, and organic chemical aspects had been ignored.This situation has been changed rapidly in recent years; organic chemists have started to synthesize new types of molecules that spontaneously assemble in specific ways.The word ‘synkinesis’ has been minted for the synthesis of molecular assemblies with a defined structure and/or function, and ‘synkinons’ for the corresponding monomers. Membranes and molecular assemblies do not ‘self- organize’, but follow the ‘synkinetic’ plans of a chemist. Self- organization is unsatisfactory for producing assemblies with a DTAB MICELLES EFFECTS f PR + Cr(VI) + DTAB PRO, THE OXIDATION OF PR BY V(V) YIELDING PREFERENTIALLY A TERNARY COMPLEX PR + V(V) + DTAB 4 PR - V(V)-DTAB, COMPLEX I I /-----DTAB PRODUCES BATHOCHROMIC SHIFT AND HYPERCHROMIC EFFECT ON THE ABSORPTION SPECTRUM OF THE PR + Ti(IV) e PR, - Ti(IV) COMPLEX PR + Ti(lV) + DTAB PR, - Ti(IV)-DTAB COMPLEX I I Fig. 2 Reaction products formed with Pyrogallol Red (PR) in the absence and presence of DTAB micelles.42R Analyst, April 1996, Vol.121 defined stereochemistry and functionality or with nanopores and receptors which are characteristic of biological membranes. These features have to be planned by organic chemists; synkinetic planning is a presupposition of a successful sys- tem. Micelles can be target assemblies of synkinesis if they answer a well defined purpose. Thus, one may wish to produce a spherical micellar particle with fixed boundaries and a long lifetime. In this case, the hydrated head-groups which repulse each other must be replaced by head groups which form strong hydrogen bonds and possess a concave shape. Today it is known that a number of amphiphiles with a rigid hydrophobic core also form micelles, indicating that a flexible hydrocarbon chain is not a prerequisite for micellization, and that these assemblies are particularly efficient solubilizing agents.128,129 Vesicles which are long-lived are even more appropriate as target assemblies of synkinetic planning. The preparation of asymmetric vesicle membranes in which the outer and inner surfaces act as electron donors and acceptors, or vice versa, are of high relevance. A membrane of this type may support light- induced charge separation. A large body of molecular assemblies have been described using the synkinetic approach. Synkinesis of assemblies containing intelligent combinations of synkinons gives systems with new material properties and optimal environmental conditions for their eventual activities. What remains to be done is to integrate the described assemblies into society.This is being tried in many application laboratories throughout the world. Reactivities in self-assembled systems with a defined stereochemistry and functionality or with nanopores and receptors, which are characteristic of biological membranes, are now being intensively investigated with excellent results.3 An example is the first efficient hydrolysis of an amide at room temperature and at pH 8. When a cationic amide is mixed with anionic palmitate, at pH 8, an undefined molecular cluster is formed in which the water-stable amide (tl/2 > 1 year) rapidly hydrolyses (tl,2 = 3.1 min). l30 The ‘long-time’ contact of reactants, a state thought to be essential for enzyme-like reactions, can obviously not only be enforced by neighbouring group effects in rigid molecules or in complexes between enzyme clefts and substrates.131 It may also occur in very simple micellar-like clusters of extremely low c.m.c.We hope that kinetic analysis can profit as soon as possible from the synkinetic approach. Planning and synthesizing the synkinon yielding the adequate self-assembled systems, which has the ability of resolving a determined reactivity problem, is undoubtedly an extremely attractive idea. Conclusions In this review we have attempted to cover some of the most important areas in the kinetics of self-assembled systems and their implications in kinetic analysis. Although the systems employed are diverse there is a growing understanding and confidence regarding how one can manipulate chemical reactions by intervening at the microscopic level of the distribution and interactions among molecules.The fear that microheterogeneous media are messy, uncontrollable systems is no longer appli~able.13~ Certainly, many more novel applica- tions of these microheterogeneous media in kinetic analysis are yet to come. Future progress in this area will obviously depend on the intense collaboration and dialogue between analytical chemists and physicists and/or organic chemists and, when this is not possible, on the profound knowledge on the physico-chemical and organic literature on this topic. Recent studies on the physico-chemical area are being addressed not only to the development of better kinetic models but also to increase the understanding of colloidal structure and of ionic interactions with association colloids composed of ionic, non-ionic, zwitterionic, and amphoteric surfactants and their mixtures, which are more typical of biological membranes and commercial applications.In this context, it is to be noted that the potential of surfactant aggregates in creating bio- mimetic microenvironments is not limited by the possibility of the strict control of the size of such aggregates, but also can be realized through the use of aggregates with the most favourable geometric shape. The latter approach is still awaiting its implementation. 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Lontie, R., CRC Press, 1984, vol. 3, p. 1.44R Analyst, April 1996, Vol. 121 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 Martinek, K., Khmelnitsky, Y. L., Levashov, A. V., and Berezin, I. V., Dokl. Akad. Nauk SSSR, 1982,263,737. Hilhorst, R., in Structure and Reactivity in Reverse Micelles, ed. Pileni, M. P., Elsevier, New York, 1989, vol. 65, p.323. Kurganov, B. I., Tsetlin, L. G., Malakhova, E. A., Chebotareva, N. A., Lankin, V. Z., Levashov, A. V., Glebova, G. D., Berezovskii, V. M. Martinek, K., and Berezin, 1. V., Dokl. Akad. Nauk SSSR, 1985,282, 1263. Belyaeva, E. I., Brovko, L. Y., Ugarova, M. N., Klyachko, N. K., Levashov, A. V., Martinek, K., and Berezin, 1. V., Dokl. Akad. Nauk SSSR, 1983,273,494. Visser, A. J. W. G., and Santema, J. S., in Analytical Applications of Bioluminescence and Chemiluminescence, ed. Kricka, L. J., Torpe, G. H. G., and Whitebread, T. P., Academic Press, London, 1984, Hoshino, H., and Hinze, W. L., Anal. Chem., 1987,59,496. Igarashi, S., and Hinze, W. L., Anal. Chem., 1988, 60,446. Sanchez-Ferrer, A., Satema, J. S., Hilhorst, R., and Visser, A. J. W. G., Anal. Biochem., 1990, 187, 129. Eremin, A. N., Savenkova, M. I., and Metelitsa, D. I., Bioorg. Khim., 1986, 12, 606. Kabanov, A. V., Khrutskaya, M. M., Eremin, S. A., Klyachko, N. L., and Levashov, A. V., Anal. Biochem., 1989, 181, 145. Kumar, C., and Balasubramanian, D., J . Phys. Chem., 1980, 84, 1895. Menger, F. M., and Elrington, A. R., J. Am. Chem. Soc., 1991, 113, 9621. Lowe, M. B., and Phillips, J. N., Nature (London), 1962, 194, 1058. Luisi, P. L., Angew. Chem., 1985, 24, 439. Martinek, D., Levashov, A. V., Klyachko, N., Khmelnitski, Y. L., and Berezin, I. V., Biocatalysis, 1987, 1, 9. Fletcher, P. D. I., and Parrott, D., in Structure and Reactivity in Reverse Micelles, ed. Pileni, M. P., Elsevier, New York, 1989, vol. 65, p. 303. p. 559. 120 121 122 123 124 125 126 127 128 129 130 13 I 132 Zhou, D. L., Gao, J., andRusling, J. F., J . Am. Chem. SOC., 1995,117, 1127. O’Connor, C. J., Ramage, R. E., and Porter, A. J., Adv. Colloid Interface Sci., 1981, 15, 25. Bunton, C. A., Pure Appl. Chem., 1977, 49, 969. Bunton, C. A,, and Bacaloglu, R., J. Colloid InterfaceSci., 1987,115, 288. Menger, F. M., and Whitesell, L. G., J. Am. Chem. Soc., 1985, 107, 707. Menger, F. M., Gan, L. H., Johnson, E., and Durst, H. D., J. Am. Chem. Soc., 1987,109,2800. Magid, L. J., in Reverse Micelles. Biological and Technological Relevance of Amphiphilic Structures in Apolar Media, ed. Luisi, P. L., and Straub, B. E., Plenum, New York, 1984, p. 95. Sunamoto, J., Iwamoto, K., Akutagawa, M., Nagase, M., and Kondo, H., J . Am. Chem. Soc., 1982,104,4904. Hoshino, K., Saji, T., Suka, K., and Fujihara, M., J. Chem. Soc., Faraday Trans. 1, 1988,84, 2667. Barrelt, D. G., and Gellman, S. G., J. Am. Chem. Soc., 1993, 115, 9343. Menger, F. M., and Fei, Z. X., Angew. Chem., 1994,106,329; Angew. Chem., Znt. Ed. Engl., 1994, 33, 346. Menger, F. M., Angew. Chem., 1991, 103, 1104; Angew. Chem. Int. Ed. Engl., 1991, 30, 1086. Kalyanasundaram, K., and Gratzel, M., in Kinetics and Catalysis in Microheterogeneous Systems, ed. Gratzel, M., and Kalyanasundaram, K., Surfactant Science Series, Marcel Dekker, New York, 1991, vol. 38, ch. 1 . Paper 51071 16J Received October 30, 1995 Accepted January 2,1996
ISSN:0003-2654
DOI:10.1039/AN996210033R
出版商:RSC
年代:1996
数据来源: RSC
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Analyst,
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1996,
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C. J. Peacock,
