Organic Ion Radicals: Chemistry and Applications. By Zory V. Todres (Columbus, OH). Marcel Dekker, Inc.: New York and Basel. 2003. xvi + 444 pp. $185.00. ISBN 0-8247-0810-5.
book, I suspect, will be limited to purchase by libraries, which I recommend they do. R. Daniel Little, UniVersity of California, Santa Barbara JA0253080
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The book covers a wide range of topics. It is organized into eight chapters dealing, in broad terms, with the nature of organic ion radicals, their formation, identification, and synthetic utility. Practical applications are also described, including, for example, the role of ion radicals as organic metals, magnets, and lubricants. Those interested in using these intermediates in their research efforts will welcome the chapter entitled “How to Optimize Organic Radical Reactions”. It is useful to have such broad coverage accessible in a single treatise. An unfortunate result, however, is that the coverage of some topics is occasionally incomplete. A reader’s personal tastes will obviously dictate his or her viewpoint in this regard, of course. In my opinion, Chapter 6, entitled “Organic Ion Radicals in Synthesis”, misses many beautiful examples that fit the guideline established by the author for inclusion within the chapter (p 302). Where, for example, is a discussion of the beautiful electrooxidative work that has been explicitly directed toward the construction of natural products (see, for example, a recent review in Tetrahedron 2000, 56, 9527-9554)? There are also a few odd phrases that are used in the chapter, including, for example “defense group” (rather than “protecting group”), and “synthone” in place of “synthon”. I see no need to develop new descriptors for well-established terminology. Each chapter is accompanied by a list of references, sorted by first author and referred to within the chapter by that name and the year of publication. There is also an author index appearing at the end of the book. These adjuncts will undoubtedly prove useful. I am less impressed by the subject index. I would think, for example, that one should be able to find “oxidation” and “reduction” listed among the topics, particularly for a book titled “Organic Ion Radicals”. My greatest concern, however, focuses upon the structural representations. It is most unfortunate that current software was not used to generate structures; indeed, some readers may be turned away from the book because of the poor quality drawings. Numerous violations of standard bond angles and lengths are found throughout. In addition, the size of structures varies dramatically from one scheme to another. Furthermore, perspective, as illustrated by a break in a bond that lies behind another, is often not illustrated. The cost of the book is prohibitive ($185 plus tax). It is unfortunate that this, like so many other books, will not be readily available to students, particularly in a classroom setting, or simply as a resource book to have on their bookshelf. The 6338
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Polymer Films with Embedded Metal Nanoparticles. Springer Series in Materials Science. Volume 52. By Andreas Heilmann (Fraunhofer-Institut fu¨r Werkstoffmechanik). Springer-Verlag: Berlin, Heidelberg, New York. 2003. x + 216 pp. $79.95. ISBN 3-540-43151-9. Nanostructure-property relationships in metal-polymer nanocomposites are the timely subject of this book. The breadth of this field required the author to narrow the topic to metal nanoparticles embedded in polymer thin films deposited by vacuum processes, thus allowing for ample discussion and details on their formation, nanostructure, and properties. Throughout each chapter, experimental procedures and data are presented, including schematics for equipment, sample preparation, transmission electron micrographs, and graphical analysis of particle size and shape. A significant amount of theory, including some explanation of plasma resonance absorption and a longer explanation of optical calculations, has been incorporated. The book consists of six chapters, the first of which is a succinct introduction that leads the reader through the definitions, beginning with simple composite materials, filling volumes, and a chart of patterns of particle distribution. Modern methods of characterization are listed, and advantages of supporting metal nanoparticles in thin polymer films are discussed. The remaining chapters provide details of the fabrication, nanostructure, and properties of plasma-deposited films with and without metal nanoparticles. Tables and figures are often used and provide quick overviews of such information as method of fabrication, monomer, metal, power density, and film thickness. Discussions of the particle shape, size, and distribution as affected by factors including composition of the polymer matrix, the nanoparticle, thermal treatment, and laser or electron irradiation are well presented along with TEM and XPS data and graphical analysis. Mechanisms for the latter factors, for example, Ostwald ripening, coalescence, and oxidation of the nanoparticles, are also included in Chapter 4. The last two chapters are devoted to electrical conductivity and optical properties, including the effect of thermal treatment on these properties. Although the book focuses only on nanocomposites produced by plasma processes, the methods for characterizing them and forstudying their properties are applicable to other nanomaterials. 10.1021/ja0253080 CCC: $25.00 © 2003 American Chemical Society
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Hence, this book will be useful to those new to the field of nanocomposites as well as to specialists in plasma-deposited films. Patty Wisian-Neilson, Southern Methodist UniVersity JA025352F 10.1021/ja025352f
