We take great pleasure in presenting Vol. IV of Biological Magnetic Resonance, a series that continues to give us pride. In this volume, we are pleased to have our first chapter on the applications of ESR to problems in medicine, written by Butterfield. Armitage and Otvos describe their extensive Cd-l13 NMR study in a chapter that should delight the spectroscopists as well as the biochemists, since the systems investigated have not yet been modeled. Kaptein presents an eloquent exposition of the principles and applications to biological systems of the photo-CIDNP technique, to which he has made pioneering contributions. Perkins tells everything one always wanted to know about the applications of ring current calculations in structural studies of biological macromolecules. Our philosophy has been, and continues to be, to present topics of current interest by authors who are active in their field, while maintaining the inter national flavor of the series. Ideally, the coverage of each topic should approach that found both in a textbook and in a reference book, rather than being a mere literature review. We are grateful to the authors for their cooperation in this respect. We continue to solicit the comments and suggestions of our readers and our colleagues, and thank those who have already responded, including the reviewers in the periodicals. Lawrence J. Berliner Jacques Reuben ix Contents Chapter 1 Spin Labeling in Disease D. Allan Butterfield 1. Introduction ...................................... . 2. Membrane Structure . . . . . . . . . . . . . . . . . . . . . . . . . . 2 . . . . . . . 2.1. General Principles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 2.2. The Erythrocyte Membrane. . . . . . . . . . . . . . . . . . . 4 . . . . .

Interplay between Metal Ions and Nucleic Acids provides in an authoritative and timely manner in 12 stimulating chapters, written by 24 internationally recognized experts from 8 nations, and supported by nearly 1500 references, about 20 tables, and 125 illustrations, many in color, a most up-to-date view on metal ion-nucleic acid interactions; the characterization of which is covered in solution and in the solid state. The volume concentrates on modern developments encompassing topics in the wide range from G-quadruplexes via DNAzymes, catalysis at the DNA scaffold, and metal-mediated base pairs to peptide nucleic acids (PNAs) being thus of relevance, e.g., for chemistry and nanotechnology but also for molecular biology and (genetic) diagnostics.

This is the third volume in the Reviews in Fluorescence series. To date, two volumes have been both published and well received by the scientific community. Several book reviews have also favorably described the series as an "excellent compilation of material which is well balanced from authors in both the US and Europe". Of particular mention we note the recent book review in JACS by Gary Baker, Los Alamos. In this 3rd volume we continue the tradition of publishing leading edge and timely articles from authors around the world. We hope you find this volume as useful as past volumes, which promises to be just as diverse with regard to content. Finally, in closing, we would like to thank Dr Kadir Asian for the typesetting of the entire volume and our counterparts at Springer, New York, for its timely publication. Professor Chris D. Geddes Professor Joseph R. Lakowicz August 20*^ 2005.

Chemical vapor sensing arrays have grown in popularity over the past two decades, finding applications for tasks such as process control, environmental monitoring, and medical diagnosis. This is the first in-depth analysis of the process of choosing materials and components for these "electronic noses", with special emphasis on computational methods. For a view of component selection with an experimental perspective, readers may refer to the complementary volume of Integrated Microanalytical Systems entitled "Combinatorial Methodologies for Sensor Materials."

Numerous works on non-destructive testing of food quality have been reported in the literature. Techniques such as Near InfraRed (NIR) spectroscopy, color and visual spectroscopy, electronic nose and tongue, computer vision (image analysis), ultrasound, x-ray, CT and magnetic resonance imaging are some of the most applied for that purpose and are described in this book. Aspects such as theory/basics of the techniques, practical applications (sampling, experimentation, data analysis) for evaluation of quality attributes of food and some recent works reported in literature are presented and discussed. This book is particularly interesting for new researchers in food quality and serves as an updated state-of-the-art report for those already familiar with the field.

