42 N ANALYST, APRIL 1993, VOL. 118 Book Reviews Concise Encyclopedia of Biological and Biomedical Measurement Systems Edited by Peter A. Payne. Pp. xiii + 490. Pergamon Press. 1992. Price f 140.00; US$240.00. ISBN 0-08-0361 88-9. In order to keep up-to-date and disseminate the information to as wide an audience as possible, it was decided to follow up the eight-volume Systems and Control Encyclopedia with a series of Concise Encyclopedias. This supplementary series is presented under the title ‘Advances in systems, Control and Information Engineering’. This volume is devoted to Biolog- ical and Biomedical Measurement Systems. It contains 85 articles, which are written by 81 authors and are arranged alphabetically with an extensive cross-referencing system. In addition to describing the fundamental measurement processes of transduction, signal processing and display, the articles illustrate the influence of anatomy and physiology on both the choice of measurement technique and the type of information obtained.The authors maintain a remarkably high standard and consistency when the diversity of both the techniques used and the influences on interpretation are considered. A large number of entries are related to investigating the function and imaging of specific organs and tissues. Biome- chanics, the development of mathematical models and the design of artificial or replacement organs also feature pro- minently. Whilst this is an essential reference work for biomedical engineers, it provides chemical and biochemical analysts with a refreshingly different insight into the problems of measurement.Some articles (e.g., absorption spectro- scopy, blood gas analysis, computer aided data acquisition and analysis, electrical safety, electrodes and magnetic resonance spectroscopy) are obviously relevant to many readers of The Analyst. There are others, such as those related to olefactory, taste and visual systems, which this reviewer found broadened his perception of the biological processes of the natural world. Amongst those few articles which this reviewer felt com- petent to subject to detailed criticism, there was one disap- pointment. It also illustrates the problem of keeping up-to- date. The section on clinical analysis i n the article on absorption spectroscopy did not review advances after 1979.It therefore omitted references to both centrifugal analysers and their suitability for rapid kinetic measurements, and to multi-layer so called ‘dry chemistry’ systems which employ various light reflectance procedures for mcasurernent. Analysts should be aware of this Encyclopedia as it would seem to have more relevance to their work than is superficially apparent. It can be a source of inspiration and may provide a solution to a difficult measurement challenge. R . S . Ersser Physical Methods of Chemistry. Second Edition. Volume IV. Microscopy Edited by Bryant W. Rossiter and John F. Hamilton. Pp. xi + 540. Wiley. 1991. Price f 109.00. ISBN 0-471 -08026-8. I found the title of this book rather misleading. I thought it could be useful as a source book for the application of a variety of methods of microscopy to a range of problems in the physical characterization of chemical systems.It is not. Instead its main theme is a small sub-sct of microscopic techniques. Of the ten chapters in the book, no lcss than eight are devoted to electron microscopy with a considerable emphasis on transmission and diffraction techniques. This represents over 65% of the text and cannot be described as a balanced view of the role of microscopy in the physical sciences. Despite these concerns, the subject matter is well laid out and the text is very readable. Seven chapters have been contributed by authors from the Center for Solid State Science, Arizona State University, and this brings a welcome coherence to a multi-author volume.This group of researchers are very well known, and they write authoritatively on the principles of electron microscopy, applications in biological systems, the imaging of crystal defects, high resolution imaging of materials, diffraction and microanalysis tech- niques. Much of the information has been published pre- viously in a variety of places, but this volume brings a great deal together in a very useful way. A short chapter on scanning electron microscopy does not come up to the standard of those on transmission techniques. It gives some fundamental background on contrast mechan- isms and analytical techniques, but is weak on applications. Walter McCrone is the almost inevitable choice for a substantial chapter on light and other microscopies. Again much of the material has been published many times before, but it is convenient to have it alongside the electron techniques. The final chapter deals with particle size measurement.Thc