Analyst, September, 19741 613 Book Reviews QUANTITATIVE THIN LAYER CHROMATOGRAPHY. Edited by JOSEPH C. ToucHsTom. Pp. xvi + 330. New York, London, Sydney and Toronto : Wiley-Interscience. 1973. Price k7-50. In a book with such a general title, one might expect to find up-to-date information on all aspects of quantitative thin-layer chromatography, including fundamental aspects, some critical assessments of the various techniques that have been reported and are in present use as well as critical reviews of the applications of the techniques in biochemical, inorganic, pharmaceutical and organic problems. The book deals mainly with biochemical aspects, the chapters dealing with the fundamental aspects of the techniques are not sufficiently critical to be of much practical use.The sole paper dealing with the use of quan- titative thin-layer chromatography in air pollution does not contain references to work after 1968! As the contributions are from several workers, the editing in such a book must be fairly ruth- less in order to avoid much overlap and the impression is that we are presented with semi-review articles intermingled with some research papers that would probably not be accepted, in their present form, by most international journals dealing with chromatography. The editing has not been ruthless, the standard of the chapters varies considerably and in some it is low even with respect to grammar. Although there is a fair amount of good work in the book, for those workers already in the field it offers little, and for those who wish to start in the field it is too superficial in its treatment of the fundamental aspects to be of much use.The contents of the book do not justify the title. L. S . BARK THERMAL ANALYSIS. By T. DANIELS. Pp. 272. London: Kogan Page Ltd. 1973. Price k6. Dr. Daniels is to be Congratulated on producing a volume that can be recommended without reservation to everyone interested in thermal analysis, be he novice or expert. It is indeed refreshing these days to be able to make such a statement, especially on a work relating to a subject that has recently generated such a volume of literature as has thermal analysis. This book very neatly closes a gap in the literature, as there was previously no single treatise covering in such an easily digested manner all the important thermoanalytical techniques, their instrumentation and their main applications. As a measure of coverage, thermogravimetry, differential thermal analysis, differential scanning calorimetry, dilatometry, mechanical, electric and magnetic methods in thermal analysis, evolved gas detection, evolved gas analysis and corn- binations of various techniques are all considered.Major emphasis is laid on instrumentation and in such a way that aspects relevant to the production of reliable results are well brought out. Criticism might perhaps be levelled a t the small amount of space devoted to applications, yet these are well chosen to illustrate the type of information that each method yields and are probably adequate to satisfy the author’s criterion “. . .that each reader can critically assess the approach most suited to his particular problem.” The novice to thermal analysis will therefore find this book a mine of information and the expert in one technique, while he might perhaps cavil at the coverage given to his particular hobby-horse and observe omissions, will undoubtedly garner facts about other techniques that were previously unknown to him. Having read this book, one is left not only with an awareness of the wide variety of techniques that come under the heading of “thermal analysis” but also with some impression of the enormous range of materials and problems thev can be applied to with success. The book is well written and easy to read, although the pedant might object to the occasional split infinitive, and the author is to be congratulated on giving due attention to standards for nomenclature and methods of reporting results enunciated by the International Confederation for Thermal Analysis.The references are well selected for illustrative purposes but do not always represent the first recorded observation, e.g., the system described in the first few lines of p. 21 was used much earlier by both Czech and American workers. Commendably, there are few misprints and those that do occur, such as that in equation 3.5 on p. 62, should cause no difficulty. Although the expert might perhaps question some observations, the only mis-statement noted was on p. 114 : IITA peak areas in (degI2 are particularly sensitive to heating-rate variation and the correct dimensions here should be deg s.All the figures are reproduced in a particularly clear and lucid form and full indexes are provided. Overall, this book is excellent value for money and should be on the bookshelves not only of those already interested in the subject but also of those who wish to know “what thermal analysis is all about.” R. C. MACKENZIE614 BOOK REVIEWS [Analyst, Vol. 99 CHEMICAL ANALYSIS OF ORGANOMETALLIC COMPOUNDS. ELEMENTS OF GROUPS 1-111. By T. R. CROMPTON. A n International Series of Monographs, No. 4. Pp. x + 258. London and New York: Academic Press. 