The intrinsic or natural fluorescence of proteins is perhaps the most complex area of biochemical fluorescence. Fortunately the fluorescent amino acids, phenylalanine, tyrosine and tryptophan are relatively rare in proteins. Tr- tophan is the dominant intrinsic fluorophore and is present at about one mole % in protein. As a result most proteins contain several tryptophan residues and even more tyrosine residues. The emission of each residue is affected by several excited state processes including spectral relaxation, proton loss for tyrosine, rotational motions and the presence of nearby quenching groups on the protein. Additionally, the tyrosine and tryptophan residues can interact with each other by resonance energy transfer (RET) decreasing the tyrosine emission. In this sense a protein is similar to a three-particle or mul- particle problem in quantum mechanics where the interaction between particles precludes an exact description of the system. In comparison, it has been easier to interpret the fluorescence data from labeled proteins because the fluorophore density and locations could be controlled so the probes did not interact with each other. From the origins of biochemical fluorescence in the 1950s with Prof- sor G. Weber until the mid-1980s, intrinsic protein fluorescence was more qualitative than quantitative. An early report in 1976 by A. Grindvald and I. Z. Steinberg described protein intensity decays to be multi-exponential. Attempts to resolve these decays into the contributions of individual tryp- phan residues were mostly unsuccessful due to the difficulties in resolving closely spaced lifetimes.

Biological membranes play a central role in cell structure, shape and functions. However, investigating the membrane bilayer has proved to be difficult due to its highly dynamic and anisotropic structure, which generates steep gradients at the nanometer scale. Due to the decisive impact of recently developed fluorescence-based techniques, tremendous advances have been made in the last few years in our understanding of membrane characteristics and functions. In this context, the present book illustrates some of these major advances by collecting review articles written by highly respected experts. The book is organized in three parts, the first of which deals with membrane probes and model membranes. The second part describes the use of advanced quantitative and high-resolution techniques to explore the properties of biological membranes, illustrating the key progress made regarding membrane organization, dynamics and interactions. The third part is focused on the investigation of membrane proteins using the same techniques, and notably on the membrane receptors that play a central role in signaling pathways and therapeutic strategies. All chapters provide comprehensive information on membranes and their exploration for beginners in the field and advanced researchers alike.

In 1988 the Mossbauer effect community completed 30 years of continual contribution to the fields of nuclear physics, solid state science, and a variety of related disciplines. To celebrate this anniversary, Professor Gonser of the Universitat des Saarlandes has contributed a chapter to this volume on the history of the effect. Although Mossbauer spectroscopy has reached its mature years, the chapters in this volume illustrate that it is still a dynamic field of science with applications to topics ranging from permanent magnets to biologi cal mineralization. During the discussion of a possible chapter for this volume, a potential author asked, "Do we really need another Mossbauer book?" The editors responded in the affirmative because they believe that a volume of this type offers several advantages. First, it provides the author with an opportunity to write a personal view of the subject, either with or without extensive pedagogic content. Second, there is no artificially imposed restriction on length. In response to the question, "How long should my chapter be?," we have responded that it should be as long as is necessary to clearly present, explain, and evaluate the topic. In this type of book, it is not necessary to condense the topic into two, four, or eight pages as is now so often a requirement for publication in the research literature."

In virtually all types of experiments in which a response is analyzed as a function of frequency (e. g., a spectrum), transform techniques can significantly improve data acquisition and/or data reduct ion. Research-level nuclear magnet ic resonance and infra-red spectra are already obtained almost exclusively by Fourier transform methods, because Fourier transform NMR and IR spectrometers have been commercially available since the late 1960.s. Similar transform techniques are equally valuable (but less well-known) for a wide range of other chemical applications for which commercial instruments are only now becoming available: for example, the first corrmercial Fourier transform mass spectrometer was introduced this year (1981) by Nicolet Instrument Corporation. The purpose of this volume is to acquaint practicing chemists with the basis, advantages, and applica of Fourier, Hadamard, and Hilbert transforms in chemistry. For tions almost all chapters, the author is the investigator who was the first to apply such methods in that field. The basis and advantages of transform techniques are described in Chapter 1. Many of these aspects were understood and first applied by infrared astronomers in the 1950.s, in order to improve the otherwise unacceptably poor signal-to-noise ratio of their spec tra. However, the computations required to reduce the data were painfully slow, and required a 1 arge computer."