only link with the rest of the book is that microscopy is sometimes applied to this area, but the link is weak, and the chapter seems to belong to another book altogether. A surprising feature of thc book is that it does not seem to be very up-to-date. Confocal microscopy, which is busy revolutionizing the application of light microscopy to charac- terizing all kinds of physical systems, gets only a couple of paragraphs. Scanning tunnelling microscopy, which is having a major impact on the visualization of the surfaces of materials of all kinds, gets even less. Even in the area of electron microscopy, the use of cryo-techniques to stabilize and handle dynamically changing systems, such as multiphase fluids, is very poorly dealt with.Although published in 1991, the book gives a picture of microscopy which belongs to the mid 1980s. In summary, this book gives an excellent grounding in the use of the transmission elcctron microscope for materials characterization, although i t is not fully up-to-date. The remaining third of the book could have been omitted without much loss, and is unlikely to add to the argument for buying i t . R. M . Miller Ions, Electrodes and Membranes. Second Edition By Jiri Koryta. Pp. xiv + 198. Wiley. 1991. Price f12.95. ISBN 0-471-93080-6. This book sets out to introduce the reader to somc fundamen- tal aspects of electrochemistry by relating natural phenomena to underlying principles.It i(; written in a remarkably interesting and informative manner that gives a readability more akin to a good novel than a textbook. The introductory comments indicate the book is aimcd towards people entering the field from other areas; it fulfills this need rather well. Koryta takes a systematic approach of describing rather idealized experiments, explaining the general laws that relate to them and then discussing the consequenccs. This methodol- ogy works well, the reader is led gently through a subject thatANALYST, APRIL 1993, VOL. 118 43 N might otherwise be confusing and the essential science is put into context. This second edition reflects some of the recent progress in the field of membranes, membrane transport and new materials and the introductory sections have been simplified.The book is divided into three chapters each subject being named in the book title, thus it covers many important aspects of electrochemistry but is by no means comprehensive. However, each section is supplemented by a useful list of relevent and up-to-date references which make it easy for the reader to obtain supplementary information. The chapter on ions includes sections on: the formation of ions; conduction, conductors and solvation; electrolytes and non-electrolytes, acidity, protons in solvents, equilibria and dissociation, intracellular pH, macro acids and particle motion. The second chapter on electrodes describes aspects of oxidation and reduction, electrode potentials, galvonic and electrolytic cells, electrode reactions, rates and elcctrocataly- sis, electrolysis, corrosion, interfacial structure, electrochem- ical analysis, ultramicroelectrodes, light and electrodes. The third chapter on membranes has a distinct biological slant, it includes short sections on synthetic polymer mem- branes, analysis by membrane systems, biosensors, electro- chemical extraction, cell walls and biological membranes, active and passive transport and nerve action.Some of these sections are very short, barely an introduc- tion, but they serve to wet the readers appetite. This comment is not a criticism, too much information would change the admirable style of the text. The book is relatively inexpensive in softback form and I think it represents good value for money.I will recommend all my students read a copy! Jonathan Sluter Unified Equilibrium Calculations By William Benton Guenther. Pp. xvi + 314. Wiley. 1992. ISBN 0-471-53854-X. The problem of acid-base equilibria is all pervasive in chemistry. As acid-base equilibria are often involved in mechanisms of both inorganic and organic reactions, their role must be understood in interpretation of kinetic and equilib- rium data both in inorganic and organic chemistry. In analytical chemistry acid-base equilibria play an essential role in qualitative analysis, in all modes of titration, control efficiency of extractions of compounds with acidic and basic properties, they affect the absorbance of numerous organic and inorganic compounds, result in variations in measured values in potentiometry as well as polarography and voltam- metry.Separation processes in liquid chromatography are influenced by changes in acidity and analytical reactions in strongly acidic and strongly alkaline media commonly involve acid-base equilibria. In many instances the role of these equilibria is dealt with in an ad hoc