摘要:

766 Analyst, June, 1983 Com m u n i cat i on Material for publication as a Communication must be on a n urgent matter and be of obvious scientific importance. Rapidity of publication i s enhanced if diagrams are omitted, but tables and formulae can be included. Communications should not be simple claims for priority; this facility for rapid Publication i s intended for brief descriptions of work that has progressed to a stage at which it is likely to be valuable to workers faced with similar problems. A fuljer paper may be offered subsequently, if justified by later work. Cortisol Antibody Electrode Keywords : Potentiometry ; membrane electrodes ; cortisol ; antibodies The development of sensors for antibodies or antigens represents one of the challenging contem- porary directions for potentiometric membrane electrode research.One possible approach involves the use of immobilised ion-carrier immunogen conjugates and such an electrode for a low relative molecular mass model compound has been de~cribed.~g Unfortunately, these electrodes had sensitivities limited to the micrograms per millilitre range. We now describe the successful development of an electrode with selective response for antibodies of cortisol, a steroid hormone of clinical i n t e r e ~ t . ~ It will be seen that the proposed electrode attains a nearly 1000- fold increase in sensitivity over the sensors reported previously2* and has a measurement capability in the nanograms per millilitre range. Experimental Apparatus Potentiometric measurements were made with a Corning, Model 12, pH/mV meter and recorded on a Heath-Schlumberger SR 204 strip-chart recorder.All measurements were made in cells thermostated a t 25 OC with a Haake, Model FS, temperature controller. Electrode membranes were assembled in Orion Research 92 series electrode bodies and operated against Orion 90-01 single-junction reference electrodes. As an extra precaution, freshly prepared potassium chloride - agar salt bridges were employed to avoid the possibility of contamination from the reference electrode and final potential readings were taken with the cell inside a Faraday cage for maximum potentiometric stability. Reagents All chemicals used were of analytical-reagent grade. The cortisol antibody, of ca. 22.4 p g ml-l stock, was obtained from Miles Laboratories (Elkhart, IN, USA) as rabbit anti-cortisol - 21- thyroglobulin antiserum.y-Globulins (Cohn fraction 11, rabbit 99% pure) were purchased from Sigma (St. Louis, MO, USA). Procedures Pveparation of the immunogen - ion carrier conjugate The ion carrier, dibenzo-18-crown-6, was modified by the introduction of two amine groups via nitration and catalytic hydrogenation.6 The resulting diaminodibenzo-18-crown-6 was coupled to the cortisol in the cortisol-21-hemisuccinate form4 through amide bonds using N-hydroxy- s u c ~ i n i m i d e ~ ~ ~ in the presence of dicyclohexylcarbodiimide. The cortisol - ion carrier conjugate was purified by gel filtration with Sephadex LH-20 (bed dimensions 2.2 x 34 cm; 1 ml Inin-' methanol flow-rate) and its relative molecular mass was confirmed using low-resolution mass spectrometry (Kratof MS 50).Construction of the membrane electrode The conjugate was immobilised in 0.2 mm thick PVC film plasticised with dibutyl sebacate3 and cut into 4 mm diameter discs for placement into the Orion 92 series electrode bodies as previously d e ~ c r i b e d . ~ ~ ~ The electrode internals Each disc contains approximately 16 pg of the conjugate.COMMUNICATION 767 were completed with 0.01 M potassium chloride filling solution. The integrity of the electro- chemical arrangement was conveniently checked, as the crown compound used is a potassium ion carrier, by running potassium calibration graphs. Antibody response nzeasurernents On the basis of previous experience,2 all immunomeasurements were carried out in 0.1 M Tris - hydrochloric acid buffer (pH 7.5) with a fixed Kf concentration of 3 x M.The cortisol antiserum was repeatedly dialysed against 3 1 of this buffer solution to ensure that the observed potential changes are the result of the immunoreaction and not due to changes in pH or ion activity levels. Dialysis also serves to remove any possible ionic interferences from the antiserum. Cali- bration graphs for cortisol antibody were then constructed by serial dilution of the stock antibody solution with the background buffer solution in a constant total volume of 2 ml and with constant stirring. For each measurement, the electrode system was allowed to reach a stable background potential in the background buffer, dialysed antibody was then added and the new potential recorded.Between measurements, the antibody electrode was briefly (30-60s) placed in pH 4 citrate or pH 2.8 glycine - hydrochloric acid buffer, washed with de-ionised water and placed back into the background buffer to re-establish the base-line potential. Results and Discussion Fig. 1 shows a typical potentiometric response curve of the membrane electrode to anti-cortisol antibody over the 3.5-168 ng ml-l concentration range. This electrode is thus approximately 1 000 times more sensitive than the hapten-antibody electrode reported previou~ly.~~~ The potential axis, AE, in Fig. 1 indicates the potential difference (in millivolts) observed when the electrode is exposed to various concentrations of dialysed antibody in the background buffer compared with the base-line potential obtained in background buffer alone.The potential readings are reproducible to better than k0.5 mV on replicate runs and steady potential readings are obtained within 3-9 min after addition of antibody. The electrode response is fully reversible; brief exposure of the electrode to pH 4 buffer serves to remove the antibody from the electrode surface and base-line potentials are re-established when the electrode is placed into the background buffer solution. 