1073. Price i 5 . 8 0 ; $16.25. From the generic heading of this series, The Analysis of Organic Materials, and the titles of the monographs that have already appeared, or are likely to appear in the series, it is evident that an extensive coverage is contemplated.For good measure, “Chemical Analysis of Organometallic Compounds” adds to this coverage by its incursion into the field of inorganic analysis. The author is not new to the analysis of organometallic compounds, and this publication can be regarded as a logical sequence to his earlier book, “Analysis of Organoaluminium and Organozinc Compounds” (Pergamon Press Ltd.) . The latter, together with three proposed volumes in this series on “Chemical Analysis of Organometallic Compounds,” are intended to cover the most important compounds. This volume (Volume 1) deals with elements in the conventional Groups I to 111, with major chapters devoted to lithium, magnesium, mercury and boron and short chapters on sodium, potassium, copper, beryllium, calcium and thallium, for example.Each (element) chapter contains a review of the most important aspects of the particular organometallic compound. This is followed by critical comments on the relative importance and weaknesses of published methods for determining the element and its functional groups. Here is a publication that is destined to be well received by the busy analyst (and others) who requires reliable information quickly without undue recourse to the original literature. There is one small complaint: like most analysts, I prefer the word “determination” to the presumed equal alternative used extensively and almost invariably throughout the book. Volume 1. W. T. ELWELL NEW DEVELOPMENTS IN GAS CHROMATOGRAPHY. Edited by HOWARD PURNELL.Advances in New York, London, This book contains a collection of seven reviews on different aspects of gas chromatography. Each review is written by an acknowledged expert and all are backed by a comprehensive list of references. The first chapter, on the “Application of Gas Chromatography to Forensic Science,” is an interesting illustration of the use of the technique for practical purposes. Methods for the deter- mination of alcohol in blood and urine and the detection and identification of drugs are well described. The effort required to place a gas-chromatographic system under computer control is considerable and David Leathard has produced a useful guide to what is involved; this is mainly directed to those whose knowledge of computers is minimal.The second half of this chapter is devoted to the problems of curve fitting and the resolution of overlapping peaks. While this is an important aspect the use of a computer should not be seen to be an excuse for the promotion of inferior chromatographic separation. Phase changes in gas-chromatographic stationary phases have usually been regarded as a nuisance factor. However, discontinuous retention time behaviour over temperature ranges showing such phase changes can be recognised as falling into one of six categories, characteristic of the different log Vg versus 1/T relationships. P. F. McCrea shows how the phenomenon can be put to many different applications, which include the choice of specialised stationary phases for enhanced separation factors and the characterisation of solid - solid, solid - liquid, liquid - liquid, etc.transitions. A more specialised application of this phenomenon, for the study of the physical properties of polymers, e.g., crystallinity and surface properties, is dealt with in a separate chapter by J . E. Guillet. The use of gas chromatography for the production of pure compounds on an industrial production scale is well described in technical and economic detail by John Condor and a favourable comparison is made with contemporary distillation techniques. Studies in complex formation between the gas-phase component and the stationary phase are reviewed by C. A. Wellington and the theme is continued in another review by S. H. Langer and J. E. Patton, where chemical interaction between the gas-phase components and the stationary phase enables this technique to be used as a chemical reactor to study reaction kinetics.As well as citing actual applications, e.g., isomerisation, a fairly comprehensive mathematical treatment is given of the theory behind the application. Undoubtedly this book will be of interest to students of gas chromatography who wish to keep abreast of recent developments, and to research workers seeking basic information and further references in these particular aspects of the technique. Analytical Chemistvy and Instrumentation, Volume 11. Sydney and Toronto: John Wiley & Sons. 1973. Price L l O . Pp. viii + 408. W. R. MCLEANSeptember, 19741 BOOK REVIEWS 615 GUIDE TO MODERN METHODS OF INSTRUMENTAL ANALYSIS. Pp.xiv + 495. New York, London, Sydney and Toronto: Wiley-Interscience. 