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Contrast Agents II: Optical, Ultrasound, X-ray and Radiopharmaceutical Imaging. Topics in Current Chemistry. Volume 222 Edited by Werner Krause (Scher...
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Advances in Chemical Physics. Volume 123. Edited by I. Prigogine (University of Texas at Austin and Universite´ Libre de Bruxelles) and Stuart A. Rice (University of Chicago). John Wiley & Sons, Inc.: New York. 2002. x + 680 pp. $175.00. ISBN 0-471-21453-1. This series is well known to the chemical physics community as covering a broad range of topics to stimulate new and creative research and to provide a learning tool for newcomers to a field. The current volume certainly follows in this tradition, although there are both successes and disappointments in its contents. The first three chapters are largely concerned with different aspects of chemical reaction dynamics. The first chapter (Dellago, Bolhuis, and Geissler) is a truly excellent review of the recently introduced transition path sampling method of Chandler and co-workers. Not only are many details of the theory and methodology described, but specific algorithms are explicitly provided, making the implementation of the method transparent. The technique is also compared to other approaches for studying rare events, and difficulties with more traditional treatments in terms of simple reaction coordinates and associated transition states are discussed. This chapter will likely be a highly useful and frequently cited reference for anyone interested in implementing, employing, or further developing the transition path sampling approach. The second and third chapters address the subject of chaotic behavior in chemical reaction dynamics. Chapter 2 (Komatsuzaki and Berry) follows a somewhat more traditional viewpoint with respect to the preceding chapter, that is, one based on transition state theory, and questions of how to extract a dividing hypersurface as free as possible from recrossings and how specific features of the potential energy surface affect the dynamics of saddle-point crossing as the energy of the system is increased above threshold values are considered. These questions are treated using an elegant formulation of the classical perturbation theory, the so-called Lie canonical perturbation theory, and the analysis in this chapter is beautifully described. A possible weak point of this contribution is that it contains only a small number of literature citations from the last five years. The third chapter (Toda) addresses the problem of the breakdown of statistical assumptions commonly invoked in transition state theory and looks at the problem of dynamical correlations between motion in wells using ideas from the theory of chaotic systems. Although this chapter is light on mathematical analysis and is somewhat narrow in its focus (the bibliography contains only 30 citations), the detailed descriptions are well written, and the author makes a strong case by analyzing direct experimental evidence for these dynamical correlations. The fourth chapter (Jung, Barkai, and Silbey) contains a pedagogical treatment of the recently emergent single molecule spectroscopic technique. The authors present a detailed analysis of a simple two-level model system, examine various important limits, and describe the prediction of various time correlation Unsigned book reviews are by the Book Review Editor. 6596

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functions. They also show that their model can be directly related to experiments in glasses in the “slow modulation” limit. Although many steps of the mathematical analysis are omitted, the ambitious reader can fill in most of these in the course of reading the article, a highly worthwhile exercise. In the next chapter, Altenberger and Dahler present a fascinating look at scaling and self-similarity, topics that are beginning to impact areas well beyond the traditional realms of physics and chemistry, where they are well known. The authors expound in detail on the role of scaling and self-similarity in a number of renormalization group theories and use these theories in several illustrative applications ranging from polymer physics and fluid thermodynamics to quantum electrodynamics. Unfortunately, only about 10% of the references cited in this article are from the last five years. The sixth chapter (Gauss and Stanton) is concerned with the important problem of computing NMR chemical shifts, and the authors nicely describe the technical issues associated with the gauge-origin problem in its first few pages. After this introduction, however, the article is somewhat disappointing. The notation is confusing (for example, no distinction is made between vector dot products and tensor products), overly terse, and many quantities are unsatisfactorily defined. Moreover, the article is rather myopic, focusing mainly on technical issues that arise in standard quantum chemistry, thus rendering the article difficult to follow for a beginner not necessarily familiar with the details of quantum chemical technology and/or notation. In addition, the authors focus on only one particular solution to the gauge problem, the gauge-including atomic orbitals method, and fail to mention other solutions, such as the continuous set of gauge transformations, individual gauges for atoms in molecules, or the method of Mauri, Pfrommer, and Louie [Phys. ReV. Lett. 1996, 77, 5300]. Finally, concerning density functional theory, the authors ignore an entire body of recent work from the plane-wave community (see, for example, papers by Mauri et al., Car and co-workers, and Parrinello and co-workers) that attempts to address many of the issues raised in the article via, for example, techniques using density functional perturbation theory and that extends computational methods for NMR chemical shifts to condensed phase systems. The next two chapters are concerned with computational issues in acidic solutions and hydrogen-bonded systems. The seventh chapter (Silva and Nascimento) is an excellent introduction to problems arising in the computational chemistry of acids, such as continuum solvation models, proton and anion solvation, and thermodynamic cycles for use in calculating pKa’s. Computational aspects of hydrogen-bonded systems are the subject of the next chapter (Karpfen). This chapter contains a lengthy bibliography (336 citations), with numerous citations to computational papers on hydrogen bonding, but the article itself seems to be little more than a description of the performance of different quantum chemical methods on a variety of specific systems. Although some of the comparisons are useful as a reference, the larger purpose of this article is lost in the details. 10.1021/ja025297a CCC: $25.00 © 2003 American Chemical Society