manner with varying degrees of detailed understanding and rigorousness. This reviewer agrees fully with the author that a unified approach to the role of acid-base equilibria promises better undcrstand- ing of special cases. The author expresses his debt to the pioneering work by J . E. Ricci (Hydrogen Ion Concentration, Princeton University Press, 1952) and his assessment that this book was often praised and little understood is probably correct.He is also right that the plethora of symbols was of considerable detriment to the use of this book. The present reviewer remembers even after some 30 years the struggle to follow the derivations in Ricci’s book, but the effort was worth it. Consequently, this reviewer appreciated the idea that a shorter, more focused treatment was presented by Guenther, which uses a more restricted number of symbols. Unfortu- nately this book, which in addition to general problems of acid-base equilibria covers also the problems of metal ion-ligand equilibria as well as the effects of acidity on solubility, does not fulfil all expectations. In numerous cases the author does not define clearly and unambiguously the terms being used and often uses shorthand descriptions, which might be understandable to the initiated, but are not rigorous enough.For example, the definitions of C,,, CAB, C,, C1, C,, and C, should be more clearly formulated and demonstrated by examples. In the statement (p. 5 ) . . . cx3 is the fraction as H3A . . . ‘as’ should probably be replaced by ‘of‘. The statement . . . (still using the K , direction) (p. 5 ) probably means that all equilibria are considered as acid dissociations. To restrict the number of common strong acids to those enumerated on p. 234 is misleading. At least fluorosulfuric and trifluoroacetic acids should be included, but also all acids used as Hammett-type indicators as well as carbocations. Volatility of 7 mol 1-1 HCl is not a simple expression of incomplete ionization, but reflects also the solvation equi- libria.Statement ‘Acids do not really “dissociate”’ is rather misleading (p. 234). Every acid-base reaction whether between an acidic compound and water (as a base) or reaction of an acidic compound with a basic one in benzene involves interaction of an acid with a base and if the base is a solvent we call such processes by convention ‘dissociation’. The statement ‘Unfortunately, there is no way to predict acid-base behaviour’ (p. 234) would not find positive accep- tance by D. D. Perrin, J . Shorter, and many of us. As pH is defined as -log aH+ and a glass electrode measures activity rather than concentrations of hydrogen ion, boldface used for activities by Ricci seems to be more logical than the use of boldface for concentrations (molarities) used here.Overall the differentiation between thermodynamic and practical equilibrium constants is not consistent; there are also surpris- ing omissions. The seminal text by A. Ringbom, Complexa- tion in Analytical Chemistry, Krieger, Huntington, New York, 1979, used at many European universities as the text for introduction of metal ion-ligand (author often uses abbre- viated form metal-ligand) is not quoted. Similarly, in the section dealing with pH-effects on solubilities, which is of particular interest to the pharmaceutical industry, the fun- damental paper on General Treatment of pH-solubility Profiles of Weak Acids and Bases and Effects of Different Acids on the Solubility of a Weak Base by W. H. Streng, S. K. Hsi, P.E . Helms, and H . G. H. Tan, J . Pharm. Sci., 1984,73, 1679 is not quoted. The use of spreadsheets for calculations in analytical chemistry has recently been reviewed by H. Freiser (CRC, Boca Raton) but this text might not have been available at the time when Guenther’s manuscript was finished. To summarize, for various reasons the present text cannot be recommended for tcaching purposes or student use, but will be appreciated by an experienced researcher in the area. Let us hope for a second edition, possibly with a more presentation minded co-author, which would keep the essen- tials, but eliminate the pitfalls. Petr Zuman Fiber Optic Chemical Sensors and Biosensors. Volume II Edited by Otto S. Wolfbeis. Pp. 358. CRC Press. 