1972. Price k7.75. The first impression made by this book is of the very wide yet detailed knowledge required by the modern analytical chemist. The range of techniques of which he has to be knowledgeable is covered (with some glaring exceptions) in the text a t a level sufficient to give a reasonable apprecia- tion of their theory and practice, and to help the reader to make a critical selection of the best approach to a particular problem. The twelve chapters deal in turn with Gas Chromatography (J. F. Johnson), High Resolution Liquid Chromatography (T. H. Gouw and R. E. Jentoft), Thin Layer and Paper Chromatography (D. J. Shapiro and V. W. Rodwell), Gel Permeation Chromatography (M. J. R. Cantow and J .F. Johnson), Visible and Ultraviolet Spectroscopy (C. R. Hare), Infrared and Raman Spectroscopy (3. B. Colthup), NMR Spectroscopy (D. L. Rabenstein), ESR (C. P. Poole, Jr.), Gas Chromato- graphy - Mass Spectrometry (R. A. Flath), Mass Spectrometry (D. H. Smith), Electroanalytical Methods (D. D. Gilbert) and Differential Thermal and Thermogravimetric Analysis (E. M. Barrall, The book will be most useful for analytical chemists dealing with organic compounds. It contains relatively little inorganic material, and the absence of accounts of flame spectroscopy and of X-ray fluorescence in this respect is regrettable. Also, the treatment of all electrochemical techniques in 40 pages, although comprehensive, is necessarily lacking in detail. The description of applications of the techniques is deliberately left brief, with references made to other sources of information.These criticisms apart, this book provides a very acceptable treatment of modern instrumental analytical techniques. It is well written and presented, with few typographical errors, and achieves a standard higher than that of many of its predecessors. Edited by T. €3. Gouw. 111). A. TOWNSHENU METHODS OF BIOCHEMICAL ANALYSIS. Volume 21. Edited by DAVID GLICK. Pp. x + 572. New York, London, Sydney and Toronto: John Wiley & Sons. D. Zakim and D. A. Vessey of San Francisco discuss techniques for the characterisation of UUP-glucuronyltransferase and other tightly bound microsomal enzymes. They describe the preparation and sub-fractionation of microsomes and review the choice of aglycones for assaying the transferase enzyme.An absorption peak a t 400 nm for p-nitrophenol is lost on formation of the glucuronide while, as an alternative, o-aminophenol-glucuronic acid can be diazotised selectively in the presence of unreacted o-aminophenol (by careful control of pH) and the diazotised glucuronide can then be complexed with N- (-naphthyl) ethylenediamine dihydrochloride (Amax. 555 nm ; c, 2.9 x lo4 cm2 mol-l). Glucose-6-phosphatase is multifunctional and differential assay pro- cedures are given. The preparation and purification of phospholipases is described together with the effects of these enzymes on UDP-glucuronyltransferase and glucose-6-phosphatase. 0. E. Olson, I. S. Palmer and E. J. Whitehead of Brookings, South Dakota, deal with the determination of selenium in biological materials.The element occurs naturally a t widely different concentrations and methods are needed for determining less than 1 p.p.m. and up to a few per cent. The organic moiety can be destroyed and the element oxidised to Se4+ or Se6+ and then determined. Neutron-activation analysis has become popular as a non-destructive method. The details of procedures for destructive analysis are described and different methods of determining selenium are assessed critically. Selenious acid reacts with o-diamines ; thus 3,3’-diaminobenzidine (DAB) forms yellow monopiazselenol (Amax. 420 nm), which can be extracted with toluene. DAN (2,3- diaminonaphthalene) gives a complex that can be extracted with cyclohexane and is very strongly fluorescent (606-nm filter) ; a method based on this is fully recorded and found to be particularly suitable for samples containing less than 2 p.p.m.of selenium. A second method separates selenium from interfering materials by arsenic coprecipitation. A gravimetric method is described for determining large amounts of selenium. C. Horvath of Yale University offers a long article on high-performance ion-exchange chroma- tography with narrow-bore columns. He devotes particular attention to the rapid analysis of nucleic acid constituents a t the sub-nanomole level. Thin ion-exchange resin shells on the surface of glass beads act as a skin (pellicular ion-exchange resin). A similar product (Zipax, made by Du Pont) consists of a porous crust of resin on a spherical silica core; it makes efficient columns for the analysis of nucleic acid constituents.Pellionex resins (Reeve-Angel) are deposited on glass micro- beads and their