12 10 8 > E a h 6 4 2 0 I I I 0 40 80 120 160 Cortisol antibodying ml-’ Fig. 1. Potentiometric response of the elec- trode to (A) dialysed cortisol antibodies and (B) Cohn fraction I1 y-globulins in 0.1 M Tris - HCl buffer (pH 7.5) containing 3 x M KCl. Fig. 1 also illustrates the selectivity of the electrode.When the cortisol antibody is replaced by dialysed y-globulins in the same concentration range, there is essentially no observed potential change from the base-line value. As the Cohn fraction I1 y-globulins employed also contain numerous proteins, including other antibodies, it is apparent that the electrode is not only selective for the cortisol antibody over other antibodies, but also displays no non-specific protein effect over the concentration range studied. The electrode showed no response, in separate experiments, to anti-dinitrophenyl antibodies over the same concentration range, further confirming the anti- body selectivity.768 COMMUNICATION Electrode membranes containing the cortisol - carrier conjugate were found to be stable for a t least 3 weeks when stored at 4 OC. We gratefully acknowledge the financial support of National Institutes of Health Grant GM-26308. References 1. 2. 3. 4. 5. 6. 7. Meyerhoff, M. E., and Fraticelli, Y. M., Anal. Chem., 1982, 54, 27R. Solsky, R. L., and Rechnitz, G. A., Science, 1979, 204, 1308. Solsky, R. L., and Rechnitz, G. A., Anal. Chim. Acta, 1981, 123, 135. Gebauer, C. R., and Rechnitz, G. A., Anal. Biochem., 1982, 124, 338. Feigenbaum, W. M., and Michael, R. H., J. Polym. Sci., 1971, 9, 817. Anderson, G. W., Zimmerman, J. E., and Callahan, F. M., J. Am. Chem. Soc., 1964, 86, 1839. Bolton, A. E., and Hunter, M. M., Biochem. J., 1973, 133, 529. Received March 14th, 1983 Department of Chemistry, University of Delaware, Newark, DE 19711, USA M. Y. Keating G. A. Rechnitz

ISSN:0003-2654    

DOI:10.1039/AN9830800766

出版商:RSC    

年代:1983

数据来源: RSC

摘要:

Analyst June 1983 Book Reviews 769 ANALYSIS OF PESTICIDES IN WATER. VOLUME I. SIGNIFICANCE PRINCIPLES TECHNIQUES AND CHEMISTRY OF PESTICIDES. Edited by ALFRED S. Y. CHAU B. K. AFGHAN and JAMES W. ROBINSON. CRC Series in AnaZysis of Environmental Control. Pp. xii + 202. CRC Press. 1982. Price $69.50 (in USA) ; $80 (outside USA). ISBN 0 8493 5210 X. This volume is the first of three the other two of which have yet to be published and has chapters entitled “Environmental Impact and Significance of Pesticides,” “Basic Principles and Practices in the Analysis of Pesticides,’’ “Positive Identification of Pesticide Residues by Chemical Derivatiz-ation Techniques” and “The Chemistry of Cyclodiene Insecticides.” The authors are almost entirely Canadian and the chapters reflect North American experience and practice The three volumes together attempt to present a detailed survey of the subject Volume I1 being entitled “Chlorine- and Phosphorus-containing Pesticides” and having chapters on organochlorine pesticides, organophosphorus pesticides and phenoxyalkyl acid herbicides and Volume 111 being entitled “Nitrogen-containing Pesticides’’ and containing chapters on carbamates substituted urea herbi-cides and triazine herbicides.Volumes I1 and I11 contain the analytical detail and although the anticipated subject matter is not totally comprehensive it covers the main groups of pesticides likely to be encountered in environmental water analysis. It does not cover some of the materials likely to be deliberately added to waters by control Authorities for water mains disinfestation weed control in drainage channels etc.The first chapter of Volume I gives a good general background to pesticides and the environ-mental problems they cause covering types and their chemical properties transport and movement in the biosphere accumulation and degradation. It gives a short introduction to toxicology and monitoring and discusses models of environmental behaviour. It is well referenced for North American experience but with little information from elsewhere. Chapter 2 again gives a good general picture of basic principles and practices in pesticide analysis. However I found myself disagreeing in many places with detailed comment particularly with what I regard as some popular misconceptions. For instance item 2 page 43 states “It has been shown that packed columns with smaller internal diameter are more efficient than those with iarger internal diameter.’’ For practical purposes this is not so and the column efficiency is dependent on internal diameter mesh size of packing column configuration operating conditions and instrument in use.The use of benzene as an extraction solvent would no longer be recommended in Europe and I would have liked to have seen more emphasis on HPLC and capillary gas chromatography. The authors preferences are evident in Chapter 3 which nevertheless gives a very good and detailed account of chemical derivatisation techniques for confirming pesticide identity. The advantages and limitation of this approach are discussed. A short general discussion of confirma-tory techniques begins the chapter.The final chapter details the chemistry of the cyclodiene insecticides with respect to synthesis and chemical reactions. Although very interesting I had some reservations as to the usefulness of its inclusion particularly in the absence of similar information on other pesticide types. Overall a useful first volume to a series that will deal comprehensively with a subject matter covered at present by a number of scattered publications. As such it cannot properly be judged until all the volumes have been published. B. T. CROLL RECOMMENDED METHODS FOR PURIFICATION OF SOLVENTS AND TESTS FOR IMPURITIES. Edited by J. E. COETZEE. Pp. viii + 59. Pergamon. 