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Analyst, April 1996, Vol. 121 41N Book Reviews Quality in the Analytical Chemistry Laboratory By Elizabeth Prichard. Analytical Chemistry by Open Learning. Pp. xxiii + 308. John Wiley. 1995. Price f19.75 (Paper); €45.00 (Cloth). ISBN 0-471-95470-5 (Paper), 0-471 -95541 -8 (Cloth). After effectively completing their coverage of analytical techniques the ACOL texts have started on more general topics, firstly environmental analysis and now, quality. This book marks a new departure in a couple of other ways; it is written by a team of five authors, all from the Laboratory of the Government Chemist coordinated by Dr Elizabeth Prichard and it comes out in association with the Government sponsored VAM (Valid Analytical Measurement) initiative. It is pleasing to note that the editorial control has been such that the joins do not show and it reads as well as a single author text.There are 250 pages of instructive text and a further 40 pages of answers to self-assessment questions, which is a rather higher ratio of text to question than in the other ACOL volumes. The level is definitely that of the analytical technician and does not go far enough for the professional analyst. But by the end of their study a technician should have a good appreciation of why they do things the way they do even if they will not be fully equipped to devise there own quality assurance procedures from scratch. Even before the text starts there is a useful brief summary of basic statistics and a glossary of terms used in the discussion of quality of measurement.Then chapter one sets out the basic concepts and nomenclature used in quality systems and gives some telling examples of the need for quality measurement with the classic cautionary tales from interlaboratory trials. ‘it will be really valuable to give analytical technicians an understanding of the why and how of the quality procedures they will meet in their work.’ After the reader has been convinced of the need for quality systems, they should be inspired to tackle the section on sampling. The author covers not just how to take a sample but also the essential awareness needed to ensure the integrity of the sample. Then the reader is lead gently through statistical sampling plans according to IS0 2859 (not in great detail and not enough to set up a scheme themselves, but enough to give them an understanding of how any scheme that they are using was arrived at).Chapter three is on selecting and validating analytical methods. Unusually it includes a section on costs with one of the three self-assessment questions being on costing out an analytical determination. A large part of the chapter looks at the criteria needed to assure correct identification of an analyte by spectroscopy or chromatography. Perhaps some is a bit too prescriptive, like the insistence that using mass spectrometry requires the molecular ion or that infrared spectra are recorded between 4000 and 625 cm-l only. The validation of methods fights shy of any statistical treatment and just discusses the need for replication, recovery tests, blanks and checking interfer- ences and what approaches can be used to check for problems in an analytical method. The following short chapter is on selecting and monitoring equipment; purchasing consumables; preparing, storing and labelling reagents and some advice on laboratory design.Chapters five and six are rather more ‘meaty’. Firstly comes a basic common sense list of things an analyst needs to do before starting work and follows with what needs to be checked whilst working and what needs to be carried out afterwards. All pretty basic, but if only we did them all! Such a list should be given to all students working in a lab (or even in the kitchen). But the heart of these chapters is a discussion of statistical methods: control charts in chapter five and for measurement uncertainty in chapter six.The latter starts with basic ideas of distribution and combination of errors and then looks at their overall effect on analytical measurement and how this is to be interpreted. Finally the student is led through a discussion of quality systems in chemical laboratories. The basic ideas behind GLP, IS0 9000, NAMAS, etc., are covered as is the setting up and running of internal quality audits. I do like the description of implementing a quality system as being like combing tangled hair-the result is pleasing to behold and easier to manage but the process is time consuming and often painful! I am not sure that the book succeeds in being an ‘indis- pensable volume for . . . laboratory managers wishing to introduce quality assurance methods into their laboratories’, for it does not go far enough though there is a good bibliography to point the reader further.However, it will be really valuable to give analytical technicians an understanding of the why and how of the quality procedures they will meet in their work and will also serve to introduce undergraduate and higher level BTEC students to the concepts that they are bound to meet once they start work. I shall certainly use it in my teaching. C. J . Peacock 519003 71 Lancaster University Practical Guide to Infrared Microscopy By Howard J. Humecki: Practical Spectroscopy Series, Volume 79, Pp. x + 472. Marcel Dekker, New York. 1995. Price US $150.00. ISBN 0-8247-9449-4. The most popular specialist accessory for an FTIR spectrometer nowadays is a microscope, and the variety of samples that can be examined makes it an indispensible tool for a good analytical laboratory. Individual samples down to about 10 microns in size can be readily examined, and complex or layered structures deciphered.Even with large samples it is often easier to examine using microsampling techniques than to deal with an intransigent mass by traditional means. To get the best out of the instrument, the operator has to learn the skills of both microscopy and spectrometry. A book such as this is a useful bridge between the specialities. ‘To get the best out of the instrument, the operator has to learn the skills of both microscopy and spectrometry. A book such as this is a useful bridge between the speci- alities. ’ The last volume on the subject (Infrared Microscopy- Theory and Applications, now out of print) appeared in this series in 1988.Since then, the number of instruments and the range of applications has risen dramatically. In the early days, use was limited to well funded research groups and industries where small contaminants meant ‘big buck’ problems, such as the semiconductor and computer disk companies. The falling price of computers and FTIR spectrometers (and to some extent the microscopes themselves) has made the technique more widely accessible.42N Analyst, April 1996, Vol. 121 For converts to the field it is not necessary to say much, other than buy the book (if you haven’t already) then keep it chained down. For newcomers and prospective users, however, some details are in order.Do not expect a step-by-step user manual, despite the title. This is a collection of essays, each capable of standing alone, which address applications of the technique to different areas of work. However, the experiences of a practiced user in one field may well help a novice in another, and in the absence of a structured tutorial guide to the subject this book is the best information source around. As in the previous volume, the first chapter is concerned with instrument design and optimization of performance. A quick guide to choice of sampling technique is next, then a description of point by point mapping. In my view, the book’s real strength lies in the chapters that follow. Written by specialists in particular application areas, they give justification to the book’s title.In each you will find personal views on the best way to tackle problems, and collections of hints and tips from many years of combined experience. Here are chapters on polymer films and laminates, automobile paints, fibres, artworks, pharmaceuticals and miner- ology, each with an individual flavour. This approach does result in some overlaps but makes each section readable as an en ti ty . Sample mounting is included, a real problem for beginners to microscopy (most spectroscopists!) and the cause of much bad language when one’s sole tiny fragment flies off onto the lab carpet. The final chapter could be better called ‘Microsample Degradation Techniques’ rather than ‘Microsample Preparation Techniques’, but gives useful hints on identifying complex polymers.In the future, more applications of ATR microscopy and new instrument designs will arise. For now, however, this volume is reasonably up to date. It is aimed at a specialist but expanding market, which may also tempt those considering the possibil- ities. If you do plan to buy an FTIR microscope, negotiate for a copy as part of your discount! David Crowther 5190025E Sheflield Hallam University Techniques and Practice of Chromatography By R. P. W. Scott. Chromatographic Science Series, Volume 70. Pp. xii + 396. Marcel Dekker. 1995. Price US $1 15.00. ISBN 0-8247-9460-5. As declared by the author in the preface, this book has been designed to provide an insight into chromatographic procedures for scientists who are non-chromatographers. As such it deals with chromatography as a general subject with a view to covering some of the various chromatographic procedures and in this case, the chromatographic methods selected are liquid chromatography (particularly as HPLC), GC and TLC.The book has 4 parts. Part 1 goes under the title ‘The Chromatographic Process’ and consists of 5 chapters which deal with the theory of chromatography and covers the history and principles of chromatographic procedures: the mechanism of retention; mechanisms of peak dispersion and column effi- ciencies; separation ratios (a values) and qualitative applica- tions of chromatography: resolution and quantitative applica- tions. Part 2 is concerned with GC, part 3 describes HPLC. Both parts consist of 4 chapters which deal with the components of the chromatographs, detection systems, columns and applica- tions.Part 4 consists of 2 chapters which describe the apparatus and techniques of TLC. As intended by the author, this book has been designed to provide a good introduction to the potentials of chromatography for scientists working in non-chromatographic disciplines, and in the opinion of this reviewer, many important aspects of the subject have been well covered. However some reservations are as follows. The history and theory of chromatography is very thoroughly treated within part 1 but since this has been so well covered in many previous publications, often by the current author, it is questioned whether such an extensive treatment is appropriate in this context. It is considered that although parts 2 and 3 contain much useful information for the non-chromatog- rapher on the topics of GC and HPLC, they are