Despite achievements in the application of enzymes, antibodies and biological receptors to diagnostics and sensing, the last two decades have also witnessed the emergence of a number of alternative technologies based on synthetic chemistry. This volume shows how synthetic receptors can be designed with characteristics that make them attractive alternatives to biological molecules in the sensory and diagnostics fields, with contributions from leading experts in the area. Subjects covered include synthetic receptors for a range of biomolecules, the use of antimicrobial peptides for the detection of pathogenic microorganisms, the development of molecularly imprinted polymer (MIP) nanoparticles, the in silico design of MIPs and MIP-based sensors, and two chapters examining the development of sensors from an industrial point of view. The particular focus of all chapters is on practical aspects, either in the development process or the applications of the synthesized materials. This book will serve as an important reference work for business leaders and technology experts in the sensors and diagnostics sector.

The development of chemicals to selectively control the growth of weeds has been a fascinating success story which has unfolded largely during the last four decades. The dramatic growth of herbicide research that followed the wartime discoveries of the auxin-type herbicides (phenoxyalkanoic acids) resulted in a whole range of compounds and mixtures which are used to eliminate broad-or narrow-leaved weeds from agricultural, horticul tural, or forestry crops. Today, the safe use of this armament of compounds requires our understanding of their mode of action, metabolism, and environmental persistence. The most recently developed herbicides are highly effective inhibitors of specific enzyme systems, and formulation may be an important factor determining their efficient delivery at specific target sites. In this book, the major target sites of herbicide action are discussed in Chapters 1-5, with particular reference to photosynthesis; amino acid, lipid, and carotenoid synthesis; and other primary target sites. The effects of synergists or antagonists as modifiers of herbicide action are described in Chapter 6. The importance of efficient target site delivery as a fundamental factor in herbicide activity and selectivity is generally recognized. Delivery of a potentially lethal dose of active ingredient may depend on a whole range of factors including the efficiency of application, retention, absorption, translocation, immobilization, and detoxification. These aspects are con sidered in the remaining chapters, with particular reference to the pathways and mechanisms involved in the uptake, translocation, and metabolism of soil-and foliage-applied herbicides."

- __ * ___ __ * - __ e _e __ M-A-S-S S-P-GBP-C-T-R-O-M-GBP-T-R-Y in Morse code This volume collects descriptions of selected recent developments in state-of- the-art mass spectrometric methods and reflects the broad-based approaches that mass spectroscopists apply to a variety of important clinical and bio- medical problems. One chapter reviews current mass-spectrometric instrumen- tation and techniques, and other chapters describe the use of mass-spectro- metric methods for the analysis of diacylglycerylphospholipids; modifications to DNA molecules; the characterization of variant hemoglobins; and charac- terization of urinary nucleosides. The final chapter describes the new technique of combined microdialysis/mass spectrometry. This volume represents the collected efforts of several highly productive researchers who have developed new methods and instrumentation and have applied them to current research problems, such as lipid storage diseases, cancer, hemoglobinopathies, and brain neurochemistry. The chapters in Vol- umes 1 and 2 define the outlines of clinical and biomedical mass spectrometry and attest to the flexibility and creativity of mass spectroscopists and their interaction with biologic and clinical scientists. The authors in this volume are to be congratulated for their writing efforts, their scientific vigor and rigor, their intellectual contributions, and the ex- perimental details that are described in these chapters. I thank each author for collaborating with me on the production of this volume, and I hope these chapters will help the practitioners of, and the newcomers to, the field of mass spectrometry.

