BOOKS
Chromatography and Spectroscopy Selectivity and Detectability Optimizations In HPLC. Satinder Ahuja, 610 pp. John Wiley & Sons, 605 Third Ave., New York, NY 10158.1989. $85 Reviewed by Joseph Glajch, E. I. du Pont de Nemours & Co., 331 Treble Cove Rd., North Billerica, MA 01862 This book (Vol. 104) is the latest in a series of monographs on chemical analysis. Although it is not designed to replace an introductory textbook on HPLC, the author does provide a theoretical background of the separation process and goals in optimization before delving into the specifics of selectivity and detectability optimization. Chapter 1 describes some of the basics of optimization and parameters used in most procedures, such as resolution and experimental design techniques. Chapter 2, written by Lloyd Snyder, discusses the physicochemical basis for retention for the different modes of chromatography. Chapter 3 logically follows with a discussion of separation mechanisms and how to probe for other measurements, such as the use of molecular probes. The heart of the optimization portion begins in Chapter 4, where the author describes some of the conventional approaches to mobile-phase selection. Included are a discussion of mobile-phase effects as well as different modes of chromatography that can be employed, column types, and additives. In Chapters 5-10, each of the various modes of HPLC (normal-phase, reversed-phase, ion-exchange, ionpair, macromolecular, and isomeric separations) is handled in greater detail. These chapters, which are fairly complete and well referenced, include a number of useful graphs, tables, and monographs, many from previous works. They are well organized and appropriately concentrate on the basis behind selectivity optimization in each mode, rather than trying to discuss individual methods of optimization, as other reviews have done. Chapter 11 deals specifically with the important aspect of computer optimization, and the author describes the various published methods in great detail. Howev-
er, I believe that placing this chapter late in the book and making it only a small portion of the volume is the author's way of putting computers in their appropriate place (they are important, but not crucial to the process). The last two chapters discuss selective detectors and the optimization of detectability in HPLC. Detection is clearly an important part of the entire process (an optimized separation that is not detectable is useless!), and the author has provided a bonus not usually found in reviews of optimization. I believe this should be a useful addition to the libraries of many practicing chromatographers, especially those involved in method optimizations.
Included are a discussion of mobilephase effects as well as different modes of chromatography that can be employed, column types, and additives. Chiral Liquid Chromatography. W. J.
Lough, Ed. 276 pp. Routledge, Chapman & Hall, 29 West 35th St., New York, NY 10001.1989. $112 Reviewed by Kenny B. Lipkowitz, Department of Chemistry, Indiana University—Purdue University, 1125 East 38th St., Indianapolis, IN 46205 The purpose of this book is to provide the nonspecialist with practical aspects of enantiomer separation in liquid chromatography. The book presumes some knowledge of chromatography and organic stereochemistry, but not much. Because chiral chromatography transcends traditional boundaries, scientists in diverse disciplines such as food sciences, health sciences, and environmental studies as well as the more
traditional domains of organic, pharmaceutical, and medicinal chemistry will find this book especially useful. The 276-page book is divided into five sections. Part 1 (33 pages) is the Introduction, which consists of the following chapters: "Molecular Asymmetry" (Matlin), "The Importance of Enantiomer Separation" (De Camp), and "Chiral Liquid Chromatography: Past and Present" (Pryde). Part 2 focuses on chiral derivatization and consists of a single chapter (34 pages) on that topic by Ahnoff and Einarsson. This section is incongruous with the rest of the book because it deals with formation and separation of diastereomers rather than enantiomers, but it is an informative section nonetheless. Part 3 is dedicated to direct chiral resolution and constitutes the majority of the text (125 pages). Chapters include: "Chiral Ligand Exchange Chromatography" (Lam), "Synthetic Multiple-Interaction Chiral Bonded Phases" (Doyle), "Immobilized Proteins as HPLC Chiral Bonded Phases" (Wainer), "Cyclodextrin Inclusion Complexation" (Coventry), "Binding to Cellulose Derivatives" (Johns), "Binding to Synthetic Polymers" (Johns), "Ion Pairing" (Szepesi), and "Other Direct Chiral Resolution Methods" (Lough). Part 4, on strategies for development of LC enantiomeric determination methods (30 pages), includes these chapters: "Consideration of Other Techniques" (Lough and Matlin), "Choice of Chiral LC Systems" (Lough and Wainer), and "Optimization" (Noctor, Fell, and Kaye). Part 5 (23 pages) is a single chapter, "Future Trends and Requirements," by D. R. Taylor. This book meets the goal of condensing and explaining, for the nonspecialist, most of what is known in the field of chiral liquid chromatography. The chapters are informative (but not overly technical), concise, and well-written assessments of the state of the art. They are replete with up-to-date references and provide honest, nonbiased appraisals of the techniques and chiral stationary phases in use today. Most of the chapters provide useful tables containing well-organized generalizations about how best to use commercially
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BOOKS available columns, pitfalls to avoid, and time- and money-saving hints. The book is virtually error free, well organized, and especially timely because there are many nonspecialists who have the tools for, and interest in, enantiomer separation but who lack the insights provided by the authors of this book. If you intend to do chiral chromatography you should purchase this book and read it from cover to cover to avoid wasting time and money.