somewhat out- of-date.This is mostly from the point of view of applications. More could have been said about photodiode array detectors, GC and LC-MS, modern chromatographic software systems including optimization systems as applied to method develop- ment and validation of chromatographic procedures. Many chapters include insufficient up-to-date references which would introduce the non-chromatographer to the modern chromatog- rap h y literature. ‘This book has been designed to provide a good introduction to the potentials of chro- matography for scientists working in non- chromatographic disciplines’ In conclusion, this reviewer considers that this publication contains much which will be of interest to the non-chromatogra- pher.However, to encourage such scientists to make greater use of chromatography, a preferred treatment would include less theory but provide more examples of applications and highlight how some of the more modern approaches which are currently available may be applied to solve a wide variety of problems. G. P. Carr 51900340 Chiroscience, Cambridge ~ ~ ~~ ~ ~ ~~ Quality Assurance in Analytical Chemistry By W. Funk, V. Dammann and G. Donnevert. Pp. xxii + 238. VCH. 1995. DM. 125.00. ISBN 3-527-28668-3. This monograph is the latest in a number of similar books published in recent months reflecting the enhanced importance of the subject. It is a well-executed translation of the original German-language edition first published in 1992 having been commissioned by the German Environmental Ministry to provide a basis of an analytical quality assurance (AQA) system for the water industry.The content has a much wider application than the original brief might suggest. During preparation of this version the text has been extended and updated. Originally written with the requirements of EN 45 000 and I S 0 9OOOff in mind, other national accreditation standards (eg. , NAMAS in the UK) are equally well accommodated. The processes involved in setting up an appropriate AQA system are identified as a sequence of four phases which constitute the four chapters of the book. The first of these describes the steps leading to the introduction of a new analytical procedure by applying statistical methods to the preparation of standard samples, calibration, internal standards, etc.The process is continued in the three subsequent chapters commencing with the introduction of a candidate analytical procedure. The applications of various statistical control charts are detailed. These include the ARL, Shewart, R- and s-charts, Cusum and V-mask. Chapters 3 and 4 address internal and external QA and include further statistical techniques to monitor analytical results by means of the Youden plot, F-tests, outlier tests, and total standard deviation estimation. The text is supplemented by two appendices including worked examples of sample calculations and associated statistical tables.Analyst, April 1996, Vol.121 43N Although the index is adequately comprehensive, location of a specific aspect of laboratory QA is facilitated by the extremely detailed contents listing where individual paragraphs are extensively decimalized (e.g., 1.2.3.1.2. Mandel’s fitting test). There is also a useful glossary of pertinent QA definitions. The book successfully combines the role of authoritative textbook and reference manual, with that of a practical handbook and guide to the selection of an appropriate AQA strategy. Presentation is at a level suitable to professionally qualified QA staff either as managers or practitioners. ‘The book successfully combines the role of authoritative textbook and reference man- ual, with that of a practical handbook and guide to the selection of an appropriate AQA strategy.’ I found little to criticize in either the content or presentation. To be hypercritical, I would have appreciated a more extensive discussion of certainty of the statistical techniques, although the 154 references do supplement the text where necessary. More expensive than many of its potential rivals, this is nevertheless a book which I can wholeheartedly recommend to all those engaged in the AQA field. 5190077H J. K. Corbett Chemically Modified Surfaces Edited by J. Pesek and Ivan E. Leigh. Pp. xi + 224. The Royal Society of Chemistry. 1994. Price. f49.50. ISBN 0-851 56-595-X. This collection of seventeen camera ready papers represents the proceedings of a conference held in June 1993. The papers cover a wide variety of interface science, and as such the book provides a useful overview of a technologically important aspect of surface chemistry.Note, however, that the breadth of coverage does not extend to the UHV single crystal area. Interest for The Analyst readers lies in the novelty of some of the analytical techniques applied, as well as simply the range of the techniques brought to bear. I will attempt to give a flavour of the book by briefly describing a paper from each of the headings chosen for the symposium. These are ‘modification of polymer surfaces’, ‘membranes and thin films’, ‘modification and characterisation of catalysts’, ‘industrial applications of mod- ified surfaces ’, and finally ‘characterising oxide surfaces ’. In the first category, David Bergbreiter (Texas A&M) summarizes work of his group which has investigated chemical grafting onto polymer surfaces.This has potential as a means of maintaining the bulk properties while modifying the interfacial properties. One example given is of the radical grafting of methacrylonitrile onto a polyethylene film containing poly- ethylenepoly(ethy1ene glycol) trichloroacetate groups as macro- initiators. Evidence of grafting is achieved using transmission IR, ATR-IR, X P S and contact angle analysis using an appropriate text fluid. Buckyball fans will be encouraged to see as another example the grafting of CG0 molecules onto polyethylene. ‘a useful overview of a technologically im- portant aspect of surface chemistry.’ In the second category, and of particular relevance to The Analyst readers, an article by Ulrich Krull’s group (University of Toronto) compares the use of a number of analytical techniques in the study of thin films and membranes.Of principal interest are ellipsometry, XPS and surface plasmon resonance (SPR) techniques. As an example of the use of SPR, the authors use the technique to investigate the in situ dynamic properties of self-assembled long chain thiol films on gold substrates. SPR, which is sensitive to the thickness of the organic layer was used to follow the immobilisation of concanavalin A (a lectin) by the mercaptan layer. In the ‘modification and characterisation of catalysts’ section, Ronald Heck and Robert Farrauto (Engelhard Corporation) describe the use of catalysts for environmental control and the in-use modification of the catalytic surfaces.Perhaps the most visible catalyst for environmental control is that associated with automobile emission reduction. One variety contains Pt and Rh highly dispersed on alumina, which forms the coating on a ceramic honeycomb monolith. This acts as a so-called three- way catalyst, oxidizing CO and unburned hydrocarbons to CO2 and water, and reducing nitrogen oxides to nitrogen. For this catalyst, which typically operates at 300-600 OC, microprobe analysis reveals that P, Zn and S all contaminate the inlet of a used device. P and Zn reduce performance by forming an impenetratable amorphous glaze overcoat, while S is thought to poison the catalyst by selectively reacting with the active sites. A paper by Gregory Hickey and Pramod Sharma (Jet Propulsion Laboratory, California Institute of Technology) describes surfactant-assisted coal liquefaction.SEM-EDS, FTIR, NMR, GC-MS and XPS were used to investigate the origin of an increase in liquefaction yield from 83 to 92% when using a sodium lignosulfonate surfactant. This appears to result mainly from the breakage of crosslinks of the associated coal molecules, leading to greater access of hydrogen to the coal fragments. Finally, in the ‘characterising oxide surfaces’ section, Joseph Pesek (San Jose State University) describes means of convert- ing from hydroxide to hydride termination of silica surfaces. The particular application in mind here is as a separation medium for various forms of chromatography. Two methods were compared, one using chlorination/reduction, the second using silanisation.A variety of techniques were used to assess the effectiveness of the two methods in the conversion process, including DRIFT, Si-29 CP-MAS NMR, and DSC. The conclusion is that silanization-hydrosilation does hold prom- ise as a method for modifying oxide surfaces for chromato- graphy and capillary electrophoresis. G. Thornton 41901 56H Manchester University Applied Pyrolysis Handbook Edited by Thomas P. Wampler. Pp. x + 362. Marcel Dekker. 1995. Price US $135.00. ISBN 0-8247-9446-X. This ‘incomparable guide’ (as the publishers optimistically claim) views some facets of thermal degradation in analytical practice. Perhaps the most pertinent of observations in that context is found on p. 126-‘in spite of growing interest in the pyrolysis technique, one should not overstate its apparent superficial simplicity ’-implication that the method is a recent development is erroneous as pyrolysis-gas chromatography (PGC) was reported in the early 1950s.The first chapter reviews analytical pyrolysis, which is really the substance of the book as opposed to its title! Brief, but sound to a point. ‘Instrumentation and analysis’ lightly dismisses the recognized potential of laser heating, however, the approaches described are thorough (note that possible physical changes in a much used filament leading to modified pyrolysis behaviour are ignored). Tabular comparisons would clarify essentials for would-be users.44N Analyst, April 1996, Vol. 121 ‘Sampling and sample presentation’ happily emphasizes the ‘thin film concept’ and warns of difficulties inherent in preparing non-homogeneous and/or intractable samples as well as problems unique to the pyrolysis of large samples.As most of the content is dedicated to PGC, pyrolysis-mass spectrometry might be considered almost an intrusive alien, one instrument only is sketchily described and ensuing paragraphs on data acquisition/reduction are naively brief. Surely the Dutch group in Amsterdam are better informed than the present authors? ‘the contents of this book vary-some very good and well worth having-unfortunately, others less so.’ There follows a succession of contributions exampling a variety of applications ‘Micro-structure of polyolefins’ and ‘Degradation mechanisms of condensation polymers’ by Shin Tsuge and Hajime Ohtani are exemplary of specific applica- tions, pyrolysis/hydrogenation in the elucidation of hydro- carbon polymers and PGC-mass spectrometry in studies of the breakdown of poly-condensates.Next, pyrolysis as an aid in conservation and authentification of art works and archaeo- logical artefacts is discussed. The authors, regrettably, seem unaware of studies reported by workers at SMU in Dallas, Texas. Munson concisely summarizes and examples the vast complexity of environmental applications without imposing arbitrary limits. His contribution is understanding, penetrative, well referenced and all-embracing as the underlying philosophy is that of ‘there is nothing in Heaven or on Earth that is NOT environmental’, refreshing reading indeed.The chapter on forensic applications is coldly factual being little more than a list of (admittedly well chosen) examples. Surely, statements such as ‘routine methods used should preferably employ relatively inexpensive instrumentation’ and ‘the method should preferably not be labor intensive’ are hardly designed to enhance the validity of scientific testimony! Pyro-taxonomy is playing an increasingly important role in the classification and characterization of micro-organisms and a lucid, widely cast, well referenced and contemporaneous review of the state-of-the-art is pre-fixed by a brief history of its development, another substantial, informed contribution. The final chapter on ‘polar macromolecules’ has already been covered by fact or inference and therefore seems superfluous.‘Sample’ pyrograms form an appendix which, as correlation trials have shown, are only implication of what may be expected from similar samples. Alas, the contents of this book vary-some very good and well worth having-unfortunately, others less so. Editor, a small point, please note that incomplete chemical formulae can confuse. The text is happily free from typographical error and random reference checks show them pleasingly reliable. Last the index is far from comprehensive and gives the impression of being a hurried, last-minute compilation. C. E . R . Jones 519001 8B Surrey, UK Official and Standardized Methods of Analysis. 3rd Edition. Edited by Colin Watson for the Analytical methods Committee of The Royal Society of Chemistry. Pp.xxiv + 778. The Royal Society of Chemistry. 1994. Price f 110.00. ISBN 0-851 86-551 -4. The work of the Analytical Methods Committee (AMC) of the Royal Society of Chemistry (RSC) (and its predecessors) has continued uninterrupted for over forty years and in that time, many collaboratively tested methods for the determination of a wide range of substances have been established. These methods and accompanying reports are scattered throughout many volumes of The Analyst and in order to make reference to them easier, this book and its earlier editions have been published. The time-lag (21 years) between the publication of the second and the present editions is certainly unusually long and rather begs the question of the need for this book, if analytical practice has done without it for so long.It does appear, however, to have been worth the wait. In compiling the new edition the editor has faced a daunting mountain of accummulated material dating back to 1973. Analytical practice has radically altered over the last two or three decades and these developments in the subject are reflected in the methods selected for inclusion. All of the AMC methods up to 1992 are given in full. Although some of the older methods have been omitted because of obsolescence, where they provide a useful practical alternative to their usually more sophisticated successors they have been retained. Relevant work of other organizations such as MAW and Yorkshire Water Authority on the analysis of water is included for the first time, although only summaries of methods are given.Similarly, appropriate British Standards are cited. A detailed review of this volume would inevitably result in the monotonous listing of the subject matter it contains, reminiscent of the late Beachcomber’s ‘List of the Huntingdon- shire Cabman’. It is perhaps sufficient for present purposes to say that experienced editing has ensured the inclusion of all current standard methods for the analysis of a wide range of materials such as animal feeding stuffs, fertilizers, essential oils, fats and oils, cosmetics, trace elements and so on. Summaries of reports of the Statistics Committee of the AMC are also given. ‘This is an indispensible reference book to take its place alongside other such essential volumes as the AOAC Handbooks. For the many practicing analysts in industrial and public service laboratories, this is an indispensible reference book to take its place alongside other such essential volumes as the AOAC Handbooks.A useful and timely feature of this new edition is the attention given to the use of hazardous reagents and the techniques involving them, helpful reminders that safe laboratory practice is paramount. Errors in the text are minimal, but this reviewer cannot accept ‘2-aminopyrimidine’ for ‘2-aminoperimidine’ as the reagent for sulfate (p. 607). All in all, this book is an important contribution to the literature on standardized methods of analysis and a valuable source of reliable and tested methods used in the United Kingdom. W. I . Stephen 5l9001 OG Aberdeen Femtosecond Chemistry Edited by J.Manz and L. Woste. Pp. xxiv + 916. VCH. 1995. Price DM398.00; f 16.00 (Two volumes). ISBN 3-527-29062-1. This is a detailed and up-to-date text concerning this emerging field. There are two volumes for a total price of DM398, a very reasonable sum given the care that all concerned have taken in their production. It is a book that is aimed squarely at researchers in the field and those with aspirations in that direction. It is not for the mathematically faint-hearted and I would not recommend it for students below the graduate level.Analyst, April 1996, Vol. 121 45N For the target audience, however, this book is excellent, it is comprehensive, the contributors are some of the most capable in the field, and it is very much up-to-date.The editors and the contributors should be congratulated, - The book is split into five sections, each of which contains a number of chapters written by different researchers in the field. Volume 1 opens with two chapters which comprise section I of the book and essentially set the scene for what follows. The first is by George Porter, who sets the historical perspective, and details the rapid improvements in time resolution which have followed his first millisecond experiments in 1949. The use of lasers and the discovery of white light continuum generation allowed transient absorption measurements to reach femto- second resolution, and these processes are described. The second chapter is by Ahmed Zewail who details the types of molecular processes which are particular to the femtosecond timescale and introduces the concept of probing the transition state of reactions.This chapter also describes the control of pulse sequences and has an appendix giving the latest ultrafast experimental arrangements. The two chapters serve to bring the reader up to date with the present status of the field and describe the kinds of experiments possible and the information which may be expected to result from them. The remainder of the two volumes is broken into four sections (11-V), volume 1 ends with section I1 and volume 2 comprises sections 111-V. The first three of these are concerned with different categories of chemical systems which have been and are in the process of being studied. The final section is appropriately concerned with speculations on future directions in which the field may be expected to progress.The final chapter should be considered as a section on its own. The author, M. Quack, reminds us that the femtosecond time domain is one amongst many, and places it in perspective with respect to events taking place on both faster and slower timescales. ‘this book is highly recommended for all established researchers in the field of femto- chemistry and those who propose to enter it.’ Section 2 contains nine chapters concerned with the spectro- scopy of simple molecules, the first three are primarily experimental and the remaining six largely theoretical. Chapters 3,4 and 5 deal with broadband absorption, threshold ionization and coherence spectroscopies, respectively. All three are very clear, have descriptions of the experimental arrangements used, and show representative examples of experimental data.Chapters 6 to 11 are either largely or wholly theoretical dealing with models of excited states, dissociation, and ionization. These chapters vary in clarity but are for the most part interesting . In volume 2 the systems studied become more complex, part 111 deals with clusters and part IV with liquids, solids and photosynthetic reaction centres. Part 111 comprises 6 chapters; the first, by T. Baumert, R. Thalweiser, V. Weiss and G. Gerber, is particularly interesting and deals with clusters of sodium atoms and diatomics of other alkali metals. The photo- fragmentation of small sodium cluster ions Nanf and the two photon ionization spectroscopy of sodium clusters Nan (where n < 22) is described.The following two chapters concern mercury-rare gas and mercury nitrogen clusters and ammonia clusters, both are well written. Chapter 15 by J. A. Syage covers a large area of chemical dynamics in clusters including aspects of solvation and proton transfer. All four of these chapters contain good experimental sections and representative exam- ples of the data obtained. The final two chapters deal with theoretical aspects of cluster dynamics. In part IV of the book the most complex chemical systems, liquids, solids, surfaces, and photosynthetic reaction centres, are considered. The section consists of five chapters; the first three deal with liquids, solids and surfaces, whilst the final two deal with experimental and theoretical aspects of photosynthesis.All these chapters are clearly written and comprise some of the most easily understood material in the text. Finally, part V contains four chapters devoted to future directions the field may take and the final chapter by M. Quack. The first four chapters are theoretical and are heavy going for an experimentalist. The subject matter is, however, fascinating, particularly the possibility of laser control of chemical reac- tions. The book closes with short sections on each of the editors and contributors, including photographs of the individuals and their addresses, an author index and a subject index. The subject index is fairly comprehensive and useful. A major strength of the book is the bibliography, each chapter is comprehensively referenced and the references are very up-to-date.In conclusion this book is highly recommended for all established researchers in the field of femtochemistry and those who propose to enter it. S . J . Atherton 5190022 K University of Rochester New York, USA The Laboratory Environment Edited by R. Purchase, The Royal Society of Chemistry Special Publication No. 136. Pp. x + 258. The Royal Society of Chemistry. 1994. Price f49.50. ISBN 0-851 86-605-0. The Royal Society of Chemistry and the Society of Chemical Industry jointly organized a one-day symposium to consider the safe handling of dangerous substances in the laboratory. The scope of the symposium included radioactive and infectious agents as well as toxic substances. ‘The Laboratory Environ- ment’, the resulting proceedings volume, will be useful to a wide audience including chemists, laboratory managers and specialists in occupational health and safety.The broad appeal stems from the selection of topics presented in a concise manner from a variety of new vantage points. Book chapters are arranged in three sections: (i) surveillance, (ii) handling and disposal; and (iii) control of exposure. Chapter one outlines activities and efforts of the Royal Society of Chemistry (RSC) in the health and safety arena. The RSC is open minded and progressive in addressing chemist’s health issues. Its mortality and RECAP surveys are yielding invaluable information regarding the health and longevity of chemists in relation to both work place and lifestyle factors.Wrightson’s chapter illuminates the insurance company view. Only a small portion of the cost of accidents is covered by insurance, and thus accidents erode profits and income. Today, legislation is useful in providing guidance to employers, but the real impetus for compliance is liability and the ruinous costs associated with ignoring accident prevention. ‘useful to a wide audience including chem- ists, laboratory managers and specialists in occupational health and safety. ’ The role of medical surveillance in a comprehensive health and safety programme is considered by Agius and Yardley- Jones. As they point out there are relatively few circumstances where health risks are sufficiently great and where the requirements of sensitivity, specificity and ease of interpretation justify medical monitoring.medical surveillance even when appropriate should only be considered a failsafe or quality46N Analyst, April 1996, Vol. 121 control measure. These initial chapters provide a useful introduction and backdrop to the following sections. The subsequent chapters vary in their detail. Castegnaro’s discussion on disposal of laboratory carcinogens provides an appendix with validated methods for treatment of specific classes of carcinogens. Of particular value, he advises the reader of hazards associated with inappropriate treatment (e.g., conversion of nitrosoamines to nitramines or hydrazines). Detail provided regarding classification of carcinogens (chapter 5 ) is substantial, and more useful to a regulatory toxicologist than the target audience.The handling of cytotoxic drugs and radiopharmaceuticals presents hazards to chemists as well as pharmacy and nursing staff. Most antineoplastic drugs are either mutagenic, terato- genic or carcinogenic. Lee’s chapter outlines requirements for safe handling and discusses current thinking regarding medical surveillance. A very basic discussion of radiation hazards is provided in chapter 8 which touches on methods of protection, monitoring of radiation and contamination, and disposal. The article should be required reading for anyone setting foot in a radiochemistry laboratory. Anyone working with low-level radioactivity will want a good deal more information than is provided in this useful chapter. Handling and disposal of infectious agents, also handled by chemists in the work place, is outlined in a brief chapter by Collins. Again, those handling pathogenic organisms would want to peruse the references cited. Particularly useful to the synthetic chemists is the chapter on runaway reactions. The chapter introduces HAZOP and HAZAN, methods developed by chemical industry in the UK to identify and manage unexpected hazards, and cites additional resources. New laboratories and new ways of thinking about laboratory design can go a long way to minimize risks associated with laboratory work. The final two chapters emphasize worker protection via design and construction of safer laboratories. Lessons learned in developing the RhGne-Poulenc Rorer Chemical Research Laboratory are recounted by J. Salmon. The modern philosophy of laboratory design holds that laboratory, office and writing-up areas are entirely separate. Statutory requirements for ventilation and fume hood construction to meet these requirements have advanced. Because of complexity of such systems there is no substitute for performance and containment testing of the completed system under a variety of operating regimes. The chapter also describes many modem laboratory design features and materials. Every chemist is aware of the minimum requirements for safety equipment: a lab coat and safety spectacles. The papers assembled in this volume provide an enjoyable means to enhance awareness and elevate the level of expertise regarding current safety matters. Health and safety is not a ‘top down’ or mandated job function, it requires awareness and commitment throughout an organization. The topics are treated at a level that will be useful to bench chemists, technicians and others actively working in the laboratory, as well as their managers and corporate staff who need to understand the challenges and implications of laboratory health and safety issues. William M. Draper 5190066B California Department of Health Services California, USA
ISSN:0003-2654
DOI:10.1039/AN996210041N
出版商:RSC
年代:1996
数据来源: RSC
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6. |
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Analyst,
Volume 121,
Issue 4,
1996,
Page 47-51
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Analyst, April 1996, Vol. 121 47N Conference Diary Date 1996 May 5-8 6-8 6-10 9-1 1 13-14 14-15 19-22 19-24 20-22 20-23 20-24 23-25 29-3 1 June 4-7 Conference Location Contact International Colloquium on Process Related Analytical Chemistry in Environmental Investigations Gramado, Brazil Centro de Ecologia, Universidade Federal do Rio Grande do Sul, C.P. 15007, 91501-970 Port0 Alegre, Brazil Tel: +55 51 2281 633. Fax: +55 51 3361 568. E-mail: Cenecmif 1 .ufrgs.Br Dr. N. Haagsma, Utrecht University, Faculty of Veterinary Medicine, P.O. Box 80.175, NL-3508 TD Utrecht, The Netherlands Tel: +31 30 535365. Fax: +31 30 532365 Francoise Chavel, Executive, Secretary, European Optical Society, B.P. 147-91403 Orsay Cedex, France Tel: +33 1 69 85 35 92. Fax: +33 1 69 85 35 65. E-Mail: francoise.chavel@iota.u-psud.fr Swedish Academy of Pharmaceutical Sciences, P.O.Box 1136, S-111 81 Stockholm, Sweden Tel: +46 8 723 50 00. Fax: +46 8 20 55 11 Spring Innovations, 185A Moss Lane, Bramhall, Stockport, Cheshire, UK, SK7 1BD Tel: +44 (0)161 440 0082. Fax: +44 (0)161 440 9127 Ms. Paula Elliott, Secretary Analytical Division, The Royal Society of Chemistry, Burlington House, London W1V OBN, UK Tel: +44 (0)171 437 8656. Fax: +44 (0)171 734 1227 Mercedes Gomez, Laboratory of Toxicology and Biochemistry, School of Medicine, c/o San Lorenzo 21, E-43201 Reus, Spain Tel: +34 77 759376. Fax: +34 77 759322 Mary L' Abbe, Nutrition Research, Health Canada, Ottawa, ON K1A OL2, Canada Tel: +1 613 957 0924. Fax: +1 613 941 6182 E-mail:mlabbe@hpb.hwc.ca Michael Carl, Milschwirtschaffliche Untersuchungs und Versuchsanstalt Mempten, Postfach 2025, D87410, Kempten, Germany Tel: +49 8315 2900.Fax: +49 8315 290100 BESB 2; Anita Moberg, Swedish Environmental Protection Agency, S- 10648 Stockholm, Sweden Tel: +46 8 698 1000, Fax: +46 8 689 1504 E-mail: amo@environ.se Professor D. P. Sandra, IOPMS, Kennedypark 20, B-8500 Kortrijk, Belgium Tel: +32 56 204960. Fax: +32 56 204859 Romanian Society of Analytical Chemistry, 13 Boulevard Republicii, Sector 3, 70346 Bucharest, Romania Tel: +40 1 631 00 60. Fax: +40 1 631 2279 Carole Franks, Biosensors 96, Congress Secretariat, 24 Quentin Road, London, SE13 5DF UK Fax: +44 (0)181 318 3932 Veldhoven, The Netherlands EuroResidue 111, Third International Conference on Residues of Veterinary Drugs in Food 2nd European Symposium and Exhibition on Photonics in Manufacturing I1 Paris, France 2nd Symposium on Biotechnology-From the Gene to Finished Product Stockholm, Sweden Boston, USA