1991. Price f 127.00. ISBN 0-8493-5509-5.This second volume moves from the fundamentals of optica! sensing devices dealt with in Volume I to the specifics of targeted solute assay, device construction and applications in a series of 13 wide ranging multi-author chapters. The volume is timely, given that much has been written about chemical and biosensors, but with an emphasis invariably upon electro-44N ANALYST, APKII, 1993, VOL. 118 chemical devices. Indeed, the future may well lie with optical detection with perhaps (as the editor opines) special possibili- ties shown by luminescent-based probes. The various chapters present logical progressions of constructional and application complexity on the whole, though segregating the chapter on pH sensors into Volume I and the inclusion of a chaptcr on temperature sensors seems rather incongruous.Chapter 1 provides a brief overview of the many ion recognition strategies used in the detection of inorganic ions. While by no means an in-depth analysis, a full range of ingenious receptor molecule options reported to date are itemized. Oxygen sensors rightly have a complete chapter devoted to them, and receive the full treatment of principles, problems, fabrication and operational outcomes in a well illustrated chapter. The next chapter gives a general outline of other gas measuring techniques that exploit fibre optics and includes useful descriptions of methane, CO, nitrogen oxide and water vapour detection, along with a more standard coverage of NHJ, C 0 2 and H2 sensors. Adaptation to environmental analysis is considered next; the description of the ‘hardware’ and various field spectroscopic arrangements, which take up much of this chapter are, however, of more value to the instrumentation engineer than to the chemist with ambitions to apply recognition chemistry to improved chem- ical sensing.A short chapter on fibre optic use in titrimetry reminds us of a possible laboratory niche for fibre optic technology, particularly where visual end-point determination is difficult. To include a chapter on sensors for nuclear plants is, in principle, attractive but perhaps falls short of scientific relevance given that most of the systems amount to conven- tional spectrophotometry, with fibre optics simply providing the optical plumbing. The chapter on thermal sensing, though a little misplaced, is, nevertheless, a well rcsearched and liberally illustrated description of what is clearly an active research area with a diversity that equals anything in chemical sensors.As with electrochemical sensors, integration with an enzyme is the surest way of achieving an operational biosen- sor. Systems exploiting product (NH3, NADH, H+) or co-substrate ( 0 2 ) detection by optical fibre have been allocated a chapter, but more detailed descriptions of indivi- dual devices would not have gone amiss in view of the high interest and activity of this area. For many, the ncxt stagc of biosensors is the immunosensor, which though a potentially powerful system, presents the drawback of a non-revcrsiblc response, and lack of an end product for the sensing event.Adaptation of conventional immunoassay strategics to fibre optics are well reviewed, though with rather too much space devoted to standard immunochemistry and insufficient on the fast developing area of surface optical devices. Two succeed- ing chapters deal with medical applications, and give useful practical examples of structures designed for pH, pco2 and yo, monitoring that can be reliably (and safely) interfaced with blood or implanted into tissue. Bio- and chemiluminescence reactions are capable of extreme sensitivity and avoid the need for a light source; the operational principles of these promising probes are presented in a separate chapter along with indication of the biocatalysts with which thcy can be used. The final chapter includes a generally useful discussion of mol- ecular parameters that determine biorecognition, with special emphasis on cell membrane receptors and their incorporation into natural and artificial lipid bilayers; if the engineering and biophysics can be sorted out, therein surely lies the future.A balance is t o be struck between a perfectly presented and extensive monograph that is out-of-date by the time of publication, and one that is a communications failure by being rushed off to press. This issue achieves a satisfactory balance between the two extremes and, accordingly, is of value to anyone with a specialist or indeed non-specialist eye for optical sensors. Pankuj Vadgumu Target Sites for Herbicide Action Edited by Ralph C. Kirkwood. Topics in Applied Chem- istry. Pp.xiv + 339. Plenum. 