Photometric Determination of Trace Metals, Part MB: Individual Metals, Magnesium to Zirconium. 4th ed. Hiroshi Onishi, 821 pp. John Wiley & Sons, 605 Third Ave., New York, NY 10158.1989. $180 Reviewed by Dennis Jenke, Baxter Healthcare Corp., William B. Graham Science Center, Round Lake, IL 60073 This book represents the third part of the latest revision of the classic text Colorimetric Determination of Traces of Metals (E. B. Sandell, 3rd éd., 1959). Part I, co-authored by Sandell and H. Onishi (1978) dealt with the general aspects of photometric trace metal analysis. In Part IIA (H. Onishi, 1986) the determination of metals from aluminum to lithium (including lanthanoids) was detailed. Part IIB continues (and presumably completes) the series by dealing with individual metals ranging from magnesium to zirconium. The book is methods oriented in that it deals with the specifics and mechanics of preparing the sample for photometric measurement and outlines instrumental operating parameters. Photometric instrumentation and theoretical aspects of photometric measurement are not considered in this text. Each chapter of the book, devoted to a particular metal, is structurally similar and consists of three main subdivisions. Section I, Separations, essentially deals with sample preparation issues (species concentration, removal of matrix interferences) and considers (as appropriate) precipitation methods, chromatographic methods, extractions, and others. In Section II, Methods of Determination, a general survey of available procedures is given and several useful methods are detailed. Although emphasis is placed on more or less well-established techniques, methods involving more recent technology are reviewed in each chapter. Section III, Applications, is subdivided into portions related to a specific sampling medium (e.g., air, water, rocks, minerals and ores).
The previous parts of the 4th edition were well received by scientific reviewers; Part IIB keeps the tradition alive in spades. The discussion is comprehensive, clear, concise, and complete. Readers looking to solve a particular problem will undoubtedly come away with several useful strategies that can be implemented immediately. Readers with a more general interest (perhaps in terms of method development) will come away with an appreciation of the chemistry associated with the quantitation of any number of species. Strong points of the book include the use of tables to present comparative performance data and provide an overview of available methods. Pertinent diagrams illustrating spectral properties and method optimization data are provided in virtually every chapter. Tables of absolute sensitivities for the various methods provide information that is absolutely vital for the rigorous assessment of a particular method's utility. The literature cited, although mostly pre-1980, is exhaustive and contains much useful information in the form of notes. Despite the widespread use of "physical" methods for the quantitation of trace metals in complex matrices (atomic spectroscopy, electrochemistry, neutron activation, X-ray techniques), there are many applications (especially in the earth or material sciences) for which photometry represents the method of choice. Scientists involved with photometric determinations will find this book a valuable (perhaps indispensable) reference well worth the price.
