BOOKS
Quantitative Analysis, Chromatography, Spectroscopy, and Protein Purification Quantitative Chemical Analysis, 3rd ed. Daniel C. Harris, xv + 782 pp. W. H. F r e e m a n and Company, 41 Madison Ave., New York, NY 10010. 1991. $55 Reviewed by Robert de Levie, Department of Chemistry, Georgetown University, Washington, DC 20057 The t h i r d edition of Quantitative Chemical Analysis by Harris is a furt h e r i m p r o v e m e n t on a n a l r e a d y quite successful textbook. As in the earlier editions, the style is clear and conversational, and there are many excursions into interesting applications, often clearly set apart from the main argument in special boxes. Its attractive elements add to the appeal of this text: legible lettertype; wide margins with extra pointers and hints; and clear illustrations, including improved color plates. The text is organized in 25 chapt e r s . After two short introductory chapters and two chapters on error analysis and statistics, the main topics are covered in 12 chapters dealing with various aspects of equilibria, gravimetry, precipitation titrations, acid-base and complexometric titrations, potentiometry, and redox titrations. There is a chapter on sample preparation, a set of 19 lab experiments, a glossary of terms, 106 pages of appendices, worked-out solutions to exercises, numerical answers to problems, and an extensive index. Like many other recent textbooks on quantitative analysis, this book covers much more than is traditionally taught in such courses; it makes major excursions into the domain of instrumental analysis. Consequently, there are chapters on electrogravimetry and coulometry; voltammetry; two on spectrophotometry; and one each on atomic spectroscopy, separations, and chromatography. Together, these constitute more than a third of the text. Perhaps this has been done to make the book useful for nonmajors, even though the level of de-
tail is geared to the chemistry major, who will still have to buy a textbook on instrumental analysis. The problem of trying to be everything to everyone is exacerbated by the many side trips. They do make the text more interesting, but they also detract from the main message and add to the feeling of overload; there is j u s t too much material in this book to cover in one semester. There is no disagreement with the author here, who writes in his preface t h a t "there is no way for one course to cover every topic in this book." I have t h e impression t h a t many students would prefer a thinner, lighter, and less expensive volume geared to their needs. This edition is a n improvement over its predecessor in that the topics are presented in a more logical manner. Consequently, t h e pH dependence of the solubility of sulfides follows r a t h e r t h a n p r e c e d e s a discussion of acid-base equilibria. Unfortunately, this r e a r r a n g e m e n t has made the discussion of equilibria even more diffuse; it is now spread over four noncontiguous chapters (5, 7, 10, and 12). Another welcome change is found in the discussion of electrode potentials. The text no longer insists that the cell voltage depends on how we choose to write the cell reaction. Unfortunately, remnants of the earlier approach are still visible. For example, the student is challenged on p. 319 to "show that Le Châtelier's principle requires a negative sign in front of the log term in the Nernst equation" for the balanced equation aA + bB ^ ^ cC + dD, suggesting that the cell potential Ε knows that we did not write the equilibrium as cC + dD ;=± aA + bB. Unfortunately, the text still con tains one major flaw: The author in sists that the pH is the logarithm of the activity of hydrogen ions. This point is emphasized again and again, and is, of course, incorrect, as long as pH is associated with an experimen
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tally measurable quantity. As it is, it will fall to the physical chemists to set this matter straight in a subse quent semester. This is a most re grettable error, because the concept of pH is so central to quantitative analysis. One can only hope that it will be corrected in a fourth edition. This should not be too difficult, be cause the text already explains that "junction potentials are usually un known" (p. 358), mentions (albeit without explanation) that "it is usu ally not possible to adjust the activi ty of a species to 1" (p. 316), and even lists in Table 15-3 the standard buff ers on which the correct definition of pH is based.