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Annual Reports on NMR Spectroscopy. Volume 45. Edited by G. A. Webb (Royal Society of Chemistry, London). Academic Press (An Imprint of Elsevier Science): London, San Diego. 2002. x + 202 pp. $139.95. ISBN 0-12-505448-3. Applications of NMR spectroscopy are widespread in the areas of chemistry, biology, medicine, and materials science. This volume of Annual Reports on NMR Spectroscopy provides a nice balance of discussions in each of these fields. This book should appeal to NMR spectroscopists because it describes modern applications of the technique to diverse and important topics. It should also serve as a good resource from which to learn about advances in some of the most difficult applications of NMR spectroscopy. In addition, this book should draw readership from researchers in each of the specialized fields represented by the five chapters: polymers, proteins, cancer, porous media, and micelles. Each chapter has a clear presentation of the challenges within each area of the field and provides discussion of the ways in which NMR spectroscopy offers unique and valuable solutions to these problems. Chapter 1 is devoted to new techniques in solid-state NMR spectroscopy that enable the quantification of dynamics in polymeric materials. It begins with a description of the importance of these dynamics and the limitations of various techniques in quantifying and understanding them. The authors are foremost experts in solid-state NMR spectroscopy of polymer dynamics, and this is an extensive review of their work. This chapter serves as an excellent starting point for those planning to use solid-state NMR spectroscopy to study dynamics of complex systems. The chapter includes an extensive list of applications of their pulse sequences and clearly shows the value of these techniques. The NMR spectroscopy of large proteins is the subject of Chapter 2. This clearly presented review provides a historical perspective of various problems encountered in the quest to determine the structure of proteins using NMR techniques and includes a time-line of some of the key advances in the field. The authors provide a list of the most important developments and describe each one in detail. These descriptions are written in a language accessible to a novice who simply wants to know what the various techniques offer before diving into a full understanding of the physics behind each pulse sequence. However, the chapter also has applications that will be of interest to experts in the field and includes an extensive list of references that directs the reader for further study. The use of magnetic resonance spectroscopy (MRS) in the assessment of human biopsies is reviewed in Chapter 3. The authors do an excellent job of describing cancer pathology and even include a glossary of terms for those not well versed in this field. The limitations of histopathology are discussed, as are MRS techniques capable of overcoming these limitations.
The chapter focuses on the advanced data analysis needed for MRS to be successful for pathologic study and prognosis in the fight against cancer. A clear description of a three-step statistical classification strategy is also included along with an extensive list of applications to various types of cancer. This chapter is a good introduction to the exciting applications of MRS to cancer research. The focus of Chapter 4 is on studies of porous media with specific emphasis on spatially dependent distributions of porosity and permeability. The chapter begins with an introduction listing all of the practical applications of porous media in our everyday lives and goes on to do a very nice job describing porosity and flow. It is stated that traditional measurements provide only a single, average value for various physical properties of porous media, whereas advances in NMR spectroscopy as described in this chapter have led to methodologies to determine the spatial distribution of various properties within porous media; these advances can provide an improved understanding of spatially dependent processes. The final chapter provides a description of the NMR spectroscopy of micelles. It includes a comprehensive introduction to the structure and other properties of micelles as well as a discussion of the various applications of micelles in different fields. The authors review applications of NMR spectroscopy to understand micellar structure, the process of micellization, the physical properties of micelles, and the interactions of micelles with various other compounds. The organization of this chapter allows the reader to quickly find appropriate NMR experiments necessary to study different aspects of micelles depending on their area of research. As a whole, this text is an exciting look into recent advances in NMR spectroscopy. Although each chapter describes the application of this technique to a distinct field, they all have the goal of educating the reader about the successes of NMR spectroscopy in furthering each field of research. This book is an outstanding resource for researchers in any of these fields regardless of whether they are NMR spectroscopists. Mary Hatcher-Skeers, The Claremont Colleges JA025350V 10.1021/ja025350v
Solvent Mixtures: Properties and Selective Solvation. By Yizhak Marcus (The Hebrew University of Jerusalem). Marcel Dekker, Inc.: New York, Basel. 2002. xviii + 258 pp. $150.00. ISBN 0-8247-0837-7. In this well-organized short book, Professor Marcus succeeds inreviewing and organizing the vast literature on the thermodynamics, structure, and solvolytic properties of (mostly binary) solvent mixtures. The treatment ranges from a frankly phenomenonological presentation of physical, thermodynamic, and chemical properties of selected common solvent systems, through a review of the more successful empirical representations of the same, to brief presentations of the more important theoretical treatments of solvent systems. The exposition is direct, well written, and to the point throughout. The work includes numerous tables and diagrams that display the physical, thermodynamic, and chemical properties of a series of 20 aqueous cosolvent systems (including water-soluble common J. AM. CHEM. SOC.
