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.

This book, edited by Potyrailo and Amis, addresses a new paradigm-shifting approach in the search for new materials-Combinatorial Materials Science. One way to consider such an approach is to imagine an adventurous chef who decides to look for new entrees by cooking food ingredients in many pots using different combinations in every pot, and boil ing, steaming, or frying them in various ways. Although most of the pots will not have the tastiest food ever devised, some recipes will taste intriguing, and some eventually will lead to a discovery of a new fascinating cuisine. Of course, having a skilled chef design the com binatorial formulation will certainly be helpful in ensuring a successful outcome. Similar to food, each engineering material is a complex product of its chemical composition, structure, and processing. Generally, each of these components matters---change one and you get another material. Most of these "new" materials will be less good than ones we use now since existing materials have been refined with the extensive work of scientists and engi neers. At the same time if one prepares diverse materials like our adventurous chef, chang ing material composition, processing conditions and time, etc. , some of these materials will be superior to existing ones and a few might represent breakout technology.

Fluorescence spectroscopy continues its advance to more sophisticated methods and applications. As one looks over the previous decades, its appears that the first practical instruments for time-resolved measurements appeared in the 1970's. The instrumentation and analysis methods for time-resolved fluorescence advanced rapidly throughout the 1980's. Since 1990 we have witnessed a rapid migration of the principles of time-resolved fluorescence to cell biology and clinical appli- tions. Most recently, we have seen the introduction of multi-photon excitation, pump-probe and stimulated emission methods for studies of biological mac- molecules and for cellular imaging. These advanced topics are the subject of the present volume. Two-photon excitation was first predicted by Maria Goppert-Mayer in 1931, but was not experimentally observed until 1961. Observation of two-photon excitation required the introduction of lasers which provided adequate photon density for multi-photon absorption. Since the early observations of two-photon excitation in the 1960s, multi-photon spectroscopy has been limited to somewhat exotic applications of chemical physics, where it is used to study the electronic symmetry of small molecules. Placing one's self back in 1980, it would be hard to imagine the use of multi-photon excitation in biophysics or cellular imaging.

Mass spectrometry underwent dramatic changes during the decade of the 1980s. Fast atom bombardment (F AB) ionization, developed by Barber and coworkers, made it possible for all mass spectrometry laboratories to analyze polar, highly functionalized organic molecules, and in some cases ionic, inorganic, and organometallic compounds. The emphasis of much of this work was on molecular weight determination. Parallel with the development of ionization methods (molecular weight mass spectrometry) for polar biological molecules, the increased mass range of sector and quadrupole mass spectrometers and the development of new instruments for tandem mass spectrometry fostered a new era in structural mass spectrometry. It was during this same period that new instrument technologies, such as Fourier transform ion cyclotron resonance, radio frequency quadrupole ion trap, and new types of time-of-flight mass spectrometers, began to emerge as useful analytical instruments. In addi tion, laser methods useful for both sample ionization and activation became commonplace in almost every analytical mass spectrometry laboratory. In the last 5 years, there has been explosive growth in the area of biological mass spectrometry. Such ionization methods as electrospray and matrix-assisted laser desorption ionization (MALDI) have opened new frontiers for both molecular weight and structural mass spectrometry, with mass spectrometry being used for analysis at the picomole and even femto mole levels. In ideal cases, subfemtomole sample levels can be successfully analyzed. Sample-handling methods are now the limiting factor in analyz ing trace amounts of biological samples.

This volume examines the advances of invasive monitoring by means of biosensors and microdialysis. Physical and physiological parameters are commonly monitored in clinical settings using invasive techniques due to their positive outcome in patients' diagnosis and treatment. Biochemical parameters, however, still rely on off-line measurements and require large pieces of equipment. Biosensing and sampling devices present excellent capabilities for their use in continuous monitoring of patients' biochemical parameters. However, certain issues remain to be solved in order to ensure a more widespread use of these techniques in today's medical practices.