Multidimensional Chromatography: Techniques and Applications. Hernan J. Cortes, Ed. viii + 378 pp. Mar cel Dekker, 270 Madison Ave., New York, NY 10016. 1990. $100 Reviewed by Eli Grushka, Department of Inorganic and Analytical Chemistry, The Hebrew University of Jerusalem, Jerusa lem, Israel Multidimensional chemical analysis is a very powerful approach because frequently the combination of two or more methods of analysis has a syn e r g i s t i c effect. M u l t i d i m e n s i o n a l chromatography is a subset of multi dimensional analysis and, as a pow erhouse technique, is well worth pur suing. This book helps to alleviate the sparseness of literature in the field. It brings under one cover recent developments in the multidimension al approach to various chromato graphic methods. The book is highly recommended to those who use mul tidimensional chromatography and those contemplating using it. The book contains 10 chapters. The first chapter, by J. C. Giddings, lays the theoretical foundation for multi dimensional analytical separations. The chapter, based heavily on previ ous works by Giddings, amply dem-
onstrates the benefits of such a mode of operation. The second chapter, by C. F. Poole and S. K. Poole, is enti tled "Multidimensional Thin-Layer Chromatography" (TLC). The title of the chapter is somewhat misleading as most of it deals with conventional or "unidimensional" TLC. Chapter 3, by W. Bertsch, deals with multidi mensional GC and presents a nice balance between instrumentation and applications. The chapter is well illustrated and well referenced, al though it is not as up to date as it should be for a book published in 1990. The fourth chapter, by P. Sandra and F. David, is actually out of place in this book. The chapter deals with selectivity optimization in capillary GC. Although the topic is very impor tant, its direct connection to the sub ject at hand is minimal. Chapter 5, by U. K. Goekeler and F. Mueller, covers the use of multidimensional chromatography in process control. The chapter presents detailed infor m a t i o n on injection s y s t e m s a n d switching valves. The major draw back of this chapter is in the very skimpy (and greatly outdated) list of references. C h a p t e r 6, by H. J. Cortes and L. D. Rothman, covers multidimen sional high-performance liquid chro matography (HPLC). The authors de scribe various instrumental aspects and provide some applications. The instrumental part is not too detailed, and the interested reader will have to h u n t down the original papers for more information. Chapter 7, also by Cortes, deals with coupling HPLC to GC. Such a coupling is a true exam ple of multidimensional chromatog raphy, and interest in it is growing. The chapter presents a good starting point for those wishing to exploit the combined power of two chromato graphic methods. Chapter 8, by I. L. Davies, Κ. Ε. Markides, M. L. Lee, and K. D. Bartie, describes several options for mul t i d i m e n s i o n a l s u p e r c r i t i c a l fluid chromatography (SFC). SFC/SFC is described in detail; both instrumen tation and applications are covered. The authors are actively involved in this area of research, and many of the references are to their own work. The combination of SFC with GC or HPLC is much less popular, and few published papers can be found on these approaches. The combination of supercritical fluid extraction (SFE) and SFC was also described by these authors. M. Saito, T. Hondo, and M. Senda devote Chapter 9 to SFE/SFC. Although this technique is not really
multidimensional chromatography, it is surely multidimensional analysis. The last chapter in the book, by L. D. Rothman, deals, in general terms, with hardware in multidimensional chromatography. This chapter should have been much larger because hard ware requirements can be quite be wildering to the neophyte. The book suffers from some short comings typical of multiauthored (no pun intended) books. Some chapters were better proofread t h a n others. There is a lack of uniformity in the terminology and in the symbols used. Symbols are introduced without be ing defined. However, these short comings are minor and, on balance, the positives outweigh the negatives. Those using multidimensional chro matography and those planning to use it will find the book useful.