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alcohols and diols, low-molecular-weight ketones, ethers, amines, and amides, and dimethyl sulfoxide) as functions of concentration, generally at nominal room temperature (298.15 K) and pressure (0.1 MPa). These “more important” solvent systems occupy the bulk of the tabular materials and much of the discussion, although the author has also selected seven solvents (benzene, CCl4, acetone, acetonitrile, nitromethane, methanol, and ethanol, and their binary mixtures) as representatives of nonpolar, polar, aprotic, and protic solvent and cosolvent systems. Thus, the reader is never more than a few pages removed from tabular or graphic presentations of experimentally observed data. This is a major strength of the book. It is frankly concrete and phenomenonological in its point of view. Although abstract theory is given its due, it is never emphasized. “Solvent Mixtures” is organized into five chapters. The first (15 pages) comprises a brief introduction. The next chapter, “Properties of Binary Solvent Mixtures” (105 pages, nearly half the book), is a review of the physical and thermodynamic properties of the 20 aqueous and seven nonaqueous solvent systems specified in Chapter 1, such as eutectic and azeotropic temperatures and compositions, refractive index, static and dynamic viscosities, permittivities, surface tensions, as well as thermodynamic and excess thermodynamic properties, including molar and partial molar Gibbs free energies, energies, enthalpies, molar volumes, compressibilities, etc. In this chapter, the author includes useful and clear presentations of numerous empirical and/or thermodynamically based correlating equations, tabulates numerical values of the correlating parameters, and discusses trends as one proceeds from nonassociated to associated cosolvent systems, etc. Citations here and in other chapters are by and large confined to the secondary (review) literature because, as the author states, “such data ought to have been already critically evaluated and selected by the authors of such sources.” Chapter 3, “ The Structure of Solvent Mixtures”, is a brief (21 page) overview of neutron and X-ray diffraction and NMR and IR spectroscopic investigations of structure in binary solvent systems, as well as a perfunctory nod of recognition to computer-based simulation studies. As expected, the bulk of the discussion focuses on the measurement and calculation of pair correlation functions. Interesting examples are chosen, but the brevity of this chapter permits no more than a superficial treatment. “Preferential Solvation in Binary Solvent Mixtures”, Chapter 4 (37 pages), offers brief discussions of associated liquid mixture theory, solvation shells, microheterogeneity, etc. The more common theoretical formulations for thermodynamic excess functions are reviewed. Wilson’s equations and the nonrandom two liquid, the quasi-lattice quasi-chemical and the universal quasi-chemical formalisms for the excess free energy and its derivatives are developed in an orderly fashion. These similar kinds of approaches are then contrasted with methods based on the Kirkwood-Buff integral equation, which connects the paircorrelation function with excess thermodynamic properties on one hand and preferential solvation parameters on the other. Numerous specific examples for aqueous cosolvent systems are briefly discussed, and their preferential solvation parameters are reported. Much of this work was due to Marcus himself. The next chapter, “Preferential Solvation of Solutes” (58 pages), is naturally divided into sections treating solutions of 6340 J. AM. CHEM. SOC.