Bath, UK Chiral USA '96 Analytical Measurements and Their Interpretation for Regulatory Purposes 4th International Symposium on Metal Ions in Biology and Medicine Barcelona, Spain 9th International Symposium on Trace Elements in Man and Animals Banff, Canada Symposium on Dairy Quality Assurance Sonthofen, Germany 2nd International Symposium & Workshop on Biological Environmental Specimen Banking (BESB 2) Stockholm, Sweden 18th International Symposium on Capillary Chromatography Riva del Garda, Italy XIIIth National Conference on Analytical Chemistry Craiova, Romania Biosensors 96 Bangkok, Thailand 3rd Nordic Festival of Mass Spectrometry Lund, Sweden Thorleif Lavold Jr./Gunilla Hugo, Fisons Instruments, Nordic AB, Gardsfogdevagen 16, S-161 70 Bromma, Sweden Tel: +46 8 629 24 00.Fax: +46 8 627 52 2048N Analyst, April 1996, VoE. 121 Date 5-7 9-13 10-1 1 10-14 13-14 16-21 17-2 1 30-517 Conference Locat ion Eurolab Symposium on Testing and Analysis for Industrial Competitiveness and Germany Sustainable Development Berlin, 8th International Conference on Metalorganic Cardiff, Vapour Epitaxy UK 6th Conference on Total Reflection X-Ray Fluorescence Analysis and Related Methods (Part 1) Eindhoven, Netherlands 11th International Converence on Prague, High-Power Particle Beams (BEAMS '96) Czech Republic 6th Conference on Total Reflection X-Ray Fluorescence Analysis and Related Methods (Part 2) Dortmund, Germany HPLC '96: 20th International Symposium on High Performance Liquid Phase Separations and Related Techniques California, USA 2nd European Symposium and Exhibition on Optical Instrument and Systems Design Glasgow, UK Resonance Ionization Spectroscopy and Its Applications, RIS-96 USA Pennsylvania, July 1-3 9th International Symposium on Polymer Oxford, Analysis and Characterization (ISPAC-9) UK 8-12 XVI International Congress of Clinical London, Chemistry UK 15-19 9th International Conference on Quantitative Surrey, Surface Analysis UK 17-19 8th Biennial National Atomic Spectroscopy Norwich, Symposium (BNASS) UK 22-25 Sixth International Meeting on Chemical Gai thersburg , Sensors USA Contact Dr.Jiigen Lexlow, Bundesanstalt fur Materialforschung und Priifung Unter den Eichen 87, D- 12205, Berlin, Germany Tel: +49 30 8104 1003. Fax: +49 30 81 1 2029 Glenda Bland, Global Meeting Planning Tel: +44 (0)1222 700053. Fax: +44 (0)1222 700665 E-mail: 10046.1402@compuserve.com Dr. D. K. G. de Boer, Philips Research Laboratories, WB21, Prof. Holstlaan 4, NL-5656 AA Eindhoven, The Netherlands Tel: +31 40 74 2859. Fax: +31 40 74 3075 E-mail: deboerd@prl.philips.nl Dr. Jiri Ullschmied, Conference Co-Chairman, Institute of Plasma Physics, AS CR, Za Slovankou 3, Prague 182 00, Czech Republic Fax: +422 858 6389. E-Mail: BEAMS96@ 1PP.CAS .CZ Dr. D. K. G. de Boer, Philips Laboratories WB2 1, Prof. Holstlaan 4, NL-5656 AA Eindhoven, The Netherlands Tel: +31 40 74 2859.Fax: +31 40 74 3075 E-mail: deboerd@prl.philips.nl Mrs. Janet Cunningham, Barr Enterprises, 10120 Kelly Road, P.O. Box 279, Walkersville, MD 21793, USA Tel: +1 301 898 3772. Fax: +1 301 898 5596 Francoise Chavel, Executive Secretary, European Optical Society, B.P. 147-9 1403 Orsay Cedex, France Tel: +33 1 69 85 35 92. Fax: +33 1 69 85 35 65. E-Mail: francoise.chavel@iota.u-psud.fr Sabrina Glasgow, Conference Secretary, Department of Chemistry, The Pennsylvania State University, 184 Materials Research Institute Building, University Park, PA 16802-7003 USA Tel: + I 814 865 0200. Fax: +1 814 863 0618 E-mail: scg4@psuvm.psu.edu Prof. John Dawkins, Department of Chemistry, Loughborough University of Technology, Loughborough, Leicestershire, UK LE 1 1 3TU Fax: +44 (0)1509 233163 Mrs.Pat Nielsen, XVIth International Congress of Clinical Chemistry, P.O. Box 227, Buckingham, UK MK18 5PN Fax: +44 (0)1280 6487 Professor J. E. Castle, University of Surrey, Department of Materials Science and Engineering, Guildford, Surrey UK GU2 5XH Tel: +44 (0)1483 259150. Fax: +44 (0)1483 259508. E-mail: j.castle@surrey:ac.uk Ms. Brenda Holliday, BNASS Secretariat, Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge, UK CB4 4WF Tel: +44 (0)1223 420066. Fax: +44 (0)1223 423623 Howard H. Weetall, National Institute of Standards and Technology, 222/A353, Gaithersburg, Maryland, 20899, USA Tel: +I 301 975 2628. Fax: + I 301 330 3447. E-Mail: weetall@micf.nist.govAnalyst, April 1996, Vol. 121 49N Date Conference August Location 10-13 11-16 20-23 2 1-23 25-30 42nd International Conference on Analytical London, Science and Spectroscopy Canada ICORS '96: XV International Conference on Raman Spectroscopy USA 7th International Symposium on Osaka, Pharmaceutical and Biomedical Analysis Japan (PBAT '96) Pittsburgh, Fourth International Symposium on Capillary York, Electrophoresis UK XXIII EUCMOS September 1-7 4-6 8-1 1 8-1 3 9-1 1 9-1 3 9-1 3 10-14 15-20 Euroanalysis IX Balatonfured, Hungary Bologna, Italy Traceability and Comparability of 'Amount of Substance' Measurements The Netherlands Noordwijkerhout, 22nd Annual Meeting of the British Mass Spectrometry Society UK Swansea, CLEO '96: European Conferences on Lasers Hamburg, and Electro-Optics Germany Sixth International Symposium on Field Flow Ferrara, Fractionation Italy 14th International Conference on High Resolution Molecular Spectroscopy Czech Republic Prague, PRAHA96: 14th International Conference on High Resolution Molecular Spectroscopy Prague, Czech Republic International Symposium and Exhibition on Biomedical Optics IV Austria Graz, 21st International Symposium on Stuttgart, Chromatography Germany Con tact Martin Stillman, University of Western Ontario, Department of Chemistry, London, ON N6A 5B7, Canada Tel: +1 519 661 3821.Fax: +I 519 661 3022. E-Mail: stillman@uwo.ca Professor S. Asher, Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA Professor Susumu Honda, Faculty of Pharmaceutical Sciences, Kinki University, Kowakae 3-4-1, Higashi Osaka 577, Japan Fax: +81 6 721 2353 Dr.T. L. Threlfall, Industrial Liaison Executive, Department of Chemistry, University of York, York, UK YO1 5DD Tel: +44 (0) 1904 432576. Fax: +44 (0) 1904 4325 16 E-mail: js20@york.ac.uk Professor Dr. J. Mink, Department of Analytical Chemistry, University of Veszprkm, P.O. Box 158, H-8201 VeszprCm, Hungary Professor Luigia Sabbatini, Euroanalysis IX, Dipartimento di Chimica, Universits di Bari, Via Orabona, 4, 70126 Bari, Italy Tel: +39 80 544 2020. Fax: +39 80 544 2026 Linda Catterson, Workshop Secretary, Laboratory of the Government Chemist, Queens Road, Teddington, Middlesex, TW 11 OLY, UK Tel: +44 (0) 18 1 943 7423. Fax: +44 (0) 18 1 943 2767. E-mail: lc@lgc.co.uk Dr. Fred Mellon, Institute of Food Research, Norwich Laboratory, Norwich Research Park, Colney, Norwich, UK NR4 7UA Tel: +44 (0)1603 255299.Fax: +44 (0)1603 452578 E-mail: fred.mellon@bbsrc.ac.uk CLEO/Europe '96, Institute of Physics, Meetings and Conferences Department, 47 Belgrave Square, London, UK SW 1X 8QX F. Dondi, Department of Chemistry, University of Ferrara, Via L. Borsari, 46,I-44100 Ferrara, Italy Tel: +39 532 291 154. Fax: +39 532 240709 Dr. V. Spirko, Academy of Sciences of the Czech Republic, J. Heyrovsk, Institute of Physical Chemistry, Dolejskova 3, CZ-18223 Praha 8, Czech Republic Dr. Vladimir Spriko, Academy of Sciences of the Czech Republic, The J. Heyrovsky Institute of Physical Chemistry, Dolejskova 3, CZ-18223 Praha 8, Czech Republic Fax: +42 2 858 2307. E-Mail: praha96@jh-inst.cas.cz. or praha96@ wcpj .chemie.uni-wupperta1.de Francoise Chavel, Executive Secretary, European Optical Society, B.P.147-91403 Orsay Cedex, France Tel: +33 1 69 85 35 92. Fax: +33 I 69 85 35 65. E-Mail: francoise.chavel@iota.u-psud.fr GDCh-Geschaftsstelle, Abt. Tagungen, Varrentrappestr. 40-42, Postfach 90 04 40, D-6000 Frankfurt am Main 90, Germany Tel: +49 69 791 7358. Fax: +49 69 791 747550N Analyst, April 1996, Vol. 121 Date 15-20 16-18 16-20 23 24-26 29-04 Conference 1996 European Workshop in Chemometrics The Third International Conference on Applications of Magnetic Resonance in Food Science 5th International Conference on Plasma Source Mass Spectrometry 12th ICP-MS Applications Meeting Mass Spectrometry Processes for the Determination of Trace Elements 23rd Annual Conference of the Federation of Analytical Chemistry and Spectroscopy Societies (FACSS) October 3 4 Validation in Capillary Electrophoresis 20-25 Expoquimia Equiplast Eurosurfas 28-29 Monitor '96 November 4-8 International Symposium on the Industrial Application of the Mossbauer Effect 13-15 13th Montreux Symposium on Liquid Chromatography-Mass Spectrometry 21 Spectroscopic Detection in Process Analysis (11) 1997 January 4-9 The Fourth International Symposium On: New Trends in Chemistry The Role of Analytical Chemistry in National Development Location Bris tol, UK Nantes, France Durham, UK Julich, Germany Julich, Germany Kansas City, USA York, UK Barcelona, Spain Manchester, UK Johannesburg, South Africa Montreux, Switzerland Hull, UK Giza, Egypt 12-17 1997 European Winter Conference on Plasma Gent, Spectrochemistry Belgium Contact Caroline Hutcheon, School of Chemistry, University of Bristol, Cantock's Close, Bristol B58 1TS, UK Tel: +44 (0)117 928 9000 or +44 (0)117 928 7658.Fax: +44 (0)117 925 7295 G. J. Martin or V. Foucault, FacultC des Sciences, Laboratoire de Rksonance MagnCtique NuclCaire et RCactivitiC Chimique, U.R.A. - CNRS 472, 2 rue de la Houssinikre, 44072 Nantes Cedex 03, France Tel: +33 4037 3169. Fax: +33 4074 9806 Dr. Grenville Holland, Department of Geological Sciences, Science Laboratories, South Road, Durham City, UK DH1 3LE Fax: +44 (0)191 374 2510 Dr. J. S. Becker, Forschungszentrum fur Chemische Analysen, D-52425 Julich, Germany Tel: +49 2461 612698. Fax: +49 2461 612560 Dr. J. S. Becker, Forschungszentrum fur Chemische Analysen, D-52425 Julich, Germany Tel: +49 2461 612698.Fax: +49 2461 612560 FACSS, 201B Broadway Street, Frederick, MD Tel: +I 301 846 4797. 