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The final chapter, by Barzykin et al., is an impressive 105page tour de force review of solvent effects on nonadiabatic electron-transfer reactions. Its enormous bibliography, which is the most extensive in this volume, contains 381 entries, many of which cite multiple papers. Unfortunately, so much material is covered in the chapter that pedagogy is lost. Many of the formulas are simply thrown at the reader with little explanation, so that only those already familiar with the field would likely derive substantial benefit from the article. To its credit, however, the chapter can be viewed as a summary of many important results, and the ambitious reader can certainly make use of the extensive bibliography to dig more deeply if desired. In summary, the present volume is a worthy addition to the AdVances in Chemical Physics series. In seven of its nine chapters, the references are timely, and most of the topics discussed throughout the volume are current. For the beginner wishing to gain an introduction to a given area, the utility of this volume varies from chapter to chapter. Overall, however, this volume will likely serve as a useful reference for a wide range of researchers in the chemical physics community. Mark E. Tuckerman, New York UniVersity JA025297A 10.1021/ja025297a

On-Line LC-NMR and Related Techniques. Edited by Klaus Albert (Universita¨t Tu¨bingen). John Wiley & Sons, Inc.: Chichester. 2002. xiv + 290 pp. $105.00. ISBN 0-471-49649-9. This book covers techniques for the coupling of an NMRspectrometer with liquid chromatography. In addition, interfacing with other spectroscopic techniques, such as mass spectrometry, is described, and the use of other techniques for separation, such as GPC, SFC, SFE, and capillary HPLC, is discussed. The book gives a comprehensive overview of LC-NMR, its possible applications, and related methodologies. Featuring contributions from several authors, this work outlines the general experimental setup, the implementation of automated experiments, the application of these fascinating techniques in biomedical, pharmaceutical, and drug metabolism studies, as well as in natural products analysis, and their application to the analysis of food components and studies of biological tissues and environmental samples. The book begins with a review of experimental methodology and the special circumstances involving flow-NMR spectroscopy. A discussion of solvent suppression techniques-essential for a successful implementation of LC-NMR-and various LC-NMR modes (on-flow, stop-flow, and loop storage) follows. Chapter 2 provides an introduction to the automation of LC-NMR and LC-NMR/MS techniques, which is supplemented by a discussion of the numerous applications of LC-NMR to the fields described above. In the next chapter, biomedical and pharmaceutical applications are covered, and numerous examples are given that show the application of LC-NMR in combinatorial chemistry, analysis of drug impurities and natural products, and trapping of reactive intermediates, to mention a few. The application of LC-NMR to drug metabolism, probably one of its earliest successful applications, is discussed

in Chapter 4. In the following chapter, structural analysis of natural products by LC-NMR is further demonstrated on samples of saponins from marine origin, and analysis of carotenoid isomers is used as an example for the application of this technique in food analysis. The potential of LC-NMR is shown in Chapter 6 in the analysis of environmental samples, starting with structurally simple aromatic compounds and further extended toward the detection of phosphorus-containing samples, where the low sensitivity of 31P is overcome simply by comparing LC-NMR runs with and without 31P decoupling. In the remaining two chapters, examples of chromatographic techniques other than HPLC are given, GPC, SFC, and SFE. A discussion of nanoliter NMR spectroscopy includes a review of probe designs and the use of small detection volumes through applications with capillary separation techniques. Finally, some aspects for the use of HPLC-13C NMR are presented, and an outlook is provided on the development of parallel NMR detection to further improve the speed of analysis for combinatorial chemistry. Overall, numerous “real-life” examples throughout the book strengthen the discussions of LC-NMR applications and give newcomers a number of models from which to start their own experiments. A more comprehensive comparison of solvent suppression techniques, such as presaturation (NOESY), softpulse multiple irradiation, and WET, would have been welcome in the beginning chapters, because this directly affects the performance of the LC-NMR experiment. Furthermore, the value of this book would have been improved by a thorough discussion of methodologies, such as column-switching techniques, that enhance the separation process when preparing samples and thus facilitate the NMR spectroscopic analysis. Because the book is a collection of reviews by several authors, some redundancy is inevitable: for example, there are several pictures of the experimental setup of LC-NMR. Nevertheless, this book is the best compilation of LC-NMR knowledge and related techniques to date and therefore is a must for anyone who wants to use this methodology to solve everyday analytical problems. It gives an excellent overview of the state-of-the-art and an extensive list of citations to original literature. Bernhard Vogler, UniVersity of Alabama in HuntsVille JA025335Q 10.1021/ja025335q

Contrast Agents II: Optical, Ultrasound, X-ray and Radiopharmaceutical Imaging. Topics in Current Chemistry. Volume 222. Edited by Werner Krause (Schering AG, Berlin). Springer-Verlag: Berlin, Heidelberg, New York. 2002. x + 292 pp. $199.00. ISBN 3-540-43451-8. Currently, the field of clinical imaging is huge and growing. Traditional imaging modalitiessX-ray technique, gammascintigraphy, magnetic resonance imaging, ultrasonography, and computed tomographysare still developing, and new modifications as well as new modalities are also continuously being added to the list, including PET, SPECT, optical imaging, and receptor imaging. All of these approaches require the use of their own specific contrast agents, opening almost unlimited opportunities for researchers and clinicians interested in synthetic J. AM. CHEM. SOC.