1991. Price US$79.50. ISBN 0-306-43846-1. The professional analyst with an enquiring mind may desirc to know more about physiologically active molcculcs or the metabolites thereof, which he may bc detecting and mcasur- ing. If these arc herbicides and he wishes to know how they work he will be attracted by the title of this book. Ralph Kirkwood has long cxpcricnce of the subjcct. He has written one chapter himself and for thc rcst he assembled a team of 11 othcrs, mainly from the UK, but two locatcd in the USA. All are very compctcnt authorities on their topics. However, the book is largely one for the specialist and not for thc faint-hearted; it starts as it means to go on. The very first chapter is a skilled account of the interaction of herbicides with the photosynthetic process, which reyuircs a basic grasp of modern plant biochcmi\try.The ncxt three chapters consider amino acid synthesis, lipid \ynthcsis and carotcnoid biosynthcsis as targets, respectively, followed by a fifth chapter on a range o f othcr primary target sites. The second half of the book cover\ diverse but related topics. This starts with a chaptcr on chemicals that can modify the action of herbicides. Next comcs consideration of how herbicides reach their target sites. This is divided between three chapters, the first of which discusses the influence of processes in the soil. Where herbicides are applied direct t o foliagc other pathways and mechanisms of uptake arc involved and can be influenced by surfactants. Following a chapter o n that subject, comes one on the ongoing transport of herbicides within the plant. The book concludcs with a chapter on herbicide metabolism a s a basis tor selectivity.This volume is an cxcellcnt introduction to the detailed literature. Thc chapters are well illuslratcd by chemical structures, biochcmical pathways and experimental data. Each chapter has a comprehensive rcfcrcnce list, the shortest of which contains 77 and the longest 225 citations! Sadly, this book i\ let down at the end. A list of ‘Chemical names of compounds mcntioncd in the text’ is incomplete. Many chemicals referred to only by the manufacturer’s code number are not listed, evcn though the structure might even have bcen illustrated i n a figure. The index shows many inadequacies.Thcre are many examples of index entries for spccific herbicides or groups of herbicides where refcrcnce i s made to one part of thc book but n o t to an equally important consideration of its aclion elsewhere. Entrics for plants, crops or weeds, are cqually erratic. By and large, if the Latin name is i n the text it is indexed, but not if only thc English name has bccn uscd by the author o f a chapter. K . Holly Nuclear Magnetic Resonance. Volume 21 Senior Reporter G. A. Webb. Specialist Periodical Reports. Pp xxii + 594. The Royal Society of Chemistry. 1992. Price f 145.00. ISBN 0-851 86-442-2. This latest volume of this wcll-respected series retains the format and style of previous volumes and covers the literature given in CA Selects-NMR Chemical Aspects from June 1990 to May 1991.‘Thus the majority of references quoted will bc for 1990 with a number from 1991. Intercstingly, I found references from 1952 quoted in this volume, which does seem somewhat anomalous. Chapter 1 (35 pages) is a comprehensive list of books and reviews compilcd by the senior reporter; 570 in all, an amazing number. In chapter 2 (33 pages) C. J . Jameson reports onANALYST, APRIL 1993, VOL. 118 4SN Theoretical and Physical Aspects of Nuclear Shielding, covering ah initio and semi-empirical calculations and some other aspects of nuclear shielding. Chapter 3 is entitled ‘Applications of Nuclear Shielding’ (36 pages) by I . P. Gerothanassis and C. Efthimiou and covers most other aspects of nuclear shielding including shielding of particular nuclei from Groups IA through to 0.In Chapter 4 (16 pages) H. Fukui gives a resume of work on the theoretical advances in the calculation of spin-spin couplings, by both ab initio and semi-empirical methods, and Chapter 5 (49 pages) by K. Kamienska-Trela complements the above in reporting the applications of spin-spin couplings, most of which understan- dably, involve couplings with hydrogen. Chapter 6 (30 pages) by H. Weingartner is devoted to Nuclear Spin Relaxation in Liquids, including structural and dynamic aspects and selected applications, and in Chapter 7 (49 pages) C. J. Groombridge reports on the large amount of work on Solid-state NMR including organometallics and silicates. Multiple Pulse NMR is covered in Chapter 8 (20 pages) by L. Y. Lion and J.C. Yang which includes various experimental procedures and also applications to structural problems. Chapters 9 (33 pages) by H. G . Parkes and 10 (23 pages) by A. H. Fawcett cover Natural and Synthetic Macromolecules, respectively, with sections on peptides, nucleotides and saccharides (Chapter 9) and liquid crystals and solid-state studies (Chapter 10). Conformational Analysis is dealt with by C. Jones in Chapter 11 (32 pages), which includes small organic molecules and nucleic acids, proteins and carbohy- drates. Some overlap with Chapter 9 is inevitable, but is not excessive. In Chapter 12 (30 pages) P. G . Morris reviews the NMR Spectroscopy of Living Systems including experimental advances and applications to both cell and tissue studies. NMK Imaging is dealt with in Chapter 13 (40 pages) by S.C. R. Williams who reports on instrumentation, contrast agents and solid-state imaging and other developments, and liquid