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nonelectrolytes in aqueous and nonaqueous cosolvent mixtures and solutions of electrolytes in aqueous cosolvent mixtures. Both spectroscopic and thermodynamic approaches are reviewed. Considerable space is devoted to Ben Naim’s treatment of nonelectrolyte solutes in aqueous cosolvent mixtures, including permanent gas solutes. The development here, albeit brief, is lucid and to the point. Numerous specific examples are briefly discussed. The treatment of electrolyte/aqueous cosolvent mixtures is much more abbreviated. The chapter concludes with short discussions of spectroscopic (principally NMR) studies of preferential solvation and structure. The final chapter of the book, “Multicomponent Solvent Mixtures” (12 pages), gives an all too brief introduction to the systematics of thermodynamic description and preferential solvation in ternary (and higher) cosolvent mixtures. To sum up, this book is a well-written and well-organized review of the present status of solution physicochemistry of binary cosolvent mixtures. It is an excellent entry point into the voluminous literature of the field and succeeds very well in maintaining a balance between empirical observation and correlation and theory. Alexander Van Hook, UniVersity of Tennessee JA025309S 10.1021/ja025309s
Principles and Applications of Ion Scattering Spectrometry: Surface Chemical and Structural Analysis. By J. Wayne Rabalais (University of Houston). John Wiley & Sons, Inc.: Hoboken, NJ. 2003. xvi + 306 pp. $94.95. ISBN 0-471-20277-0. To many of us, ion scattering spectrometry (ISS) is a vacuum surface analysis technique that can be used to determine the elemental composition of the top monolayer of a surface. After reading this book, I became aware of just how limited my view of ISS was. The author has truly revealed the scope and future potential of this technique. The book begins with an introduction to ISS that could easily be used in a surface analysis chapter of a textbook on instrumental analysis, because it is written at the level of a junior or senior undergraduate physical science major. The remainder of the book, however, is at the level of a beginning graduate student in the physical sciences. Chapter 2 concerns the theoretical basis of ISS, which is mathematically intensive and can be quite intimidating. In this chapter, Rabalais does an outstanding job of making the math easy to follow, and, because of that, the concepts are easier to grasp. Multiple collisions can be very difficult to model mathematically, but the author introduces scattering by an atomic string to treat multiple scattering in ordered solids. With this approximation, shadowing and blocking cones can be understood using algebra and a bit of calculus. I did find a couple of flaws in the treatment of the dynamics of atomic collisions: in eq 28, the units are not balanced, and Figure 2.6 needs to be redrawn to make it consistent with eq 43. Chapter 3, entitled “Experimental Methods”, covers the full range of spectrometers, from the workhorse electrostatic cylindrical mirror and hemispherical energy analyzer-based instrumentsthat employ noble gas ion sources and channeltron
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detectors to the newer time-of-flight analyzer-based instruments that use pulsed ion sources and multichannel plate detectors. Hardware, geometrical arrangements of modules, electronics, and practical matters, such as resolution, spectrometer transmission, detector efficiency, etc., are all discussed. This is followed by a presentation of the different types of spectra that can be recorded. The familiar energy spectra are discussed only briefly and justifiably so, because there are many excellent review articles and books that cover this area. Time-of-flight spectra, which are very rich in information and unfamiliar to most researchers, are discussed extensively. The capabilities of the time-of-flight techniques for structural analysis are covered in three chapters. First, the structural analysis capabilities of time-of-flight scattering and recoiling spectrometry are presented, laying the foundation for time-offlight scattering and recoil imaging spectrometry (TOF-SARIS), a technique that is complementary to low energy electron diffraction (LEED). Because TOF-SARIS is a direct-space method for the determination of surface structure, whereas LEED is a reciprocal space method, TOF-SARIS data should be easier to interpret than LEED data. However, experimental SARIgrams are sufficiently complex that theoretical SARIgrams based on possible models for a surface are needed to interpret the results. Although very little math is used in the discussion of TOF-SARIS, this is some of the hardest material to master. Without the color plate inserts that are provided, the reader being introduced to TOF-SARIS for the first time would probably be lost. If the instrumentation were simpler, TOF-SARIS would probably supplant LEED as the primary technique for surface crystallography. An entire chapter is devoted to a variety of applications that involve both clean and adsorbate-covered single-crystal surfaces of metals and semiconductors. A single chapter is devoted to ion-surface charge exchange processes and inelastic energy loss in ion scattering spectrometry. The topic is very important, because inelastic energy losses affect the position of the peaks in the energy spectra for scattered primaries, whereas ion surface charge exchange processes affect the intensities observed in all of the ion spectrometries. The need for modeling the intensities is greater, because quantitation depends on them. The fundamental processes affecting ion intensities are discussed, and mathematical expressions are presented for the important parameters that determine ion yields. There is an apparent inconsistency between Figure 8.5 and the equations for inelastic energy losses derived on page 191. The equations come from another source and assume that both elastic and inelastic scattering commence at the close encounter, whereas the figure is premised on elastic loss beginning before the close encounter; it is unclear how this difference might affect the equations, however. Quantitative agreement between experimental results and theoretical results has not yet been achieved, but the progress being made is adequately described. A chapter on hyperthermal reactive ion scattering introduces the reader to this relatively recent technique. The technique requires that source ions spend sufficient time at the surface so that they can pick up molecules clinging to it. In that regard, hyperthermal cesium ion beams are the most useful, because (1) these heavy ions have a low overall probability of being neutralized during the scattering process, (2) they readily form cation complexes with electron-rich molecules, and (3) cesium ion sources are readily available. The author identifies the unique