1982. Price &lo; $20. ISBN 0 08 022370 2. The title of this book is rather misleading.Produced by the Commission on Electroanalytical Chemistry of the International Union of Pure and Applied Chemistry the book is a compilation of reports on ten solvents of interest mainly to workers in the field of electrochemistry. Seven dipolar aprotic solvents (acetonitrile sulpholane propylene carbonate dimethyl sulphoxide dimethyl-formamide hexamethylphosphoramide and pyridine) and three amphiprotic solvents (ethylene diamine N-methylacetaniide and N-methylpropionamide) are considered 770 BOOK REVIEWS Analyst Vol. 108 A chapter is devoted to each solvent and in two useful introductory chapters the Editor tabulates the properties and parameters of the solvents points out the adverse effects of impurities stresses the importance of purification and reviews some common purification methods.The chapters on the individual solvents have been written independently by eight authors or groups of authors some being responsible for more than one chapter and this has resulted inevitably in a lack of uniformity in presentation (particularly of data) and in the depth of study (DMSO warrants 6.5 pages while pyridine is covered in 2.5). In each chapter the solvent properties are discussed details are given of recommended purification procedures and methods for determining impurities are noted and in some instances described in detail. In any future publication the inclusion of 1 1 ,3,3 tetramethylurea N-methylpyrrolidone and even acrylonitrile (because of its availability in a very pure form) would be useful. Although this book is of a specialist nature intended for the use of experimentalists in the field of electrochemisty a t A10 for 59 pages it is still rather expensive.E. J. GREENHOW All chapters conclude with a comprehensive collection of references. The Editor points out that the number of solvents considered has been limited. WILSON AND WILSON’S COMPREHENSIVE ANALYTICAL CHEMISTRY. VOLUME XIV. ION Ex-CHANGERS IN ANALYTICAL CHEMISTRY. THEIR PROPERTIES AND USE IN INORGANIC CHEM-ISTRY. By M. MARHOL. Pp. 585. Elsevier. 1982. Price $127.75; Dfl275. ISBN 0 444 99717 2. This latest volume in a large reference work of analytical chemistry is arranged in three parts. Part 1 opens with an outline of the basic concepts of ion exchange and discusses the characteristics of ion-exchange materials.It continues with the essential theory of ion-exchange equilibria and selectivity as well as some of the more general aspects of chromatography including plate theory and gradient elution. This part is treated with commendable clarity and is appropriately compre-hensive. A detailed exposition of the physical physico-chemical and chemical properties of ion-exchange resins follows in Part 2 with a meticulous treatment of methods to determine these properties. As such detailed characterisation is most relevant when exploring new materials it seems quite extra-ordinary that the synthesis or production of ion-exchange materials does not gain even a passing reference ; surely a major omission. Part 2 then progresses through an unbelievably weak chapter on instrumentation almost a decade out of date and failing to recognise the rapid progress of HPLC and its relevance to ion-exchange methods.This is followed by a truly voluminous catalogue of ion-exchange applications the larger part of which is devoted to the separation of inorganic ions, which are dealt with by Groups. There is a short discussion of chelating resins and their practical uses as well as an abrupt mention of inorganic ion exchangers. The final part of the book provides an assorted collection of information about commercially available ion-exchange materials much of which is fairly easily obtained from the literature of the respective manufacturers. A t first glance this book seems to be a very desirable possession containing undoubtedly a mine of information for the ion-exchange chromatographer whether in the inorganic or the organic field.Unfortunately a closer examination reveals glaring deficiencies. The lack of any information on synthesis of ion exchangers and the weak instrumentation section have already been noted but the volume has clearly been much too long in the gestation. Most of the references are historical rather than contemporary and the impression is gained that the book was largely completed by 1975 and has been marginally modernised by the injection of a sprinkling of references up to 1977-78. A t the present rate of progress in chromatographic science this will not do. The major defects of this book its ludicrous price and tardy production call into question a whole area of publishing philosophy.Should a comprehensive book on ion exchange be a cheap workbook to be found on the shelves of many practising scientists with frequent new editions that modern production methods combined with high volume sales would make feasible or should it be an expensive museum piece which even large libraries will debate before they buy ? This one may end up with the author and his friends. ALAN J. THOMA June 1983 BOOK REVIEWS 771 CHEMICAL DERIVATIZATION IN ANALYTICAL CHEMISTRY. VOLUME 2 SEPARATION AND CONTINUOUS Modern Analytical FLOW TECHNIQUES. Chemistry. Pp. xii + 298. Plenum. 