Emerging Mass Spectrometric Tools for Analysis of Polymers and Polymer Additives, by Nina Aminlashgari and Minna Hakkarainen. Analysis of Polymer Additives and Impurities by Liquid Chromatography/Mass Spectrometry and Capillary Electrophoresis/Mass Spectrometry, by Wolfgang Buchberger and Martin Stiftinger. Direct Insertion Probe Mass Spectrometry of Polymers, by Jale Hacaloglu Mass Spectrometric Characterization of Oligo- and Polysaccharides and Their Derivatives, by Petra Mischnick. Electrospray Ionization-Mass Spectrometry for Molecular Level Understanding of Polymer Degradation, by Minna Hakkarainen.

To continue the support for the growing trend of chemistry involvement in nuclear medicine, the Division of Nuclear Chemistry and Technology (DNCT) of the American Chemical Society (ACS) planned for a symposium to cover this aspect. This was expressed in arequest to me, as a member of the Program Committee, to organize a symposium on topics related to nuclear and radiochemistry applications to nuclear medicine. Realizing the growing interest in imaging, specially with positron emitting radioisotopes, I invited several colleagues to study with me the idea of imaging centers and the involvement of chemists in their structure and function. The formulated Organizing Committee supported this idea which evolved in proposing an extended international symposium to be held in conjunction with the 206th ACS National meeting in Chicago, Illinois, U. S. A. on August 22-27, 1993. The following are the members of the Organizing Committee: Jorge R. Barrio, Ph. D. Thomas E. Boothe, Ph. D. J. Robert Dahl, Ph. D. Robert F. Dannals, Ph. D. Bruce R. Erdal, Ph. D. Mark M. Goodman, Ph. D. George W. Kabalka, Ph. D. James F. Lamb, Ph. D. Ronald G. Manning, Ph. D. Henry C. Padgett, Ph. D. Roy S. Tilbury, Ph. D. Steven W. Yates, Ph. D. and Ali M. Emran, Ph. D.

The Fifteenth Eastern Analytical Symposium and the Twelfth National Meeting of the Society for Applied Spec- troscopy were held jointly in New York, November 14-16, 1973. In cooperation with the Detroit Analytical Chemists' Association, the Anachem Award in Analytical Chemistry was presented at this meeting to Dr. Rosalyn S. Ya1ow, the co- inventor (with Dr. S. Berson) of the radioimmunoassay technique. It is our privilege to include in this volume Dr. Ya1ow's award address, a review of radioimmunoassay, together with a series of three papers on related subjects, respectively by Dr. Juan M. Saavedra, Drs. Claude E. Arnaud and H. Bryan Brewer, Jr., and Dr. Sheldon P. Rothenberg. This session was organized and chaired by Dr. D. S. McCann. Following this are three papers on analytical toxi- cology in clinical chemistry, by Dr. R. A. Scala, Dr. Charles L. Winek, and Dr. James E. Gibson, a session also chaired by Dr. McCann. Finally appear two papers on the general subject of analytical developments at the FDA, by Dr. Albert L. Woodson and Dr. Walter Ho1ak, from a session under the chairmanship of Dr. S. Walters. All of these contributions, written by experts in their respective fields, make worthy additions to the continuing literature of analytical chemistry. Ivor L. Simmons Galen W. Ewing CONTENTS Radioimmunoassay: Its Past, Present, and Potential ...

In this inaugural volume of a new series, experts in the field help biochemists, analytical chemists, spectroscopists, biophysicists, and other specialists keep up with the latest techniques and technologies available in fluorescence spectroscopy.

Fluorescence spectroscopy and its applications to the physical and life sciences have evolved rapidly during the past decade. The increased interest in fluorescence appears to be due to advances in time resolution, methods of data analysis, and improved instrumentation. With these advances, it is now practical to perform time-resolved measurements with enough resolution to compare the results with the structural and dynamic features of mac- molecules, to probe the structures of proteins, membranes, and nucleic acids, and to acquire two-dimensional microscopic images of chemical or protein distributions in cell cultures. Advances in laser and detector technology have also resulted in renewed interest in fluorescence for clinical and analytical chemistry. Because of these numerous developments and the rapid appearance of new methods, it has become difficult to remain current on the science of fluorescence and its many applications. Consequently, I have asked the experts in particular areas of fluorescence to summarize their knowledge and the current state of the art. This has resulted in the initial two volumes of Topics in Fluorescence Spectroscopy, which is intended to be an ongoing series which summarizes, in one location, the vast literature on fluorescence spectroscopy. The third volume will appear shortly. The first three volumes are designed to serve as an advanced text. These volumes describe the more recent techniques and technologies (Volume 1), the principles governing fluorescence and the experimental observables (Volume 2), and applications in biochemistry and biophysics (Volume 3).