Today more than 5 million chemicals are known and roughly 100,000 of them are frequently used, with both numbers rising. Many of these chemicals are ultimately released into the environment and may cause adverse effects to ecosystems and human health. Effect-directed analysis (EDA) is a promising tool for identifying predominant toxicants in complex, mostly environmental mixtures combining effect testing, fractionation and chemical analysis. In the present book leading experts in the field provide an overview of relevant approaches and tools used in EDA. This includes diagnostic biological tools, separation techniques and advanced analytical and computer tools for toxicant identification and structure elucidation. Examples of the successful application of EDA are discussed such as the identification of mutagens in airborne particles and sediments, of endocrine disruptors in aquatic ecosystems and of major toxicants in pulp and paper mill effluents. This book is a valuable, comprehensive and interdisciplinary source of information for environmental scientists and environmental agencies dealing with the analysis, monitoring and assessment of environmental contamination.

Molecular Logic Gates and Luminescent Sensors Based on Photoinduced Electron Transfer, by A. Prasanna de Silva and S. Uchiyama; Luminescent Chemical Sensing, Biosensing, and Screening Using Upconverting Nanoparticles, by D. E. Achatz, R. Ali, and O. S. Wolfbeis; Luminescence Amplification Strategies Integrated with Microparticle and Nanoparticle Platforms, by S. Zhu, T. Fischer, W. Wan, A. B. Descalzo, and K. Rurack; Luminescent Chemosensors Based on Silica Nanoparticles, by S. Bonacchi, D. Genovese, R. Juris, M. Montalti, L. Prodi, E. Rampazzo, M. Sgarzi, and N. Zaccheroni; Fluorescence Based Sensor Arrays, by R. Paolesse, D. Monti, F. Dini, and C. Di Natale; Enantioselective Sensing by Luminescence, by A. Accetta, R. Corradini, and R. Marchelli

The past decade has witnessed major advances in our understanding of the chemical composition, structure, and reactivity of the complex organic-rich fossil matter known as "coal. " Nevertheless, important scientific questions concerning molecular weight distributions, degree of crosslinking, typical duster sizes, type of interconnecting bridges, the possible role of a "mobile phase," and the nature of organic sulfur forms remain topics of heated debate. Moreover, there appears to be a notable lack of consensus regarding the overall direction and goals of structural elucidation work. Is it worthwhile to study whole coal samples, or should we separate out the various, more or less well-defined, maceral and mineral constituents before attempting to describe the structural and compositional features of coal at the molecular Ievel? Second, should there be more emphasis on key structural features and average statistical parameters, or is it necessary to identify individual chemical structures in considerable detail? From the developments of the past decade it is clear that advanced spectroscopic techniques are playing an increasingly important role in resolving difficult questions with regard to the chemical structure and composition of coal. Moreover, it has become equally clear that no single spectroscopic approach can provide all the answers but multiple techniques need to be used in a highly integrated and synergistic manner.

More and more biologists, chemists, pharmacologists, toxicologists, gov ernmental agencies, and "food control" (regulatory) ofncials around the world are nnding it increasingly difncult to keep abreast of the technical literature in the pesticide neid; indeed, many libraries do not have even a small proportion of the journals and other sources that now regularly contain research, development, and application information ab out all aspects of modern chemical pest control. As a result, a very large number of requests has come to "Residue Reviews" to publish detailed digests of information on single pesticide chemicals so that the interested person in any part of the world could easily be brought up to date with all available important in formation without having to search probably several hundred literature sources, many of them obscure or simply not available except in very large libraries. The service and convenience rendered the readership by such a series of volumes on major individual pesticide chemicals would therefore be considerable. Type and scope of coverage in this series of single-pesticide volumes will oE course vary with available information. The coverage should be as com plete as possible, however, to be of maximum value to all interested indi vi duals, industries, research institutions, and governmental agencies con cerned with the continuing production of an adequately large yet safe food supply for the world. Among the topics bracketed for a single pesticide should ideally be: I. Introduction 11."