1982. Price $39.50. ISBN 0 306 40966 6. Edited by R. W. FREI and J. F. LAWRENCE. Volume 1 in this series dealt with aspects of chemical derivatisation in chromatography. By an adept choice of title this second volume covers both separation and continuous-flow techniques and thereby includes six chapters on a variety of topics including flow injection analysis and immobilised enzymes.In general the book is well written and extremely easy to read with each chapter having a strong practical bias and a comprehensive list of references. There are however a number of irritating typographical errors throughout the text. The first chapter is a timely introduction to flow injection analysis a technique that is currently finding application in a growing number of fields including clinical and environmental analysis. Useful practical tips are included for those unfamiliar with the technique together with brief des-criptions of various ancillary methods such as stopped-flow and solvent extraction.The second chapter presents an overview of ion-pairing reactions in analytical chemistry with emphasis on their application in batch continuous-flow and chromatographic systems. There are two chapters devoted to specific applications namely the resolution of optical isomers by gas and liquid chromatography and the $ros and cons of derivatisation in the chromatographic determination of food additives. The former shows how increased knowledge of the stereochem-istry and co-ordination of enantiomeric compounds can assist in the design of selective chromato-graphic sorbents and includes a number of practical examples to illustrate the point. The latter is a comprehensive treatment of the derivatisation methods available for the analysis of food additives using both gas chromatography and liquid chromatography and again includes numerous practical examples.This volume also contains a chapter on the use of immobilised enzymes as pre-column and post-column modification reagents in liquid chromatography and a chapter dealing with pre-chromato-graphic derivatisation in liquid chromatography. The former is a useful introduction to anyone interested in using immobilised enzymes for on-line derivatisation and includes discussion of bio-luminescence and chemiluminescence coupled systems. The latter is a detailed listing of various derivatisation reactions used in liquid chromatography with particular emphasis on fluorescence and ultraviolet - visible detection systems. Overall this is an interesting and well referenced volume for any analytical chemist requiring an introduction to the topics discussed above.P. J. WORSFOLD ADVANCES IN INFRARED AND RAMAN SPECTROSCOPY. VOLUME 9. Edited by R. J. H. CLARK and R. E. HESTER. Pp. xvi + 384. Wiley-Heydexi. 1982. Price k48. ISBN 0 85501 189 0. One cannot fail to admire the persistence and dedication of Robin Clark and Ron Hester in pro-ducing yet another volume in their series “Advances in Infrared and Raman Spectroscopy” con-taining authoritative and well written articles on vibrational spectroscopy in areas of current research interest. It may be of significance that four of the articles are on aspects of Raman spec-troscopy as against one on infrared. This would certainly reflect the present research situation that any Raman spectroscopy meeting seems to produce such a crop of new Raman curiosities that the practitioners have run out of convenient acronyms and now employ nomenclature such as TR3 and TRaS as evidently even the initials now take too long to enunciate.Nevertheless time-resolved Raman spectroscopy (TR2S) the subject of the first chapter is a technique with much to commend it. The object of the studies is clearly stated; this is followed by simple descriptions of the many experimental methods that are in use for TR2S. The remainder of the chapter is devoted to a survey of applications especially to transient species both molecules and radicals. The technique seems to show particular promise in biological systems. The third chapter on high resolution stimulated Raman spectroscopy begins with some much needed remarks on the relationship of this technique to the well publicised CARS.However what was previously “stimulated Raman gain spectroscopy” and “inverse Raman spectroscopy” are apparently now considered to be part of “stimulated Raman spectroscopy. ” The initial lette 772 BOOK REVIEWS ANalyst Vol. 108 abbreviation SRS is a bit unfortunate as it could equally well stand for the more usual “spontaneous Raman Spectroscopy” although Norman Sheppard has come to the rescue by christening the latter POORS or “poor old ordinary Raman spectroscopy.” The chapter contains a good discussion of the theory with some useful diagrams which put the idea over to those such as myself who soon get lost in the mathematics. The technique has the twin advantages of high spectrum intensity with a remarkably high resolving power and can be applied with particular advantage to low pressure gases.After a review of experimental methods, the chapter concludes with applications and suggestions on the likely development of the technique. The fourth chapter is devoted to the controversial subject of Raman spectroelectrochemistry. The purpose of this study to unravel by direct observation the highly complex reactions taking place on