capabilities of the technique, as well as the current limitations. The most serious limitation is the difficulty of quantifying the technique. The final chapter is a bibliography of 835 references on ion scattering spectrometry covering the time period from 1953 to 2002. It contains a wealth of resources and is not simply a compilation of the references that appear at the ends of the chapters. I learned a lot from this book and highly recommend it to all surface scientists and mass spectrometrists. As a textbook, it could be used at the graduate level for a special topics course on ion scattering spectrometry. Vaneica Y. Young, UniVersity of Florida JA025336I 10.1021/ja025336i
Encyclopedia of Agrochemicals, Volumes 1-3. Edited by Jack R. Plimmer. John Wiley & Sons, Inc.: Hoboken. 2002. 1664 pp. $975.00. ISBN 0-471-19363-1. This encyclopedia includes self-contained articles from experts of international renown covering the following areas within the agrochemical field: analytical techniques, chemical substances, environment aspects, fungicides, herbicides, insecticides, and regulatory and toxicological issues. Chemicals used in pest management and soil fertility are emphasized. Most articles also include a glossary of definitions, tables and diagrams, literature citations, and suggestions for further reading. An on-line edition of the encyclopedia is also available. JA025361O 10.1021/ja025361o
Encyclopedia of Catalysis, Volumes 1-6. Edited by Istvan T. Horvath (Eotvos Lorand University, Budapest). John Wiley & Sons, Inc.: Hoboken. 2002. 4918 pp. $1995.00. ISBN 0-471-24183-0. This is a comprehensive encyclopedia written by worldrenowned scientists and engineers with expertise in the area of catalysis. It covers the principles of homogeneous, heterogeneous, and biological catalysis; the preparation and characterization of catalysts; the scope of catalytic reactions; use of theory and computation in catalysis; reaction engineering and modeling of catalytic processes; and existing catalytic technologies. An on-line edition of the encyclopedia is also available. JA025360W 10.1021/ja025360w
Mass Spectrometry and Hyphenated Techniques in Neuropepetide Research. Edited by Jerzy Silberring (Jagiellonian University, Krakow, Poland) and Rolf Ekman (Go¨teborg University/Sahlgrenska University Hospital, Molndal, Sweden). J. Wiley & Sons: New York. 2002. xiv + 558 pp. $99.95. ISBN 0-471-35493-7. This year’s Nobel Prize in Chemistry was awarded to Fenn and Tanaka for their research and development of new ionization J. AM. CHEM. SOC.
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methods for mass spectrometric analyses of biological molecules. This book highlights the application of these advances for the analysis of neuropeptides and provides a comprehensive review of a wide variety of mass spectrometric instrumentation and techniques for the study of peptides and proteins in general. This book contains 21 chapters, which are organized into four parts. Part One includes introductory remarks about the development of mass spectrometry for the analysis of proteins and also provides a general overview of the function of neuropeptides and current methods for their characterization. Part Two introduces the reader to selected hyphenated techniques in mass spectrometry for analyzing peptides and proteins. Some chapters in this section address methods specific to the characterization of neuropeptides, whereas other chapters focus on the development of techniques for studying a wide spectrum of protein samples. Figures are broadly distributed throughout each chapter and include illustrations of instrumentation and representative data that were obtained using the different hyphenated techniques. Part Three of the book contains seven chapters, with each describing a selected application of mass spectrometry to peptide research. Again, not all of the chapters in this section deal solely with analysis of neuropeptides. What is most striking about this section of the book is the diversity of both the research problems that are presented and the large number of different
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mass spectrometric techniques and instruments that are used to solve each challenge. The fourth and final part of the book highlights the selected application of mass spectrometry to biomedical sciences. The large amount of data included in this concluding section demonstrates the validity and analytical value of mass spectrometry to protein research. More than one-half of these chapters focus specifically on identification and characterization of neuropeptides. This book provides an overall perspective of the wide variety of mass spectrometric techniques that have been recently developed for analysis of peptides and proteins. Readers with advanced training in the field of mass spectrometry will appreciate its concise summaries of the many recent advances in the field. Its value is not limited to experts, however. The information in this book should also be useful to nonexperts interested in applying the latest technological advances in this field to their own area of protein research. Overall this is a particularly timely reference that focuses on recent progress of mass spectrometry in protein research, with emphasis on the demands associated with analysis of neuropeptides. Susan E. Martin, UniVersity of the Sciences in Philadelphia JA025294Y 10.1021/ja025294y