Computer-Enhanced Analytical Spectroscopy, Vol. 2. Henk L. C. Meuzelaar. xvii + 318 pp. Plenum P u b l i s h i n g , 233 S p r i n g St., New York, NY 10013. 1990. $65 Reviewed by Bruce R. Kowalski, Depart ment of Chemistry, BG-10, University of Washington, Seattle, WA 98195 In J u n e 1988, analytical spectroscopists and chemometricians met at the Snowbird Resort in Utah for the Second Hidden Peak Symposium to l i s t e n to l e c t u r e s on c o m p u t e r enhanced analytical spectroscopy. This symposium, like the first, pro duced an edited volume with each chapter written by one of the 12 ple nary lecturers. The topics were se lected to complement those of the first volume so t h a t together they constitute a fairly comprehensive treatment of the research done up to the time of the symposium. The volume leads off with a wellwritten contribution from Joel Har ris and the home team at the Univer sity of Utah t h a t demonstrates the link between maximum likelihood and regression methods and stan dard statistical error analysis com monly used in spectroscopy. Gemperline and Hamilton then present a brief review of two factor analysis methods used to resolve the spectra of mixtures into individual compo nents. The really excellent p a r t of this chapter examines how spectral and chromatographic overlap, as well as noise and other factors, affect the net a n a l y t e signal (as derived by Lorber) and, ultimately, resolution. In Chapter 3, Karjalainen shows, in related work, how entropy consider
ations can aid mixture resolution using GC/MS data. I found Chapters 4 and 5 to be complementary and quite interest ing. Noninvasive analytical methods such as remote IR emission are far too few in number, and advances in those methods are very welcome. Chapter 4 describes some promising signal-processing methods, and Chapter 5 gives a short but concise account of chemical analysis of the E a r t h via satellite imaging in the 0.4-2.5-μπι region. To round out Part I (rather inappropriately called Un supervised Methods) is a contribu tion entitled "Computer-Enhanced NMR Spectrometry" that briefly cov ers the many hardware and software advances t h a t have affected NMR. The emphasis in this contribution is on data analysis as opposed to pulse programming. In the second half of the book, the emphasis moves away from computa tional methods and focuses on library searching, expert systems, simula tion, and pattern recognition meth ods. W h a t book on computer-en h a n c e d s p e c t r o s c o p y w o u l d be complete without a recent contribu tion from t h e l a b o r a t o r y of Fred McLafferty? His group authored the popular STIRS system and has been m a k i n g contributions to t h e field since the 1950s. The group reports t h a t application programs such as PBM and STIRS are entering a new era. Users have less formal training in interpretation of mass spectra, so the p r o g r a m s are becoming more user friendly. For example, with help from Chemical Abstracts Service, 83% of the 140,000 stored reference spectra can be displayed with molec ular structure images t h a t greatly improve identification. Because the chapters do not repre sent detailed reviews of each topic, the reference lists do not contain key references in each field. No author index is included, but the subject in dex is accurate and useful. Finally, it should be pointed out t h a t little at t e n t i o n w a s paid to coordinating chapters and standardizing nomen clature and notation as would be ex pected in a textbook. For example, the first and final chapters cover multivariate calibration from such different perspectives and styles that a novice would probably miss the unifying theory and concepts t h a t link multilinear regression, principal components regression, and several other popular methods. Volumes such as this one serve a very useful purpose in science. This book can be read by an expert in the
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BOOKS field to see what is going on in other parallel areas of research. It is recommended, along with Volume 1, for any spectroscopist wishing to explore how computers are affecting, or will affect, different spectroscopies. For this purpose, it is certainly the more enjoyable a l t e r n a t i v e to plowing through extensive reviews.
Protein Purification Methods: A Practical Approach. E.L.V. Harris and S. Angal, Eds. Oxford University Press, 200 Madison Ave., New York, NY 10016. 1989. $40 Protein Purification Applications: A Practical Approach. E.L.V. Harris and S. Angal, Eds. Oxford University Press, 200 Madison Ave., New York, NY 10016. 1990. $36 Reviewed by S-H. Chiou, Institute of Biological Chemistry, Academia Sinica, Taipei, Taiwan and School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA 30332 Protein purification is overlooked by most graduate students of the current generation in spite of its central role in many areas of biochemical research. Most students j u m p on the bandwagon of gene cloning and splicing before gaining a strong foundation in the basic purification skills e m p h a s i z e d in t h e c o n v e n t i o n a l training of biochemists and molecular biologists. Purification of proteins and peptides is an essential skill for a successful researcher in modern life sciences. This two-volume m u l t i a u t h o r e d work describes the different methods for protein isolation and purification. It begins with basic techniques and protocols in the first volume, Protein Purification Methods, and advances to purifications of proteins for specific purposes in the second volume, Protein Purification Applications. Both the basic principles of each technique and their practical step-by-step protocols fit nicely in these medium-size comprehensive volumes of methodology. Researchers with previous exposure to protein biochemistry may feel that some chapters contain unnecessary details, and r e d u n d a n c y appears among some protocols in chapters written by different a u t h o r s . However, most of the chapters are presented in an easy-to-follow fashion for the new students in the protein purification field and are richly documented with references usually scattered in general biochemical and analytical journals and reviews.