Published as a companion to Volume 12, the current volume presents the latest advances in electron paramagnetic resonance of iron proteins, metalloproteins, and free radicals. The book features a diskette containing programs for iron ERP spectral simulation and ENDOR analyses.

Major advances in instrumentation and technology have made high-performance liquid chromatography (HPLC) a pervasive tool in virtually all areas of chemical and biomedical research today. Despite HPLC's enormous growth, technical problems still bedevil most users at least occasionally. Based on their immensely successful short courses, Dolan and Snyder's landmark new book --Troubleshooting LC Systems--now makes available to every practicing chromatographer the authors' wealth of expertise from years of hands-on troubleshooting of real-world LC problems--problems that routinely cause crises and unproductive downtime in nearly every lab. Believing that successful troubleshooting requires an understanding of the basics, Dolan and Snyder open by setting forth all the fundamental principles of LC operation, then move on to a microscopic description of all the elements of LC devices, to lay out their optimal preventive maintenance routines, and ultimately to offer an unprecedentedly thorough treatment of each and every facet of troubleshooting.Displaying a special tutorial mastery--honed to a fineness during their ongoing teaching and consulting activities, and a well-received feature column in LC Magazine--the book's chapters cover: automation and robotics * approaches to troubleshooting * reactions of samples * basic separation techniques * valves, tubing, syringes * band broadening and tailing * preventive maintenance * column packing and flushing * individual LC modules * troubleshooting principles * reagents and buffering * specific problems in separation * ghost and vacancy peaks * quantitation and calibration * pumps, seals, and pistons * gradient elution problems * column composition * concentration and blockages * sample cleanup * temperature and mixing effects * detectors and recorders * column packing and flushing. In short, Dolan and Snyder's eminently practical new guide to Troubleshooting LC Systems is an essential laboratory handbook--one that empowers expert and novice chromatographer alike to solve every sort of practical laboratory problem on a day-to-day basis. No one using an LC system should be without it

During the past 15 years, there has been remarkable progress in the analysis and manipulation of DNA and its use in nanotechnology. DNA analysis is ubiquitous in molecular biology, medical diagnostics, and forensics. Much of the readout technology is based on fluorescence detection. This volume contains contributions from many experts in the field who present an overview of many aspects of DNA technology. These chapters provide an understanding of the underlying principles and technology, rather than an exhaustive review of the literature. Written in a clear straightforward style, this book is an excellent introduction for any scientist to the use of fluorescence in DNA analysis. DNA Technology is an essential reading for all academics, bench scientists, and industry professionals wishing to take advantage of the latest and greatest in this continuously emerging field. Key Features: *Comprehensive overview of the complexities of DNA analysis, *Covers topics of universal interest to a broad field of scientists, *Accessible utility in presenting state-of-the-art DNA technology, *Chapters authored by key figures in the field.

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.

Environmental chemistry is a fast developing science aimed at deciphering fundamental mechanisms ruling the behaviour of pollutants in ecosystems. Applying this knowledge to current environmental issues leads to the remediation of environmental media, and to new, low energy, low emission, sustainable processes. Chapters review analysis and remediation of pollutants such as greenhouse gases, chiral pharmaceuticals, dyes, chlorinated organics, arsenic, toxic metals and pathogen in air, water, plant and soil. Several highlights include the overlooked impact of air pollutants from buildings for health risk, innovative remediation techniques such as bioreactors for gas treatment, electrochemical cleaning of pharmaceuticals, sequestration on Fe-Mn nodules, phytoremediation and photocatalytical inactivation of microbial pathogens.

This book will be a valuable source of information for engineers and students developing novel applied techniques to monitor and clean pollutants in air, wastewater, soils and sediments.