electrode surfaces is sufficiently important to persuade a large number of people to explore what has proved a most frustrating technique. The earliest observations in the mid 1970s, reported remarkable results from pyridine adsorbed (or perhaps chemi-sorbed) on silver; it is interesting to see that this experiment still figures prominently and its explanation seems to be in as much doubt as ever.Indeed much of the chapter is devoted to the competing explanations of the phenomenon and while this remains the case application of the technique will be limited to some special areas. This chapter concludes with a useful glossary of electrochemical terms and the terminology of other surface spectroscopies. Chapter 5 is concerned with electronic Raman spectroscopy a relatively neglected area. If the object of the present chapter is to spread the gospel it is perhaps unfortunate that the authors include in the theory section two pages filled almost entirely with formidable mathematics. The statement on p. 286 that a simplification of equation (10) is possible is of little comfort; the “simpli-fied” version equation (14) on p.287 is equally obscure. The applications section makes easier reading and useful and concise comments on the technique are offered as a tail piece. I have left till last Chapter 2 the mid-infrared spectroscopy of powdered samples as this is the only contribution not concerned with Raman spectroscopy and it is also directed at a more popular audience. The various techniques for dealing directly with powders are discussed especially diffuse reflectance and photoacoustic methods. Unfortunately the state of the theory of these techniques leaves a great deal to be desired and the much quoted Kubelka-Munk equation appears to be more honoured in the breach than the observance. The chapter contains some very clear diagrams showing experimental arrangements and spectra that illustrate some of the experi-mental curiosities of these methods.The second derivative spectrum appearing on p. 115 is perhaps not too well chosen an example; the peaks are too regular in spacing and shape to be convincing. An adverse criticism of this chapter would be its insistence on the necessity for an FT instrument for recording diffuse reflectance or emission spectra. The latter in particular do not gain signifi-cantly over more conventional dispersive methods. Nevertheless this is a good summary of the present state of the subject. For the infrared spectro-scopist the one chapter good though it is is expensive at fj48. The production standard is good, the print is clear and the reviewer found no significant errors.H. A. WILLIS The book is good and important reading for the Raman spectroscopist. GAS CHROMATOGRAPHY OF ORGANOMETALLIC COMPOUNDS. Plenum. 1982. Price $75. ISBN 0 306 40987 9. By T. R. CROMPTON. Pp. X + 589. This substantial monograph is by far the most complete compendium available of experimental data on gas-chromatographic methods of analysis and characterisation for organometallic com-pounds. The author has used the approach of a group by group-elemental survey of his subject. The information is assembled in the style of a detailed review of material with the frequent inclusion of a substantial amount of experimental information. While the information content is very high there is little attempt at a critical appraisal of experimental gas-chromatographic advances.Often, information and procedures from the 1960s are presented side by side with more recent studies and naturally much early work is outdated. However its inclusion is often valuable when the chemical systems have not been re-examined recently; here the early work may provide a strong basis for renewed study. The style is very much a compendium of laboratory methods and results while this may be inappropriate for some readers it does provide much practical information to aid the experimental scientist J w e 1983 BOOK REVIEWS 773 The author has in general been careful to confine his coverage to defined organometallic com-pounds i.e. those with sigma or pi carbon - metal bonds; however there are a few departures from this rigour ; for example the detailed inclusion of very early decomposition studies of zinc dialkyl-dithiophosphates.Such are really inappropriate but as they were included should have been related to recent direct gas-chromatographic studies of these chelates. In his introduction the author notes that there are more than 1000 papers in the organometallic gas-chromatographic literature. He has included in this book discussion of 528 of these usually with sufficient coverage to determine their importance to the reader. Frequently substantial portions of key papers are quoted verbatim or with little condensation. This necessitates lengthier coverage than may often be needed but it does provide a helpful resource for those who may not have direct access to the original literature.More than half of the book is dedicated to the Group 4B elements primarily silicon a clear reflection of the preponderance of work in this area. Organolead tin arsenic mercury and boron compounds are extensively treated and there is coverage of compounds of more than 15 other metals both transition and main group The only noteworthy omission is that of organophosphorus compounds ; this is reasonable from the definition of organometallics but would have been of practical utility. The one major omission is the absence of introductory and background chapter(s) discussing the over-all field and its analytical and gas-chromatographic problems. Similarly introductory material or commentary for each chapter would be helpful. Despite some criticisms and its high cost the amount of information gathered and organised by the author make this book a desirable if not essential acquisition for all involved in this area of analytical chemistry.PETER C. UDEN The seven chapters are organised on a Periodic Table basis. GUIDE-LINES TO PLANNING OF ATOMIC SPECTROMETRIC ANALYSIS. By B. MAGYAR. Studies in Analytical Chemistry Volume 4 . Pp. x + 273. Elsevier. 