The Springer Handbook of Enzymes provides concise data on some 5,000 enzymes sufficiently well characterized - and here is the second, updated edition. Their application in analytical, synthetic and biotechnology processes as well as in food industry, and for medicinal treatments is added. Data sheets are arranged in their EC-Number sequence. The new edition reflects considerable progress in enzymology: the total material has more than doubled, and the complete 2nd edition consists of 39 volumes plus Synonym Index. Starting in 2009, all newly classified enzymes are treated in Supplement Volumes.

Reviewing over 100 chemical and physical methods for analysis of polymers, Manual of Plastics Analysis is so detailed and comprehensive that chemists can apply the methods - many previously unpublished - directly from the book. A genuine laboratory manual, the volume supplies prodigious amounts of up-to-date information on all types of polymers, polymer additives, volatiles, adventitious impurities, monomers, metals, and pigments. Extremely well-suited for classroom teaching, research, or industrial applications, the book contains numerous tables and figures, as well as many chemical equations illustrating its analytical techniques.

I knew nothing of the work of C. G. Vayenas on NEMCA until the early nineties. Then I learned from a paper of his idea (gas interface reactions could be catalyzed electrochemically), which seemed quite marvelous; but I did not understand how it worked. Consequently, I decided to correspond with Professor Vayenas in Patras, Greece, to reach a better understanding of this concept. I think that my early papers (1946, 1947, and 1957), on the relationship between the work function of metal surfaces and electron transfer reactions thereat to particles in solution, held me in good stead to be receptive to what Vayenas told me. As the electrode potential changes, so of course, does the work function at the interface, and gas metal reactions there involve adsorbed particles which have bonding to the surface. Whether electron transfer is complete in such a case, or whether the effect is on the desorption of radicals, the work function determines the strength of their bonding, and if one varies the work function by varying the electrode potential, one can vary the reaction rate at the interface. I got the idea. After that, it has been smooth sailing. Dr. Vayenas wrote a seminal article in Modern Aspects of Electrochemistry, Number 29, and brought the field into the public eye. It has since grown and its usefulness in chemical catalytic reactions has been demonstrated and verified worldwide.

It is a great pleasure to have the opportunity to honor our distinguished colleague, Professor Leo Brewer, on the occasion of his sixty-fifth birth day, with this special volume of High Temperature Science. Leo and his wife, Rose, are personal friends of several generations of students and postdoctoral researchers at the University of California at Berkeley. Their concern and understanding has been important to many of us over the past forty years. Each paper in this volume has at least one author who was a gradu ate student or a postdoctoral researcher in Leo's laboratory at Berkeley. The variety of topics is indicative of the wide-ranging science done by Brewer-ites and by Leo Brewer himself. He has personally participated in the resolution of many of the classical problems of high-temperature science-from the heat of sublimation of graphite to the dissociation en ergy of nitrogen to the prediction of binary and ternary phase diagrams. He and his students have made major contributions to atomic and molec ular spectroscopy. He has made significant contributions to the develop ment of efficient systems for energy conversion and to ceramics. In addi tion to his research activities, Leo Brewer has been a long-time participant in the dynamic undergraduate teaching program of the Berkeley Chemistry Department. He has provided crucial insight for stu dents involved in those career-shaping experiences that one endures while acquiring the basics of inorganic, organic, and physical chemistry with that interwoven common bond of thermodynamics."