"

With the development in the 1960s of ultrahigh vacuum equipment and techniques and electron, X-ray, and ion beam techniques to determine the structure and composition of interfaces, activities in the field of surface science grew nearly exponentially. Today surface science impacts all major fields of study from physical to biological sciences, from physics to chemistry, and all engineering disciplines. The materials and phenomena characterized by surface science range from se- conductors, where the impact of surface science has been critical to progress, to metals and ceramics, where selected contributions have been important, to bio- terials, where contributions are just beginning to impact the field, to textiles, where the impact has been marginal. With such a range of fields and applications, questions about sample selection, preparation, treatment, and handling are difficult to cover completely in one review article or one chapter. Therefore, the editors of this book have assembled a range of experts with experience in the major fields impacted by surface characterization. It is the only book which treats the subject of sample handling, preparation, and treatment for surface characterization. It is full of tricks, cautions, and handy tips to make the laboratory scientist's life easier. With respect to organization of the book, the topics range from discussion of vacuum to discussion of biological, organic, elemental or compound samples, to samples prepared ex situ or in situ to the vacuum, to deposition ofthin films. Generic considerations of sample preparation are also given.

Shunsuke Hirotsu "Coexistence of Phases and the Nature of First-Order Transition in Poly-N-isopropylacrylamide Gels," Masayuki Tokita "Friction between Polymer Networks of Gels and Solvent," Masahiro Irie "Stimuli-Responsive Poly(N-isopropyl- acrylamide), Photo- and Chemicals-Induced Phases Transitions Edward Cussler, Karen Wang, John Burban"Hydrogels as Separation Agents," Stevin Gehrke "Synthesis, Equilibrium Swelling, Kinetics Permeability and Applications of Environmentally Responsive Gels," Pedro Verdugo "Polymer Gel Phase Transition in Condensation- Decondensation of Secretory Products," Etsuo Kokufuta "Novel Applications for Stimulus-Sensitive Polymer Gels in the Preparation of Functional Immobilized Biocatalysts," Teruo Okano "Molecular Design of Temperature-Responsive Polymers as Intelligent Materials," Atsushi Suzuki "Phase Transition in Gels of Sub-Millimeter Size Induced by Interaction with Stimuli," Makoto Suzuki, O. Hirasa "An Approach to Artificial Muscle by Polymer Gels due to Micro-Phase Separation."

This book has its or1g1n in a NATO Summer School organized from June 25 to July 7 1979, in Menton, France. The purpose of this School was a comparative study of the various aspects of vibra tional spectroscopy in molecular liquids and solids. This field has been rapidly expanding in the last decade; unfortunately, its development took place independently for liquids and for solids. In these circumstances, the comparison of the basic concepts and techniques used in these two branches of physics appeared as a necessity. The lectures given at the Menton Advanced Study Institute, as well as the exceptionally fruitful and lively discussions which followed them confirmed this point of view. The need of putting together these lectures, in the form of a monograph, clearly appeared during the ASI and the lecturers accepted to write down the material they presented at the Institute, improved thanks to the remarks of the participants. It is the result of this collective work which appears in the familiar Plenum Series."

The research reported in the third volume of Analytical Calorimetry covers a wide variety of topics. The variety indicates the sophistication which thermal analysis is reaching and addition ally the ever widening applications that are being developed, Advances in instrumentation include: microcalorimeter design, development and refinement of titration calorimetry, definition of further theory of scanning calorimetry, studies of the temperature of resolution of thermistors, and a refinement of the effluent gas analysis technique and its application to agricultural chemicals as well as organic materials. A wide variety of applications is reported. These cover the fields of polymeric materials, dental materials, inorganic proteins, biochemical materials, gels, mixed crystals, and other specialized areas. Contributions also include applications of important related techniques such as thermomechanical and thermogravimetric analysis. The contributions to this Volume represent papers presented before the Division of Analytical Chemistry at the Third Symposium on Analytical Chemistry held at the 167th National Meeting of the American Chemical Society, March 30 - April 5, 1974.

The Ebro is a typical Mediterranean river characterized by seasonal low flows and extreme flush effects, with important agricultural and industrial activity that has caused heavy contamination problems. This volume deals with soil-sediment-groundwater related issues in the Ebro river basin and summarizes the results generated within the European Union-funded project "AquaTerra." The following topics are highlighted: Hydrology and sediment transport and their alterations due to climate change, aquatic and riparian biodiversity in the Ebro watershed, occurrence and distribution of a wide range of priority and emerging contaminants, effects of chemical pollution on biota and integration of climate change scenarios with several aspects of the Ebro s hydrology and potential impacts of climate change on pollution.