1982. Price $76.75; Dfll65. ISBN 0 444 99699 0 (Volume 4); 0 444 4194 1 (Series). In his preface the author writes that he has chosen this title to describe the book as well as possible in a few words and goes on to explain that although analytical aspects of AAS and AES dominate the text its main object is to discuss the physico-chemical basis of these techniques.The reader is therefore not to expect the usual short discussion of principles followed by a detailed description of analytical procedures that is encountered in most books on analytical atomic spectro-metry. The author explains that he encountered the need for a text such as this in discussions with chemistry students few of whom had a detailed understanding of the photoelectric effect the Compton effect Bragg’s equation and the grating equation. This book is therefore intended to fill a gap between the theory and the practice of atomic spectrometry. It is the reviewer’s considered opinion that the author has gone a long way towards his object in this interesting and attractively set out little book but that the title is somewhat misleading in that the word planning might more accurately be replaced by understanding.The text is set out in six chapters. The first “Capacity and Comparison of the Most Important Physical Methods of Elemental Analysis’’ is an interesting though necessarily sketchy treatment. It should be mildly taken to task for mistakenly describing chemical methods p. 4 as absolute, whereas they depend on substances that are deemed to be primary standards though arguably they are less empirical than instrumental methods generally. Chemical methods are of course just as sensitive to rendering information on speciation which for most analytical purposes is an enormous boon. The historical section is excellent in recognising that much was carried out on spectroscopy before Bunsen and Kirchoff “put it all together.” I was however a little disappointed to see no mention of Brewster’s 1834 pre-Bunsen and Kirchoff explanation of the origin of the Wollaston, so-called Fraunhofer lines and I think that Thomas Melvill of Glasgow’s 1752 prismatic study of the yellow emission of sodium-loaded flames pre-dates that of Margraft though admittedly the latter did use his observation of flame colour to differentiate sodium and potassium.I t is pleasing to find Greenfield’s contribution to ICP work given due recognition p. 23 though Professor Fassel’s initials are incorrectly given and surprisingly no mention is made of the very early AAS paper by Alkemade and Milatz which is complementary to Walsh’s work. I also find it surprising as this book is specifically written for students that no literature references are made to the original papers involved only to reviews that are necessarily interpretative useful though they are 774 BOOK REVIEWS Analyst Vol.108 Chapter 2 deals with the dualism of electromagnetic radiation its generation and absorption and Chapter 3 is concerned with the factors that influence the profile of atomic-emission and -absorp-tion lines. The treatment is fairly mathematical in approach and assumes perhaps quite legitim-ately for student readership a fair knowledge of spectroscopy and its concepts. Chapter 4 treats “Atomic and Electronic Structure” in general and introduces a well explained treatment of the De Broglie hypothesis spectral series the Zeeman effect Paschen-Back effect coupling phenomena, Hund’s rule selection rules and so on.Flames electrothermal atomisers inductively coupled plasmas nebulisation techniques form the basis of discussion in Chapter 5 and there is a comparison of the relative sensitivities of the ICP emission and AAS techniques. The final chapter is orient-ated towards design factors in presently available commercial spectrometers optical systems for ICP-AES and background correction factors. The text ends with seven useful Appendices on physical constants symbols and abbreviations spectral transitions and line sensitivies. The reviewer’s impression is that this is an excellent guide book for students of analytical spectro-scopy of all ages who wish to gain a further understanding of the fundamental aspects of the subject. It is well illustrated with useful diagrams and tables of data and although the English obtrudes itself on one’s awareness in several places the text is also generally clear and unequivocal in meaning.T. S. WEST MODERN LIQUID CHROMATOGRAPHY SECOND EDITION. AUDIO COURSE. By LLOYD R. SNYDER and J . J. KIRKLAND. Twelve Audiotape Cassettes (8.1 hours) + 416 pp. Manual. American Chemical Society. 