It will be especially rewarding to read the sections in Chapter 1 of the first volume, which elucidate the most basic aspects of protein concentration determination and the powerful electrophoretic technique in protein purification and characterization. Chapters 3 and 5 of the second volume are noteworthy in t h e i r t r e a t m e n t of sample preparation for protein crystallization and purification of proteins for sequencing, topics that freq u e n t l y a r e o m i t t e d from m o s t textbooks and that will be useful for experienced and practicing protein and peptide chemists in general. The subject or keyword index of both volumes is adequate for the easy search of a specific technique in spite of a lack of author indexes.
"Purification
is an essential skill for a successful researcher in modern life sciences."
The minor shortcoming of the volumes lies in the appendix, which lists the suppliers' information for the instruments and chemicals. To readers outside of Europe, most supplier information is futile and impractical. For a practical approach to a wider audience in North America, the suppliers' information should include American sources. Recent advances in instrumentation and techniques in protein and peptide chemistry have rekindled g r e a t d e m a n d for c h e m i s t s w i t h knowledge and skill in protein purification. For new s t u d e n t s and researchers who aspire to contribute to the new developments in biotechnology and protein engineering, these two introductory, yet comprehensive, volumes will be deemed valuable
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both as an overview and as a practical manual.
Field Desorption Mass Spectrometry. Lâszlo Prokai. vi + 291 pp. Marcel Dekker, 270 Madison Ave., New York, NY 10016. 1990. $100 Reviewed by Douglas F. Barofsky, Department of Agricultural Chemistry, Oregon State University, Corvallis, OR 973316502 This book, volume 9 in the Practical Spectroscopy Series, covers the principles, experimental techniques, general practices, and applications of field desorption mass spectrometry (FDMS). It is intended for mass spectroscopists or other scientists generally familiar with the instrumentation, techniques, and terminology used in MS. The author was not a participant in the development of FDMS; his experience with the method has been that of a more recent practitioner. The first half of Chapter 1, "Principles," deals with the fundamentals of field ionization and FD phenomena as they were originally defined for field ionization microscopy. The text in this half is curt, confusing, and grossly deficient in its reference to the literature. In contrast to the first half, the second half of Chapter 1 describes and classifies the models that are currently used to explain FD phenomena, giving a good perspective and a complete bibliography. Chapter 2, "Experimental Techniques and Methods," and Chapter 3, "General Practices," comprise a thorough reference to the tools and tricks t h a t make FD practicable for MS. Portions of the text covering coupling of FD to FT-ICR (Chapter 2), ion detection (Chapter 2), coupling of FD to tandem MS (Chapter 2), redox reactions (Chapter 3), and appearance and interpretation of fragmentation patterns in FD mass spectra (Chapter 3) are confusing, misleading, or both; the primary value of these sections is their guide to the literature. Chapter 4, "Application," categorizes the applications of FDMS into five areas and supplies representative examples and a good guide to the l i t e r a t u r e w i t h i n each g r o u p i n g . However, a r e a d e r i n t e r e s t e d in knowing whether a compound or a group of compounds might best be analyzed via FDMS, an alternative m a s s spectrometric technique, or some combination of both, would not be aided much by this chapter, or, for that matter, by the rest of the book.
The author does provide a connection to literature in which FD has been compared with other ionization techniques (Table 3.2, Chapter 3), but he does not offer any unambiguous conclusions about the merits of FD relative to those other techniques. On the contrary, he equivocates on this point by m a k i n g v a g u e s t a t e m e n t s t h r o u g h o u t the book t h a t portray FDMS a l t e r n a t e l y as a v e r s a t i l e technique with far-ranging applications and a declining technique that has been superseded by more recently developed methods. The composition, style, and editing of t h e book a r e e x t r e m e l y poor. Grammatical errors and convoluted phrasings are so gross and so prevalent that the text frequently reads as if it were a rough draft, and occasionally it defies comprehension. This book provides a complete, current reference to the experimental devices, practices, and literature that make up FDMS, and it can be recommended to mass spectroscopists and other scientists generally versed in MS strictly on that basis. The book offers little insight on the utility of FD relative to other ionization techniques, although it does provide a guide to literature where this inform a t i o n can be found for specific classes of compounds. The book is difficult (at times painful) to read, but extracting information from it is still quicker than starting from scratch in the scientific literature.