21701-6501 USA Dr. T. L. Threlfall, Industrial Liaison Executive, Department of Chemistry, University of York, York, UK YO1 5DD Tel: +44 (0) 1904 432576. Fax: +44 (0) 1904 4325 16 E-mail: js20@york.ac.uk Expoquimia Equiplas Eurosurfas, Fira de Barcelona, Avda. Reina Ma Cristina, E-08004, Barcelona, Spain Spring Innovations, 185A Moss Lane, Bramhall, Stockport, Cheshire, UK SK7 1BA Tel: +44 (0)161 440 0082. Fax: +44 (0)161 440 9127 Herman Pollak, Mossbauer Laboratory, University of the Witwatersrand, Private Bag 3, WITS 2050, Johannesburg, South Africa Tel: +27 11 716 4053/2526. Fax: +27 11 339 8262.E-Mail: ISIAMEQPHY SNET.PHY S. WITS. AC.ZA M. Frei-Hausler, Postfach 46, CH-4123 Allschwil 2, Switzerland Tel: +41 61 481 2789. Fax: +41 61 482 0805 Dr. J. S. Lancaster, BP Chemicals, Hull Research Centre, Saltend, Hull, UK HU12 8DS Tel: +44 (0)1482 894803. Fax: +44 (0)1482 892171 Professor Dr. M. M. Khater, Chemistry Department, Faculty of Science, Cairo University, Giza, Egypt Tel: +57272 13. Fax: +5727288 L. Moens, Secretariat, 1997 European Winter Conference, Laboratory of Analytical Chemistry, University of Gent, Proeftuinstraat 86, B-9000, Gent, Belgium Tel: +32 9 264 66 00. Fax: +32 9 264 66 99 E-Mail: plasma97@rug.ac.beAnalyst, April 1996, Vol. 121 5 1N Date Conference Location April 14-19 Genes and Gene Families in Medical, Texas, Agricultural and Biological Research: 9th International Congress on Isozymcs USA 12-16 European Symposium on Photonics in Paris, Manufacturing I11 France June 15-2 1 International Conference on Analytical Moscow, Chemistry Russia 16-20 European Symposium on Environmental and Munich, Public Safety I1 Germany 30-3/7 6th European ISSX Meeting September 8-12 Biomedical Optics V Gothenburg, Sweden Poland October 26-29 8th Symposium on Handling of Almeria, Environmental and Biological Samples in Chromatography.26th Scientific Meeting of the Group of Chromatography and Related Techniques of the Spanish Royal Society of Chemistry Spain Contact Mrs. Janet Cunningham, Barr Enterprises, 10 120 Kelly Road, P.O. Box 279, Walkersville, MD 21793, USA Tel: +1 301 898 3772. Fax: +1 301 898 5596 Francoise Chavel, Executive Secretary, European Optical Society, B.P. 147-9 1403 Orsay Cedex, France Tel: +33 1 69 85 35 92. Fax: +33 1 69 85 35 65. E-Mail: francoise.chavel@iota.u-psud.fr Dr. L. N. Kolomiets, Scientific Council on Chromatography of the Russian Academy of Sciences Leninsky Prospect 31, 117915 Moscow, Russia Fax: +7 095 952 0065 Francoise Chavel, Executive, Secretary, European Optical Society, B.P. 147-91403 Orsay Cedex, France Tel: +33 1 69 85 35 92. Fax: +33 1 69 85 35 65. E-Mail: francoise.chavel@iota.u-psud.fr Meeting Secretariat, 6th European ISSX Meeting, c/o The Swedish Academy of Pharmaceutical Sciences, P.O. Box 1136, S-1 1 1 81 Stockholm, Sweden Tel: +46 8 723 5000. Fax: +46 8 20 55 11 Francoise Chavel, Executive Secretary, European Optical Society, B.P. 147-9 1403 Orsay Cedex, France Tel: +33 1 69 85 35 92. Fax: +33 1 69 85 35 65. E-Mail: francoise.chavel@iota.u-psud.fr M. Frei-Hausler, IAEAC Secretariat, Postfach 46, CH-4123 Allschwil 2, Switzerland Fax: +41 61 482 08 05
ISSN:0003-2654
DOI:10.1039/AN996210047N
出版商:RSC
年代:1996
数据来源: RSC
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7. |
Courses |
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Analyst,
Volume 121,
Issue 4,
1996,
Page 52-52
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PDF (94KB)
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摘要:
52N Analyst, April 1996, Vol. 121 Courses Date 1996 May 19-22 20-23 20-23 21-23 21-23 28-30 June 3-5 3-7 18-19 July 1-2 Conference 1996 International Symposium, Exhibit & Workshops on Preparative Chromatography, Ion Exchange, and Adsorption/Desorption Processes and Related Techniques Modern Practice Gas Chromatography Laboratory Health and Safety HPLC Beginners Training Course Mass Spectrometry of Peptides and Proteins Seventeenth Annual Introductory HPLC Short Course Advanced HPLC Radioisotope Techniques HPLC Toubleshooting Courses Fourier-Transform Infrared Spectroscopy 1-5 Summer School in Spectroscopic Interpretation 23-25 Problem Solving for Analytical Leaders August 18-21 Capillary Electrophoresis Course Location Washington D.C., USA West Chester, USA Loughborough, UK Macclesfield, UK Manchester, UK West Chester, USA Widener, USA Loughborough, UK Macclesfield, UK Manches ter , UK Manchester, UK York, UK York, UK Contact Janet Cunningham, Ban- Enterprises, P.O.Box 279, Walkersville, MD 21793 USA Tel: + I 301 898 3772. Fax: +1 301 898 5596 E-mail: Janetbarr@aol.com Sally Stafford, Hewlett Packard, Little Falls Site, 2850 Centerville Road, Wilmington, DE 19808- 16 10 Tel: + I 302 633 8444. Joyce Motyka, Centre for Hazard and Risk Management (CHaRM), Loughborough University, Loughborough, Leicestershire, UK LEI 1 3TU Tel: +44 (0)1509 222175. Fax: +44 (0)1509 610361 Nikki Rathbone, HPLC Technology Ltd, Macclesfield, Cheshire, UK SK11 6PJ Tel: 01625 613848. Fax: 01625 616916 Dr. N. H. P. Smith, Chemistry Department, UMIST, P.O. Box 88, Sackville Street, Manchester, UK M60 Tel: +44 (0) I6 1 200 449 1.Fax: +44 (0) 161 236 7677 Bill Champion, DuPont Merck Pharmaceutical Co., PRF Building, Chambers Works, Deepwater, NJ 08023 Tel: +1 609 540 4826. 1 QD Jim Alexander, Rohm and Haas Laboratories, 727 Norristown Road, Spring House, PA 19477 Tel: + I 215 619 5226. Dr. P. Warwick, Department of Chemistry, Loughborough University, Loughborough, Leicestershire, UK LE 1 1 3TU Tel: +44 (0)1509 222585. Nikki Rathbone, HPLC Technology Ltd, Macclesfield, Cheshire, UK SKI 1 6PJ Tel: 01625 613848. Fax: 01625 616916 Dr. N. H. P. Smith, Chemistry Department, UMIST, P.O. Box 88, Sackville Street, Manchester, UK M60 Tel: +44 (0)161 200 4491. Fax: +44 (0)161 236 7677 Dr. N. H. P. Smith, Chemistry Department, UMIST, P.O. Box 88, Sackville Street, Manchester, UK M60 1 QD Tel: +44 (0) 16 1 200 449 1. Fax: +44 (0) 16 1 236 7677 Dr. T. L. Threlfall, Industrial Liaison Executive, Department of Chemistry, University of York, York, UK YO1 5DD Tel: +44 (0) 1904 432576. Fax: +44 (0) 1904 4325 16 E-mail: js20@york.ac.uk 1QD Dr. T. L. Threlfall, Industrial Liaison Executive, Department of Chemistry, University of York, York, UK YO1 5DD Tel: +44 (0) 1904 432576. Fax: +44 (0) 1904 4325 16 E-mail: js20@york.ac.uk Entries in the above listing are included at the discretion of the Editor and are free of charge. If you wish to publicize a forthcoming meeting please send full details to: The Analyst Editorial Office, Thomas Graham House, Science Park, Milton Road, Cambridge, UK CB4 4WF. Tel: +44 (0) 1223 420066. Fax: +44 (0)1223 420247. E-mail:Analyst@RSC.ORG.
ISSN:0003-2654
DOI:10.1039/AN996210052N
出版商:RSC
年代:1996
数据来源: RSC
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Conference report. The Malaysian Chemical Congress ′95, Sarawak, Malaysia: November 13–16, 1995 |
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Analyst,
Volume 121,
Issue 4,
1996,
Page 53-53
J. D. R. Thomas,
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摘要:
Analyst, April 1996, Vol. 121 53N Conference Report The Malaysian Chemical Congress ‘95, Sarawak, Malaysia: November 13-16,1995 The annual Malaysian Chemical Congress (MCC) is aimed at supporting and sustaining the pace of economic growth in Malaysia. At the most recent Congress, MCC ’95, the ‘Symposium on Analytical Chemistry and Instrumentation’ was the main pillar of the event. This was supported by related symposia, in separate streams (Development and Environment, Chemical Education and Quality Assurance). The holding of MCC ’95 in Sarawak was appropriate as this is one of the resource-richest and fastest growing states of Malaysia, with industries based on petrochemicals, oil and gas, timber, pepper, mining and palm oil. The specialist sessions of MCC ’95 paid regard to this.The Congress was crowned by visits to the Agricultural Research Centre, Semengok- which aims at developing and promoting new and improved farming technologies, and to Universiti Malaysia Sarawak (UN1MAS)-a new university with the mission of establishing itself as an exemplary university of regionally acknowledged stature. MCC ’95 had the positive support of government ministers, with it being opened by the Minister of Industrial Development, Sarawak, after opening addresses by the Chairman of the Organizing Committee, Chan Woon Peng; M. Zawawi Ismail (Vice-chancellor, UNIMAS); and M. Mohinder Singh (Presi- dent, Institut Kimia Malaysia). The Malaysian Deputy Minister of Science, Technology and Environment addressed the closing session. Prior to splitting into the specialist symposia streams the Congress sat in a plenary session for lectures by Peter Towse (University of Leeds) on ‘Chemical Education to Meet World Needs: Public Understanding, Industry and Environment’, and J.D. R. Thomas (University of Wales, Cardiff) on ‘Selective Membrane Electrodes for Analysis’ which highlighted trends and directions of research and development and examples of roles in analytical chemistry relating to sustainable industrial development and other areas of human endeavour. The session of the analytical chemistry and instrumentation symposium took up a substantial part of the scientific programme and covered general analytical techniques (includ- ing sensors, flow analysis and radiotracer techniques), separa- tions including chromatography and capillary electrophoresis, environmental aspects, spectroscopy (including FTIR, graphite furnace AAS mass spectrometry and NMR), and hyphenated techniques of LC-MS, GC-MS, ICP-OE and SFE-HPLC.Among the areas discussed were DNA profiling, character- ization of sea anemone toxins, characterization of activated carbon from various woods and of trace elements in woods, determination of oil and grease and other aspects relating to water quality, pesticide residues, pollutants in water and sediments, process control and on-line analysis, food colours, fuel analysers, methylmercury in biological samples and polyaromatic hydrocarbons. The two-day symposium on development and the environ- ment focused on wood