1981. Price $445; additional manuals $30. Despite its widespread acceptance in many important areas over the last few years instrumental liquid chromatography is still an unfamiliar field for many chemists. The poor coverage of analyti-cal chemistry in many undergraduate courses means that even recently trained graduate chemists will often have only a superficial background knowledge. As a consequence there is an increasing need for further training in this technique for chemists in industry and government.This can take the form of individual reading which is difficult without guidance] or attendance at short course giving a concentrated introduction over a short time but inevitably limited time for assimilation. An alternative intermediate approach is an audio course which provides the encour-agement of a personalised approach with comment and discussion but can be paced to match the comprehension of the user. The present course by Snyder and Kirkland consists of 26 topics on 12 cassettes with a total running time of 8.1 hours supported by a manual of figures and tables. The manual is not a refer-ence text but the authors’ own recent text-book is frequently given as a reference and would pro-vide useful supplementary reading.The course starts with a general introduction to liquid chromatography retention and band spreading and then continues with an extended discussion of resolution and the control of separation. The basic equipment of chromatography pumps columns and detectors are described before a section on the effect of solvent strength. Most of the second half of the course is devoted to columns packing materials and their applica-tions. Due emphasis is given to bonded phases with a limited coverage of liquid - liquid and liquid -solid systems. Size-exclusion separations are well covered and the final sections deal with ion-exchange columns and ion-pairing and the selection of a liquid-chromatographic method. Reference is also made to a number of special topics to be covered in greater detail in a future course including sample pre-treatment preparative and gradient separations.Throughout the coverage is practical rather than theoretical and pace of the presentation is deliberate and fairly detailed a feature that should be welcomed by newcomers to the field. Each topic could be studied independently as a special topic or for revision. The user should not be deterred by the almost daunting concept of 8.1 hours listening] as the material is well presented and easy to listen to although a shorter less comprehension course might well have been almost as valuable for newcomers to the subject. The major reservation with the course must be its ability to remain up to date in such a rapidly advancing field with major develop-ments in liquid chromatography - mass spectrometry microbore columns and non-silica based phases occurring since its production.Inevitably it lacks one significant area that of any practical hands-on experience so important in a practical subject but despite this omission it should prove a useful although expensive introduction to modern instrumental liquid chromatography. R. M. SMITH Professional Development Courses (CataEog No. 62) June 1983 BOOK REVIEWS 775 INTRODUCTION TO CHEMICAL ANALYSIS. By ROBERT D. BRAUN. Pp. xvi + 462. McGraw-Hill. 1982. Price fj18.25. ISBN 0 07 007280 9. The author works in the Chemistry Department a t the University of Southwestern Louisiana and his book “is designed to be useful in a terminal course for non-chemistry majors as well as in the first course (in analytical chemistry) for chemistry majors.” The book is thus pitched at a level suitable for UK students a t post ‘A’-level standard though in common with most American texts does not match the UK undergraduate analytical chemistry course such a s it is particularly well.The first third of the book is devoted to classical analysis and is presented in a dull fashion. The role of analytical chemistry is dealt with in a cursory manner and students would be unlikely to have their imaginations fired by the brief introductory chapter. The physical basis of analytical reaction chemistry is handled at a very elementary level. The roles of free energy enthalpy and entropychanges are not mentioned. There are lots of worked examples of calculations but the emphasis appears to be on rote learning rather than achieving an understanding of what’s going on.The author departs from the normal “Chapter 3 syndrome” and leaves a discussion of errors till Chapter 6. This is prefaced by a chapter that deals with calibration (oddly enough this word is never used in the chapter) ; although a welcome innovation in texts of this sort it is far too brief (only 11 pages). The topics chosen for the instrumental section were done so on the basis of those “most likely to be encountered . . . after graduation,” although spectroscopies relating to structure determination (apart from ultraviolet -visible) have been deliberately omitted. Clinical laboratories would thus seem to be outside the author’s projected sphere of employment of his students as immunological methods etc.are omitted. Radiochemical methods are not mentioned either. Molecular spectroscopy gets 39 pages and atomic spectroscopy gets 23 of doubtful quality (it’s about time the total consumption burner was omitted from this chapter in student texts) but potentiometry and non-potentiometric electro-analysis get 40 and 46 pages respectively chromatographic theory and liquid chromatography occupy 48 pages and gas chromatography 28. The final 11-page chapter concerns analytical automation. There are also the usual “tables of useful constants.” Overall the aproach to instrumental analysis is “black box” ; only very sketchy ideas are given as to how the instruments actually work and what is included is rather unbalanced (more space is devoted to explaining how a PMT works than how a monochromator works).Most instruments are shown only as schematic diagrams which look