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chemistry to develop a variety of new chemical substances that meet the tough requirements for clinically acceptable contrast media. The editor of this volume did a great job. The book contains a well-balanced mix of research on successfully preparing and improving imaging agents for new and emerging areas of clinical imaging, such as optical imaging or receptor imaging, studies of the already recognized but still developing fields, such as ultrasound imaging and positron emission tomography, and discussions of the most traditional and established imaging modalities, like X-ray imaging. As expected from a book published in this series, all of the chapters provide a wealth of detailed and nicely presented chemistry, for example, synthesis, structures, properties, of various contrast agents, and also present limited clinical data showing the potential application of these new agents. Luckily, the book is not overloaded with actual medical images and clinical examples, a frequent but unwelcome occurrence with many books targeted to nonclinical audiences. The volume opens with the chapter on optical imaging. This growing area of clinical research was brought to life by the rapid development of relevant instrumentation and by the fact that nonionizing radiation could be applied. All of the major chemical groups of contrast agents are described here in adequate detail, including various dyes, chelates of lanthanides, and derivatives of 5-aminolevulinic acid. Examples of the clinical use of this approach clearly show its scope, advantages, and limitations. The next chapter covers the dozens of different markers and techniques used for the functional imaging of the liver and the kidney and provides sufficient data on their biological properties and the physiological phenomena behind the observed visual patterns. A chapter on ultrasound contrast agents follows and features a description of currently available methods of microbubble preparation with the required stability and properties as well as important data on the possible use of the microbubble approach for targeted delivery of drugs and DNA. The next three chapters provide extensive information on various X-ray contrast agents. Here, the potential reader will find a lot of excellent synthetic and analytical chemistry of iodinated low- and high-molecular-weight compounds and plenty of cutting edge information on their use for a broad variety of visualization purposes, including blood pool and liver imaging. The chemistry of β+-emitting compounds based on fluorine-18 represents the main subject of the next chapter. Because these compounds can be successfully used as contrast agents for PET, the importance of any information regarding their synthesis and properties is obvious. The last chapter deals with the emerging field of receptor-based diagnostic metalloradiopharmaceuticals, and full details of their design, structurefunction relationships, and pharmacokinetics are presented. Each chapter in this book contains very good bibliographies of relevant areas, including many references from 2000 to 2001. Together with the book Contrast Agents I, which is devoted to the chemistry of various agents for magnetic resonance

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imaging, the current book presents a clear and informative picture of what chemistry provides for the extremely important field of medical imaging and shows what kinds of future chemical studies are needed to prepare a new generation of contrast agents for both traditional and emerging imaging modalities. I certainly consider this book a success for its editor and contributors. Vladimir P. Torchilin, Northeastern UniVersity JA025324X 10.1021/ja025324x

Speciality Chemicals in Mineral Processing. Edited by D. R. Skuse (IMERYS Minerals, Sandersville, GA). Royal Society of Chemistry: Cambridge. 2002. viii + 144 pp. $129.00. ISBN 0-85404-831-6. This book was developed from the proceedings of the meeting “Speciality Chemicals in Mineral Processing” held at the University of Bath in June 2001. The 13 chapters are divided into three sections: Dispersion and Flocculation, Selective Processing, and Microbiological Control. A subject index completes the book. JA033502W 10.1021/ja033502w

Applied Homogeneous Catalysis with Organometallic Compounds: A Comprehensive Handbook in Three Volumes. Second, Completely Revised and Enlarged Edition. Edited by Boy Cornils (Hofheim, Germany) and Wolfgang A. Herrmann (Universita¨t Mu¨nchen). Wiley-VCH: Weinheim. 2002. 1450 pp. $520.00. ISBN 3-527-30434-7. The second edition of this highly successful work now comes in three volumes. Volume 1 covers applications, and Volumes 2 and 3 focus on developments. There is also an interesting historical perspective and an epilogue, both of which should provide much food for thought. The editors have collected the contributions from over 120 leading experts in homogeneous catalysis and organometallic chemistry and have produced an incredibly useful source of information. The standard of writing is uniformly high. Each chapter is concise, authoritative, and current. In fact, there is so much information that even a listing of the contents of the chapters would be well beyond the scope of this review. These volumes provide both mechanistic insights as well as details of important industrial processes. They will be of great interest to both academics as well as chemists in industry and should be on the shelves of all good chemistry libraries. Richard A. Jones, UniVersity of Texas at Austin JA0252936 10.1021/ja0252936