Ion Chromatography: Principles and Applications. Paul R. Haddad and Peter E. Jackson. 771 pp. Elsevier Science Publishing, P.O. Box 882, Madison Square Station, New York, NY 10159. 1990. $192 Reviewed by James Tarter, Talent, Inc., 306 W. Broadway, Fort Worth, TX 76104 This book is one of the latest contributions to become available to the ion chromatography (IC) community. The authors, Paul Haddad and Peter Jackson, have had distinguished careers in IC and have been instrumental in the development of this field. Their in-depth knowledge and understanding, along with their considerable scientific capabilities, have produced an excellent sourcebook. The book is divided into five parts: P a r t I covers ion-exchange separation methods; P a r t II addresses ion interaction, ion exclusion, and miscellaneous methods; P a r t III deals with detection methods; P a r t IV reviews practical aspects; and the final
p a r t discusses applications of IC. There are also an introduction, two appendices, and an index to round out the text. Although the volume covers a wide range of material, it is not necessary to read the entire book to obtain useful information. Each part is capable of standing on its own if a chemist needs only specific information regarding one aspect of IC. The introduction briefly discusses the history of IC and then provides a quick survey of some critical concepts in chromatographic theory. Although the theory is covered too quickly to be of significant use as a training tool, it does acquaint and remind the reader of the terminology that will be used throughout the book. P a r t I deals with ion-exchange sepa r a t i o n methods. This p a r t of the book introduces ion-exchange methods and discusses ion-exchange stationary phases, eluents, and retention models. This part is replete with figures and diagrams that illustrate in great detail how IC works. The structure of many common column materials is provided. Structures of many of the resin types and eluents are also provided, and these allow for a much clearer understanding of the complex chemistry underlying IC. The references are thorough and as current as possible. P a r t II covers other modes of ion chromatographic analysis. Here, as throughout the book, a significant amount of space is devoted to the presentation of theories and models. This greatly enhances the value of t h e book a n d provides t h e background and insights needed to fully utilize all forms of IC. Ion-exclusion and ion-interaction chromatography are complex methods, and Haddad a n d J a c k s o n cover these subjects thoroughly. Part III addresses detection methods used in IC. It consists of chapters on c o n d u c t i v i t y d e t e c t i o n ; o t h e r forms of electrochemical detection such as amperometry, voltammetry, and coulometry; potentiometric detection; spectroscopic detection; and detection by postcolumn reaction methods. Each chapter provides a table for species separated, specific form of detection, separation mode, detection limits, and references. The discussion of the various types of detectors seemed very thorough with adequate theoretical coverage as well as attention to the commonplace application of these methods. P a r t IV discusses the practical aspects of IC. It contains two chapters: sample handling and methods development. The chapter on sample han-
dling is a useful addition to a reference book of t h i s t y p e . S a m p l e collection, extraction, and cleanup methods are discussed. Contamination and concentration methods for ultratrace analysis are also covered. The chapter on methods development provides an overview of points to consider, key issues to address, and the possible avenues of approach when p u r s u i n g methods development in IC. Part V is the largest single portion of the book. It has seven chapters dealing with the application of IC (environmental, industrial, foods and plants, clinical and pharmaceutical, metals and metallurgical solutions, treated waters, and miscellaneous). These c h a p t e r s cover almost onethird of the book. They are almost exclusively tabular in nature; most of the nontabular material consists of references. The general organization of the tables covers solutes (with retention times in minutes), sample p r e p a r a t i o n , column used, eluent used, detection mode, and reference. These tables are one of the outstanding strengths of this book and should guarantee widespread use for years to come. Two appendices are present in this book. The first covers the growth of IC as measured by the publication r a t e . This information provides a good understanding of the field of IC and the methods by which scientists in the field communicate with each other. The second lists abbreviations a n d symbols used throughout the book. The 21-page index appears to be complete and should enhance the rapid use of the large volume of information contained in the book. There are relatively few distractions in this volume, none of which should impede its use by chemists at any level. In some cases the references are overly general, and in other cases they do not necessarily follow the logical order one would expect. Although this is somewhat disconcerting, it does not significantly detract from the overall usefulness of the book. The book was organized with great foresight. The beginning of each part contains a schematic overview of that section, which provides a grasp of the relationship between the m a t e r i a l covered in the different chapters. The large number of references, vast tabular information, and relative ease with which t h e book can be read should contribute to its utility. This is a "must have" book for all practicing ion chromatographers or those who wish to become such in an efficient, logical manner.
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