Elementary Polarization Spectroscopy. Erik W. Thulstrup and Josef Michl. vii + 167 pp. VCH Publishers, Inc., 220 East 23rd Street, Suite 909, New York, NY 10010. 1989. $35 Reviewed by N. Purdie, Department of Chemistry, Oklahoma State University, Stillwater, OK 74078-0447 The authors state clearly in the preface their reasons for writing this abridged form of an earlier, larger, and more comprehensive monograph, and indicate that the present text provides an introduction to optical spectroscopy of partially aligned molecules at the undergraduate level. This objective is in fact easily accomplished by eliminating unnecessary mathematics and allowing more space for discussion of concrete examples, of which there are many. One-fourth of the text, however, is devoted to appendices that few people
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would ever use while reading this text, and such information can be found in numerous other resources if ever required for data interpretation. The decision to include the appendices is questionable. Discussions are limited to linear dichroism and its use in the investigation of the solute orientations in anisotropic solvents. Space used for the appendices might better have been used for other topics selected from the original monograph in order to flesh out the rather grand title used for the book. At first sight the organization of the chapters seemed appropriate, but a number of disconcerting references are made in Chapters 1 and 2 to subjects that are not introduced until later. The description of the experimental techniques and procedures, in Chapter 2, was the highlight of the text. Too often authors fail to cover these important details, preferring to devote more space to data interpretation and speculation. These last two endeavors are the purpose for doing the work, but they are dependent on the conduct of careful experiments. The proper balance has been accomplished, but I did find the description of the very important strategy referred to as "stepwise reduction" extremely vague. In many instances the text is ambiguous and the syntax difficult to interpret. For example, the authors refer to "the bending of a bond" when I presume they mean the bending of a bond angle, and the meaning of "In the limit of rotation rapid relative to the emission lifetime..." is unclear. The subject matter of the text will appeal to a restricted audience. In the context of undergraduate education, the book might be included to illustrate the theoretical capabilities of the method and the experimental capabilities associated with solutes dispersed in anisotropic solvents and stretched polymer films. The authors fail to convey the real significance of the basic research, settling for an obtuse reference to its providing a sensitive test for the quality of quantum mechanical calculations. Ironically, many instances are described in which scientific intuition is correct, and for η-butane "the qualitative rules-of-thumb give a bet ter agreement with experiment than complicated calculations. . . . " A few of the book's illustrations consider the significance with respect to applied re search (e.g., dye binding to DNA), and it is not inconceivable that a brighter future exists there. I was especially in trigued with the concept and possible applications of photoselection orienta tion. Literature references are sparse and
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BOOKS are included only in the legends of figures, which for the most part are journal reproductions. The most current reference is 1986, and the majority first appeared in the early 1980s. This observation, combined with the fact that the choice of solutes for study is limited (particularly to the polyaromatics, whose dichroic spectra are described in great detail), might create the impression that the method is only of historical interest. The book would have benefited from a brief chapter providing a modern-day perspective by comparing the conclusions on molecular alignment from polarization spectroscopy data with results, or prospective results, from X-ray analyses and NMR spectroscopy. Such information could easily have substituted for the appendices.
Environmental Analysis Using Chromatography Interfaced with Atomic Spectroscopy. Roy M. Harrison and Spyridon Rapsomanikis, Eds. 370 pp. John Wiley & Sons, 605 Third Ave., New York, NY 10158.1989. $133 Reviewed by R. E. Clement and J. F. Hopper, Ontario Ministry of the Environment, Laboratory Services Branch, P.O. Box 213, Rexdale, Ontario, Canada M9W5L1
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The editors of this book state that it lies at the boundary of the rapidly advancing areas of analytical and environmental chemistry. Of the 12 chapters in the book, the first 6 cover basic principles of chromatographic separations and spectroscopic detection methods, and the remaining 6 are concerned with the practical application of these techniques in environmental analysis on an element-by-element basis. It is clear that the editors did not attempt a comprehensive coverage of the field and that the book favors atomic spectroscopy detectors rather than chromatography. Nevertheless, the subject matter presented is generally very well described and this book is recommended for those interested in the analytical or environmental applications of chromatography with spectroscopic detectors. The first chapter explains the basic principles of chromatography and atomic spectroscopy. Although important theoretical concepts are introduced, readers will find that they are somewhat at a loss to understand the difference between wall-coated opentubular column GC, packed-column GC, and LC columns. A physical description of these various columns, or