Over the last several years, the field of materials science has witnessed an explosion of new, advanced materials. They encompass many uses and include superconductors, alloys, glasses, and catalysts. Not only are there quite a number of new enhies into these generic classes of materials, but the materials themselves represent a wide array of physical forms as well. Bulk materials, for example, are being synthesized and applica tions found for them, while still other materials are being synthesized as thin films for yet still more new (and in some cases, as yet unknown) applications. The field continues to expand with (thankfully ) no end in sight as to the number of new possibilities. As work progresses in this area, there is an ever increasing demand for knowing not only what material is formed as an end product but also details of the route by which it is made. The knowledge of reaction mechanisms in their synthesis many times allows a researcher to tailor a preparative scheme to either arrive at the final product in a purer state or with a better yield. Also, a good fundamental experimental knowledge of impuri ties present in the final material helps the investigator get more insight into making it."

to the Fundamental and Applied Catalysis Series Catalysis is important academically and industrially. It plays an essential role in the manufacture of a wide range of products, from gasoline and plastics to fertilizers and herbicides, which would otherwise be unobtainable or prohibitive ly expensive. There are few chemical-or oil-based material items in modern society that do not depend in some way on a catalytic stage in their manufacture. Apart from manufacturing processes, catalysis is finding other important and over-increasing uses; for example, successful applications of catalysis in the control ofpollution and its use in environmental control are certain to in crease in the future. The commercial import an ce of catalysis and the diverse intellectual challenges of catalytic phenomena have stimulated study by a broad spectrum of scientists including chemists, physicists, chemical engineers, and material scientists. Increasing research activity over the years has brought deeper levels of understanding, and these have been associated with a continually growing amount of published material. As recentlyas sixty years ago, Rideal and Taylor could still treat the subject comprehensively in a single volume, but by the 19 50s Emmett required six volumes, and no conventional multivolume text could now cover the whole of catalysis in any depth.

The symposium which provided the incentive for this volume was conducted in San th Diego, California as a part of the 207 National Meeting of the American Chemical Society, March 13-17, 1994. It was conceived partly to continue an informal decennial sequence of sym posia dedicated to the topic off element separations. A lot has changed in the world of f ele ments over the last ten years, precipitating a change in emphasis which should be evident to most practitioners in the field. Production and reprocessing of nuclear fuels are no longer the principal drivers of f element separation technology. Separations technology for environment restoration, waste disposal, and the preparation of high purity lanthanides are now the defming parameters in this important field. These imperatives are reflected in the contributions to this volume. The symposium itself must be considered a success, as the attendance at all sessions was above expectations, despite the fact that it was conducted on the last two days of a large five day meeting. Our thanks to the speakers for their quality presentations, and to the audience who persevered to the end of a long meeting and against the temptation of the excellent weather of San Diego in the springtime. A complete list of symposium participants is given in Appendix 1. Preparation of this volume has been a relatively painless undertaking, largely as a result ofthe high quality ofthe submitted papers."

Stability constants are fundamental to understanding the behavior of metal ions in aqueous solution. Such understanding is important in a wide variety of areas, such as metal ions in biology, biomedical applications, metal ions in the environment, extraction metallurgy, food chemistry, and metal ions in many industrial processes. In spite of this importance, it appears that many inorganic chemists have lost an appreciation for the importance of stability constants, and the thermodynamic aspects of complex formation, with attention focused over the last thirty years on newer areas, such as organometallic chemistry. This book is an attempt to show the richness of chemistry that can be revealed by stability constants, when measured as part of an overall strategy aimed at understanding the complexing properties of a particular ligand or metal ion. Thus, for example, there are numerous crystal structures of the Li+ ion with crown ethers. What do these indicate to us about the chemistry of Li+ with crown ethers? In fact, most of these crystal structures are in a sense misleading, in that the Li+ ion forms no complexes, or at best very weak complexes, with familiar crown ethers such as l2-crown-4, in any known solvent. Thus, without the stability constants, our understanding of the chemistry of a metal ion with any particular ligand must be regarded as incomplete. In this book we attempt to show how stability constants can reveal factors in ligand design which could not readily be deduced from any other physical technique.