crystals is covered in Chapter 14 (30 pages) by C. L. Khetrapal and K. V. Ramanathan. Finally, in Chapter 15 (42 pages) Heterogeneous Systems is reported by T. K. Halstead and includes polymers, solids and sorption on solid surfaces. There is only an author index. In conclusion the Senior Author is to be commended for coordinating this comprehensive reporting of the advances in Nuclear Magnetic Resonance. Perhaps comprehensive is the keyword. The problem for the practising NMR scientist is the quick and efficient retrieval from the literature of whatever one is interested in at the time. One wonders, with the advent of floppy disks with databanks and retrieval programs included, that perhaps this format should be seriously considered for these volumes in future.R. J . Abraham Spectroscopy of Advanced Materials Edited by R. J. H. Clark and R. E. Hester, Advances in Spectroscopy, Volume 79, Pp. xix + 405. Wiley. 1991. Price fll5.00; ISBN 0-471-92981-6. This book is number 19 of the highly acclaimed series: Advances in Spectroscopy, originally entitled Advances in infrared and Raman Spectroscopy. Whereas the earlier volumes contained review articles covering a large variety of topics, the last four books have each been devoted to onc single topic. The present book treats the structure, constitu- tion and dynamics of processes occurring in various advanced materials, by spectroscopic techniques, which include infrared and Raman, pulsed neutrons and photoexcitation spectros- COPY.The volume contains six chapters, each ranging from 36 to 104 pages, written by experts in the fields. The chapters include organic conductors, non-linear optical matcrials, semi- and superconductors and conjugated systems. Thus, the materials covered in this book are not selected as a rcsult of mechanical strengths but rather as new materials of interest in electronics, e.g., in semiconductors, photoconductors and optical switches. In Chapter 1 t h e charge-transfer crystals and molecular conductors that can function as photoconductors and scintillators are investigated by infrared and ultraviolet spectroscopy, using reflection techniques. The new applica- tions within optoelectronics are illustrated by infrared conduc- tivity spectra.Non-linear optical spectroscopy of conjugated polymers (which are used in commercial dyes) is treated in Chapter 2. These compounds form a new class of one- dimensional semiconductors and the review examines the connection between non-linear optical properties and struc- tures of the excited states. Both two photon and third harmonic generation spectroscopies are applied to the studies of polydiacetylenes. In Chapter 3 the technique of pulsed neutron studies is presented and applied to magnetic and hydrogenous materials, and tunnelling spectroscopy is applied to interca- lated graphite; this technique is limited by the beam intensity of the nuclear reactor. The technique of pulsed neutron spectroscopy is still in its infancy, and the chapter describes the theory as well as the experimental set-up in some detail.The average spectroscopist or analytical chemist will find this chapter to be very specialized. Typical semiconductors such as GaAs, InP and ZnSe are treated in Chapter 4, dealing with photoluminescence spectroscopy of thin-film semiconductor materials. This effect arises from the radiative recombination of excited state species and charge carriers in solids, and the technique can be used in steady-state as well as in time- resolved spectroscopy. Chapter 5 contains a comprehensive review (104 pages) of vibrational spectroscopy of polyconjugated materials: poly- acetylene and polyenes. These polymers become extremely good electric conductors when they are chemically doped or when they arc photochemically excited. The applications in technology are obvious, although a full understanding of their conductivity is still lacking. The chapter contains a thorough treatment of the infrared and Raman spectroscopy of these polymers as well as normal coordinate analyses and quantum mechanical calculations and is for this reviewer the most successful chapter in the book. The photo-excitation spectro- scopy of polyaniline is treated in Chapter 6. Owing to their alternating ring-heteroatom structure the polyanilines differ from other polymers such as polyacetylene, polythiophene and polypyrrole and serve as interesting model compounds for new phenomena. There is no overlap between the chapters and there is a unified treatment throughout. The editors should be praised for using SI units and enforcing standard IUPAC nomencla- ture in the book, as they have done in all the previous volumes. The typography and quality of printing are excellent in this series as should be expected considering the high price of each volume. Peter Klaeboe