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at least a schematic drawing or photograph of them, would help novice chromatographers much more than discussions of rate theory. Discussions of the liquid phase, solid support, polarity, and other important chromatographic concepts are poor. The basics of atomic spectroscopy are better treated, although this section is also very brief. The chapters on detectors (atomic absorption, flame photometric, atomic plasma emission, and atomic fluorescence) and interfaces between LC and atomic absorption are excellent. Although the authors of these chapters are different, the editors have done a fine job in ensuring good flow through this section of the book. One strength is that the chapter authors have included drawings and descriptions of many custom-built components such as traps, atomizers, and silica furnaces. Anyone
... a good review of combined chromatographic and spectroscopic detection techniques for analytical chemists concerned with metal speciation, especially for those unfamiliar with the advantages of spectroscopic detection. attempting to construct a similar apparatus can quickly grasp the general principles of the hardware design which, when supplemented by the thorough lists of references given, can significantly reduce the time required to implement the techniques. An important omission is any description of ICP/MS. Although there is sparse literature on coupled GC/ICP/MS, this is an important and rapidly growing area that should have been included. Applications chapters on tin and germanium, lead, arsenic and antimony, mercury, selenium, and sulfur gases are valuable additions to the book. Although the emphasis is on the detectors rather than the chromatographic separations, both are treated in sufficient detail (including references) that those interested in the environmental analysis of the elements covered will find the
BOOKS
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applications chapters valuable. Other important elements are briefly men tioned. For example, the toxicity of chromium and aluminum in the aquat ic environment is dependent on their oxidation states. In addition, descrip tions of the difficulties in performing analyses of real environmental samples are somewhat incomplete with respect to sampling and sample preparation, although sufficient recent references are given to enable the reader to thor oughly research these areas. In summary, this book is a good re view of the general analytical tech niques of combined chromatographic and spectroscopic detection and a thor ough survey of techniques for a number of environmentally significant ele ments. It would be most useful as a reference for analytical chemists con cerned with metal speciation in envi ronmental samples—especially for those unfamiliar with the advantages of spectroscopic detection. Although some gaps in coverage exist, the book is a valuable reference for an important and rapidly growing area of environ mental analytical chemistry.
The Vibrational Spectroscopy of Poly mers. D. I. Bowers and W. F. Maddams, xiii + 326 pp. Cambridge Uni versity Press, 32 East 57th St., New York, NY 10022.1989. $90 Reviewed by Jack Koenig, Depart ment of Macromolecular Science, Case Western Reserve University, Cleve land, OH 44106 Upon receipt of this book, I was filled with enthusiasm because I have per sonal knowledge of the background and experience of the two authors and knew that they would do an outstanding job. The challenge that they set for them selves was to write an introductory readable text to give novices unfamiliar with IR and Raman spectroscopies, or elements of polymer science, a single text to allow them to be conversant in the combined aspects of polymer spec troscopy. This is no small challenge but is certainly a worthy objective in light of the special knowledge required to use vibrational spectroscopy intelli gently to study polymer systems. The book does not completely ac complish this objective, but it does present a sound basis for further devel opment on the part of the novice read er. Some of the conceptual discussions are well thought out and well written. The discussion of group frequencies is good and should be read by experi enced spectroscopists for the insights it
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provides. Occasionally, however, some of the oversimplifications do lead to confusion. For example, on p. 15, where the discussion of the spectroscopy of polymers is described as a function of the "many repeat units within one wavelength," one is overwhelmed by the notion that such a concept would be consistent with observed absorption of "small" molecules such as carbon mon oxide or hydrogen chloride. The treatment of the various contro versies involved in the assignments of the most studied polymer, polyethyl ene, is lucid and sound in judgment, indicating t h a t vibrational assign ments can have a lifetime of their own depending on the amount of knowledge available at the time of the assignment. The book has some oversights, such as the lack of discussion of emission, photoacoustic, and diffuse reflectance techniques for IR sampling. These techniques are now the dominant mod ern methods and should be included for the use of the active worker. A definite no-no, in my opinion, is the presentation of difference spectra in the %T mode when it is recognized that only background in the %T mode will not show up in the subtraction spectra, and only absorbance spectra corrected for baseline should be sub tracted. The novice should not be misled. Overall, I liked the book very much. To see a unified treatment of IR and Raman techniques for polymers is sat isfying because a common treatment can be made, as this book demon strates. Modern spectroscopic equip ment allows one to obtain both on the same instrument, so this book is also timely. I highly.recommend it for bud ding spectroscopists who are initially encountering polymers using IR and Raman spectroscopies.