products, peat for waste water treatment, water and sediment analysis-with attention to heavy metal, pesticide and hydrocarbon content, and exhaust emissions.These presentations contained much of analytical interest. The quality assurance symposium was very well-structured and opened with Chin Miew Lim describing the acreditation schemes of the Malaysian Accreditation Council arising from the world-wide demand for I S 0 9000 and other quality systems of certification. Other symposia on oils and fats were almost entirely on palm oil topics with just the presentation on the correlation between iodine values and composition having any connection with analysis. However, the non-palm oil paper on the ‘Surface and Pore Structure of Deoiled and Regenerated Spent Clays’, by Liew Kong Yong, was of considerable analytical relevance, for it involved SFC carbon dioxide extractions ahead of dealing with BET surface areas. The polymer chemistry symposium focused on rubbers (natural and synthetic), cellulose and lignins from hardwoods, with the last-named being directed at characterization by GPC.Finally, the organic chemistry symposium was wide ranging in content with three papers on petrochemicals, and others on polyesters and terephthalates, enzyme-catalyzed esterification, organometallic compounds, natural products (including anti- AIDS coumarins), fluorescent DNA binder, and syntheses and extractions. MCC ’95 had over 200 participants. The enthusiasm and friendliness of the participants was phenomenal. It was gratifying to be among so many who had been educated in the United Kingdom, and to witness that they had applied themselves to fostering Malaysian scientific development- much of its founded on analytical chemistry. The Joint Chairmen of MCC ’95, Chan Woon Peng and Laily Din must now be enjoying a well-earned rest in the knowledge that their efforts have been rewarded by a generally successful and well-remembered event. J. D. R. Thomas Wrexham, UK Chan Woon Peng, co-chairman of MCC ’95
ISSN:0003-2654
DOI:10.1039/AN996210053N
出版商:RSC
年代:1996
数据来源: RSC
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Papers in future issues |
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Analyst,
Volume 121,
Issue 4,
1996,
Page 54-54
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摘要:
54N Analyst, April 1996, Vol. I21 Future Issues Will Include Sulfide Interferences in Cyanide Determination Methods- Emil B. Milosavljevic, John C. Wilmot, Ljiljana SolujiC, Scott W. Rader, James L. Hendrix Extraction of Salinomycin From Finished Layers Ratio by Microwave Solvent Extraction Followed by Liquid Chromato- graphy-M. H. Akhtar, Louise G. Croteau Capillary Electrophoretic Separation of Metal Ions in the Presence of Polyethylene Glycols-Richard M. Cassidy, Costas Stathakis High-performance Liquid Chromatography Hyphenated With Array Inductively Coupled Plasma Optical Emission Spectro- metry for the Separation and Simultaneous Detection of Metal and Non-metal Species in Soybean Flour-Lothar Dunemann, Jorg Schoppenthau, Joachim Nolte Anion Mobilization From Aqueous Media by Ion Associate Extraction Into Supercritical Carbon Dioxide With On-line Detection by Flame Atomic Absorption Spectrometry-wil- liam D.Marshall, Jin Wang Bulk Acoustic Wave Sensor for Dissolved Nitrogen Oxide- Shouzhuo Yao, Yuanjin Xu, Changyin Lu, Yan Hu, Lihua Nie Method for the Sampling and Analysis of Hydrogen Sulfide- N. Balasubramanian, K. Shanthi Speciation Analysis of Some Organic Selenium Compounds- Krystyna Pyrzynska Stabilized Needle Electrode System for in vivo Glucose Monitoring Based on Open Flow Microperfusion-Geraldine P. Rigby, Paul W. Crump, Pankaj Vadgama Dithizone Anchored on Poly(viny1pyridine) as a Chelating Resin for the Preconcentration and Separation of Gold from Platinum, Copper and Mercury-Surekha Devi, Rupal Shah Reaction/Diffusion with Michaelis-Menten Kinetics in Electro- active Polymer Films.I. The Steady State Amperometric Response-Michael E. G. Lyons, James C. Greer, Catherine A. Fitzgerald, Philip N. Bartlett Development of Ultraviolet-Polymerizable Enzyme Pastes Bioprocess Applications of Screen Printed L-Lactate Sensors- Ingrid Rohm, Meike Genrich, Wendy Collier, Ursula Bilitewski Development and Evaluation of a Dipstick Immunoassay Format for the Determination of Pesticide Residues On Site- Christine Wittmann, Ursula Bilitewski, Thomas Giersch, Ulrich Kettling, Rolf D. Schmid Chemometric Techniques in Multivariate Statistical Modelling of Process Plant-Margaret Hartnett, G. Lightbody, G. W. Irwin Bispecific Multivalent Antibody Studied by Real-time Inter- action Analysis for the Development of an Antigen-inhibition Enzyme-linked Immunosorbent Assay-Richard O'Kennedy, John G.Quinn, Kurt Zanker, Heiko W. Reinartz Inductively Coupled Plasma Emission Spectrometric Determi- nation of Gallium, Phosphorus and Other 0x0-anion Forming Elements in Geological Materials-". Satanarayana, K. Subramaniam, A. V. Raghunath, G. V. Ramanaiah Determination of Toluenediamines in Urine of Workers Occupationally Exposed to Isocyanates by High-performance Liquid Chromatography-J. P. Buchet, Philippe Carbon- nelle, Sheriffa Boukortt, Dominique Lison Chemical Composition of Pork Rind-Analytical Methods Committee COPIES OF CITED ARTICLES The Royal Society of Chemistry Library can usually supply copies of cited articles. For further details contact: The Library, Royal Society of Chemistry, Burlington House, Piccadilly, London W1V OBN, UK. Tel: +44 (0)171-437 8656. Fax: +44 (0)17 1-287 9798. Telecom Gold 84: BUR210. Electronic Mailbox (Internet) LIBRARY@RSC.ORG. If the material is not available from the Society's Library, the staff will be pleased to advise on its availability from other sources. Please note that copies are not available from the RSC at Thomas Graham House, Cambridge.
ISSN:0003-2654
DOI:10.1039/AN996210054N
出版商:RSC
年代:1996
数据来源: RSC
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10. |
Technical abbreviations and acronyms |
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Analyst,
Volume 121,
Issue 4,
1996,
Page 55-55
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摘要:
Analyst, February 1996, Vol. 121 55N Technical Abbreviations and Acronyms The presence of an abbreviation or acronym in this list should NOT be read as a recommendation for its use. However, those defined here need not be defined in the text of your manuscript. AAS ac rn ADC ANOVA AOAC ASTM bP BSA BSI CEN CPm CMOS c.m.c. CRM CVAAS cw CZE dc DRIFT DELFIA DNA EDTA ELISA emf ETAAS EXAFS EPA FAAS FAB dPm FAO-WHO FIR FT FPLC FPD GC GLC HGAAS HPLC ICP id INAA IR ISFET iv im IGFET ISE LC LED LOD LOQ atomic absorption spectrometry alternating current analogue-to-digital analogue-to-digital converter analysis of variance Association of Official Analytical Chemists American Society for Testing and Materials boiling point bovine serum albumin British Standards Institution European Committee for Standardization counts per minute complementary metal oxide silicon critical micellization concentration certified reference material cold vapour atomic absorption spectrometry continuous wave capillary zone electrophoresis direct current disintegrations per minute diffuse reflectance infrared Fourier transform spectroscopy dissociation enhanced lanthanide fluorescence immunoassay deoxyribonucleic acid ethylenediaminetetraacetic acid enzyme linked immunosorbent assay electromotive force electrothermal atomic absorption spectrometry extended X-ray absorption fine structure spectroscopy Environmental Protection Agency flame atomic absorption spectrometry fast atom bombardment Food and Agriculture Organization, far-infrared Fourier transform fast protein liquid chromatography flame photometric detector gas chromatography gas-liquid chromatography hydride generation atomic absorption high-performance liquid inductively coupled plasma internal diameter instrumental neutron activation infrared ion-selective effect transistor intravenous intramuscular insulated gate field effect transistor ion-selective electrode liquid chromatography light emitting diode limit determination limit of quantification World Health Organization spectroscopy chromatography analysis mP MRL mRNA MS NIR NMR NIST od OES PBS PCB PAH PGE PIXE PPt PPb PPm PTFE PVC PDVB QC QA REE rf RIMS rmS rpm RNA SCE SE SEM SIMS SIMCA S/N SRM STM STP TIMS TLC TOF TGA TMS tris TRIS uv UV/VIS VDU XRD XRF YAG Commonly Used Symbols M Mr r S U melting point maximum residue limit messenger ribonucleic acid mass spectrometry near-infrared nuclear magnetic resonance National Institute of Standards and Technology outer diameter optical emission spectrometry phosphate buffered saline polychlorinated biphenyl polycyclic aromatic hydrocarbon platinum group element particle/proton-induced X-ray parts per trillion (lo1*; pg g-l) parts per billion (109; ng g-l parts per million (106; pg g-l) poly(tetrafluoroethy1ene) poly(viny1 chloride) poly(diviny1 benzene) quality control quality assurance rare earth element radio frequency resonance ionization mass spectrometry root mean square revolutions per minute ribonucleic acid saturated calomel (reference) electrode standard error scanning/surface (reflection) electron microscopy secondary-ion mass spectrometry soft independent modelling of class signal-to-noise ratio Standard Reference Material scanning tunnelling (electron) standard temperature and pressure thermal ionization mass spectrometry thin-layer chromatography time-of-flight thermogravimetric analysis trimethylsilane 2-amino-2-( hydroxymethy1)- propane- 1,3-diol (ligand) 2-amino-2-( hydroxymethy1)- propane- 1,3-diol (reagent) ultraviolet ultraviolet-visible visual display unit X-ray diffraction X-ray fluorescence yttrium aluminium garnet emission analogy microscopy molecular mass relative molecular mass correlation coefficient standard deviation atomic mass
ISSN:0003-2654
DOI:10.1039/AN996210055N
出版商:RSC
年代:1996
数据来源: RSC
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