rather like computer program flow charts. Nearly every chapter has a list of suggested supplementary reading and some problems (for which answers are given). There are very few printing errors and not many explanations that one would take issue with. On the whole the book has nothing to recommend it over the existing multitude of American texts aimed a t this sector of the US student population. J F. TYSON This is done well and a useful section on sampling is included. The remaining two-thirds of the book are devoted to instrumental analysis. The index is comprehensive. APPLICATIONS OF CHEMICAL ANALYSIS.By ROBERT D. BRAUN and FRED H. WALTERS. Pp. x + 370. McGraw-Hill. 1982. Price fj9.95. ISBN 0 07 007282 5. This book designed as a companion volume to Robert Braun’s “Introduction to Chemical Analysis,” is a student laboratory manual. Production costs have been minimised; the book has the appearance of being duplicated on recycled paper and has paper covers. Unfortunately there is no indication of the authors’ philosophy concerning the role of practical work in the teaching of analytical chemistry. A glance down the list of contents however suggests that their ideas in this area have not yet fully crystallised. The manual is virtually self-contained in its appproach. There is an introductory section concerning safety handling of volumetric glassware laboratory note-books mass measurements and treatment of results (this is too brief and does not include enough on errors and their treatment).Each experiment is presented in a standardised format ; length of time required introduction references pre-laboratory assignment (usually a calculation with dummy data) apparatus and chemicals needed an extremely detailed procedure and instructions on how to perform the required calculations. The 59 experiments cover topics roughly in parallel with the companion text-book and thus th 776 BOOK REVIEWS Analyst Vol. 108 same unbalanced picture appears. There is one experiment concerning errors (in pipettes) 3 gravi-metric and 15 titrimetric experiments. There are 7 experiments on solution spectrophotometry, 4 on fluorimetry and 1 on turbidimetry; 2 on atomic absorption and 1 on atomic emission.There are 5 potentiometric experiments (only 1 involves use of a pH electrode) and 9 non-potentiometric electrochemistry experiments and finally 1 1 experiments on chromatography (including 1 on electrophoresis). A t no point do the students ever have to think about what they are doing the approach is pure “cook-book.” The experiments are therefore presumably designed (if that’s not too strong a word) to teach the students manipulative skills as they certainly won’t learn any chemistry from them. The same criticism applies to the instrumental experiments as to the classical ones in that the approach is pure “black-box,” none of the experiments involves investigating the effects of changing operating parameters or testing the instrument performance.There are no experiments on sampling nor is any encouragement given to think critically about the errors that might be involved, a particularly serious omission for the instrumental methods. There are no experiments involving automation or any indication of the impact of the microcomputer in instrumental analysis. As with the companion text there are few errors the index is good and solutions are provided for the pre-laboratory exercises. Assuming the experiments to be tried and tested in the authors’ teaching laboratories this com-pilation makes a useful basis for the design of a laboratory course in analytical chemistry. J. F. TYSON TECHNIQUES IN LIQUID CHROMATOGRAPHY. Edited by C. F. SIMPSON. Pp. x + 464.Wiley-Heyden. 1982. Price L27. ISBN 0 471 26220 X. This book has its origins in the Residential School in High Performance Liquid Chromatography held at the University of Sussex in 1980 under the auspices of the Royal Society of Chemistry. I t represents albeit in an expanded form the lectures presented on this Course. For a book that has 14 chapters and 12 contributors it is remarkably readable and the Editor is to be congratu-lated on achieving a cohesive whole. The topics covered are by and large those one would expect to find in a book of this type, although additional topics such as microbore columns preparative chromatography and gel permeation chromatography are well covered. The scope of the work may be judged from the titles of the chapters and their authors many of whom are well known to those actively involved in liquid chromatography An Introduction to Liquid Chromatography and some Fundamental Relationships C. F. Simpson; Kinetic Factors Influencing Column Design and Operation J. H. Knox ; Conventional Column Systems; Instrumentation and Current Practice G. B. Cox; Micro-bore Columns in Liquid Chromatography R. P. W. Scott; Preparative Chromatography C. E. Reese; Detectors for HPLC B. B. Wheals; Selectivity in Chromatography C. Horvath; Ion-exchange and Ion-pair Chromatography J. C . Kraak; Gel Permeation Chromatography J. V. Dawkins; Design of Media for High Performance Chromatography of Large Biomolecules E. A. Hill; and Practical Experiments in HPLC C. F. Simpson. The work is well and clearly presented and is substantially free from obvious typographical errors. There is certainly a place for this book on a practising chromatographer’s bookshelf and represents value for money. C. BURGESS The book is completed with comprehensive compound and subject indexes

ISSN:0003-2654    

DOI:10.1039/AN9830800769

出版商:RSC    

年代:1983

数据来源: RSC