Laboratory Automation Using the IBM PC. Stephen C. Gates and Jordan Becker, 322 pp. Prentice Hall, Englewood Cliffs, NJ 07632.1989. $36 Reviewed by Robert Megargle, Depart ment of Chemistry, Cleveland State University, Cleveland, OH 44115 Computer-automated instruments and equipment can be purchased for nearly all popular laboratory techniques. To attract the widest possible market, these devices must be broad in applica tion and general in design. Scientists are almost always better off buying such equipment rather than construct ing it themselves. In some situations, however, building a system in house is the preferred route.
For a variety of reasons, it may not be practical to scrap existing apparatus. Automation of old devices is frequently a custom job. Maybe the desired instrumentation is not available commercially. It might involve a prototype design or an entirely new instrumental approach. Sometimes the market is so small that vendors cannot sell enough units to make the development worthwhile. In some cases, the available commercial systems are too general for the intended applications. This situation will be more likely to occur as the use of automated information processing increases. Although the data measurement techniques are general enough to be used over a wide range of applications, the data processing requirements are not. Data processing systems tailored to particular customer needs are going to become more prevalent. Laboratory Automation Using the IBM PC addresses the needs of those who want to interface laboratory equipment to a small computer. It is aimed specifically at IBM PC-XT and PC-AT computers as well as any of the various clones on the market. It is also applicable to the IBM PS/2 or other computers of similar architecture that can run the DOS operating system. It is a good choice. These computers are low cost, widely available, and already familiar to many analytical chemists. There are extensive hardware and software products available for them, including a large number of scientific programs. The book is enhanced with numerous example programs in the text, which are also found on a 5.25-in. floppy disk inside the back cover. The examples are written in BASIC and are compatible with version 2.0 or later of BASICA (TM) or with QuickBASIC (TM). The BASIC language is also a good choice for the book. BASIC is easy to learn and is quite suitable for projects of low to medium complexity. Many scientists already know BASIC. It is easy to debug and frequently yields a working program quicker than with other languages. BASIC is often the language of choice for interfacing projects. One problem for any book on lab automation is the wide variety of interfacing hardware available to the implementer. Although they all do basically the same thing, the details of operation of the different interface circuit cards are not the same. The authors chose the model DT2801 board from Data Translation as a general analog and digital I/O board and the GPIB (IEEE 488) board from National Instruments for high-speed parallel interface examples. The interfacing strategies discussed
are appropriate to most of the hardware on the market, but the programming details needed to accomplish the objectives will differ. Readers with different hardware will have to modify the example programs found in this book, which could significantly increase the burden for the novice. The book gives a good overview of laboratory interfacing, including both hardware and software issues. Digitalto-analog and analog-to-digital conversion is explained, along with analog signal processing, signal filtering, the use of timers and counters, asynchronous serial communications applications, and the IEEE-488 bus. There is an appropriate mixture of theory and practice, the latter illustrated by useful suggestions on cabling, shielding, and grounding techniques. On the software side, the book discusses data storage, plotting, screen displays, peak detection, and image processing. There is an overview of the role of local area networks in the laboratory. When and how to use assembly language subroutines is explained in a section on advanced techniques. This section also deals with interrupts and direct memory access. This book is written in a clear and comprehensible cause-and-effect style, and there appear to be no significant errors of fact. None of the topics are covered in extensive detail. The book is most useful to give an overview, bring different possibilities and options to the attention of the reader, and provide a starting point for more detailed studies. The treatment of electronic subjects is terse, and readers with little previous knowledge of operational amplifiers and digital electronics may find it difficult to understand. Those readers should keep one of the many "electronics for scientists" type textbooks available for supplemental reading. The book also assumes that the reader is already familiar with the DOS operating system and the BASIC programming language. Attempting to read this book without t h a t knowledge may prove difficult. Although more experienced readers may already know most of the material in this book, there are still parts that may be useful. The sections on noise reduction, peak detection, image processing, local area networks, interrupts, and DMA contain useful information even for the more experienced individual. This book deserves a place on your library shelf if you are engaged in or are contemplating the use of a PC-type computer in a laboratory experiment. It is a clear and comprehensible survey of hardware and software techniques used in instrument interfacing.
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