properties make them suitable for the analysis of minute samples. Theoretical aspects of the procedures are considered and there is a useful table of molar absorptivities of RNA 1973. Price k11.50.616 BOOK REVIEWS [Analyst, Vol. 99 constituents a t 260 nm. The actual instrument used for high-pressure liquid chromatography requires “the successful solution of complex engineering problems” and although home-made systems have been successful, the author prefers to describe in detail the Varian LCS 1000 model. Many problems open to attack by high-performance liquid chromatography are truly important and new highly sophisticated analytical techniques permit great gains in separation efficiency.These advances, however, demand much improved methods for preparing small samples as well as more efficient and rapid identification of unknown components. J. Okuda and I. Miwa of Nagoya, Japan, consider newer developments in enzymic determina- tion of D-glucose and its anomers. (In water, glucose equilibrates: a, 36.5; p, 63.5; aldehyde form, 0.003 per cent.). The enzymes concerned include (2) @-D-glucose oxidase, (ii) hexokinsse and (iii) acyl phosphate : ~-glucose-6-phosphotransferase. Methods based on (i) require the use of the oxygen electrode or of colorimetry or fluorimetry ; each approach is described and evaluated. Methods based on (iz) may involve spectrophotometry, colorimetry, fluorimetry or radioisotopes.The enzyme (iii) is highly specific but the authors note that i t is not commercially available. K. G. Oldham of Amershsm surveys radiometric methods of enzyme assay in a long article covering general principles, techniques, classes of enzymes, different radiometric assay procedures and optimum conditions. The author observes that the number of labelled enzyme substrates now marketed is large and increasing steadily while counting equipment is satisfactory and widely avail- able. The run-on cost of radiometric assays has fallen and the time taken for each radiometric assay has been reduced. Conventional methods and radiometric methods are compared in an instructive and critical manner.There is increasing advantage to be gained by the use of radio- isotopes in clinical biochemistry and in pharmacology as well as in general biochemistry. ‘The article covers the ground very competently and 484 references are cited. P. J. Elving, J . E. O’Reilly and C. 0. Schniakel of Ann Arbor, Michigan, deal with polarography and voltammetry of nucleosides and nucleotides and their parent bascs as an analytical and investi- gative tool. The authors state that “one reason for the relatively small use made of polarographic techniques by chemists interested in biological compounds is their lack of sufficient theoretical back- ground in electrochemistry.” A substantial section (about 10 000 words) is devoted to a general discussion, which is followed by a somewhat longer section on pyridine (nicotinamide) derivatives.The treatment of pyrimidine and purine derivatives is systematic and thorough and includes a wide range of compounds including aza-, thio- and chloro-derivatives in addition to all the classical sub- stances. Finally, there is a shorter and instructive discussion of riboflavin and flavin nucleotides. J. R. Majer of Birmingham (England) and A. *4. Boulton of Saskatoon deal with the integrated ion-current (IIC) technique of quantitative mass-spectrometric analysis with particular emphasis on chemical and biological applications. It is difficult, despite the use of powerful physicochemical methods, to identify with certainty many unknown substances present in minute amounts in com- plex biological extracts. Precise mass analysis now allows positive identification a t the 2 p.p.m. level even when there is gross contamination, while the integrated ion-current method permits quantification in the to range, even in the presence of contaminant ions. The substances (or derivatives) must be volatile in high vacuum a t temperatures between -50 and +500 “C. Methods are described and the applications discussed include analysis of trace metals (via chelates), pollutants, detergents, surface decontaminants and isomers. The section on polln- tants includes an interesting treatment of the detection and analysis of polycyclic hydrocarbons. The authors point out that the IIC technique is the method of choice in biochemical applications, especially in problems of neurochemistry and neuropharmacology. They add however that, “the only snag would seem to be the expense of the installation (approximately $100000 to $150000) and the need for skilled and knowledgeable personnel. ” There can be no doubt that more and more difficult problems are being tackled successfully but the “snag” referred to by Majer and Boulton has its parallel in many other areas. This section is followed by a further section on applications. The present volume maintains the standard set by its predecessors. R. A . Morzi-o.~