The primary objective of the book is to lay the foundation for a better understanding of the behavior of environmental pollutants and their fluxes with respect to climate and land use changes."

This book is intended both to be an introduction to techniques and applications of liquid chromatography/mass spectrometry and to serve as a reference for future workers. When we undertook its writing, we chose not to cover the field, particularly applications, exhaustively. Rather we wished to produce a book that would be of use to people just beginning to use the technique as well as to more advanced practitioners. In this regard, we have sought to highlight techniques and applications that are of current importance, while not neglecting descriptions of approaches that may be of significance in the future. We hope that we have succeeded in this. At the same time we hope that the bibliography, with indexes classified by author and title, will make this book of value to those who may disagree with our emphasis. ACKNOWLEDGMENTS. One of us (C. G. E. ) wishes to acknowledge the en couragment of Professor J. A. McCloskey in undertaking this project. All four of us are grateful for the continuous and expert assistance of V. A. Edmonds in the preparation of the Bibliography. Alfred L. Y ergey Bethesda, Maryland Charles G. Edmonds Richland, Washington lvor A. S. Lewis London, England Marvin L. Vestal Houston, Texas v Contents 1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . 1 . . . . . . . . . . . 2. Direct Liquid Introduction Interfaces . . . . . . . . . . 5 . . . 2. 1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2. 2. Operating Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2. 3. Specific DLI Interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 2. 3. 1. Capillary Inlets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 2. 3. 2. Diaphragm Interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 2. 3. 3. Nebulizing Interfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ."

Time-resolved fluorescence spectroscopy is widely used as a research tool in bioch- istry and biophysics. These uses of fluorescence have resulted in extensive knowledge of the structure and dynamics of biological macromolecules. This information has been gained by studies of phenomena that affect the excited state, such as the local environment, quenching processes, and energy transfer. Topics in Fluorescence Spectroscopy, Volume 4: Probe Design and Chemical Sensing reflects a new trend, which is the use of time-resolved fluorescence in analytical and clinical chemistry. These emerging applications of time-resolved fluorescence are the result of continued advances in laser detector and computer technology. For instance, pho- multiplier tubes (PMT) were previously bulky devices. Miniature PMTs are now available, and the performance of simpler detectors is continually improving. There is also considerable effort to develop fluorophores that can be excited with the red/ne- infrared (NIR) output of laser diodes. Using such probes, one can readily imagine small time-resolved fluorometers, even hand-held devices, being used fordoctor's office or home health care.

Electron Paramagnetic Resonance (EPR) spectroscopy - also sometimes termed Electron Spin Resonance spectroscopy - has manifold potential uses in biochemistry and medicine. The paramount importance of EPR spectroscopy applied to biological tissues and fluids is that it identifies the changes in redox processes that contribute to disease. EPR spectroscopy has come a long way from its original use to detect malignant tumors. For example, the development and later refinement of methods of low-temperature registration of biological tissues widened the scope of EPR spectroscopy. Innovations made possible by the introduction of spin labels, probes, and traps made EPR spectroscopy ever more applicable to biochemistry and medicine, to the point where in vivo studies are being carefully considered. This comprehensive book discusses spectra of many tissues and bodily fluids, and the quantitative nature of paramagnetic centers in both normal individuals and patients suffering from a variety of diseases. Special attention is given to the EPR examination of bio-molecules, such as enzymes, polypeptides, vitamins, lipids, hydrocarbons, etc., which play an essential role in human activity. This book will be of great interest to physicians specializing in many different areas. Similarly, biologists, biochemists, biophysicists, and chemists will find this book very useful. It has also been written so that it may be used as a textbook at graduate level.

We present here the second issue devoted entirely to the spin-labeling technique as part of Biological Magnetic Resonance. Volume 14 commemorates a modifi- tion in our editorial policy with the retirement of my esteemed coeditor, Jacques Reuben. From thisjuncture into the future, each issue will focus on some special topic in magnetic resonance. Each volume will be organized in most cases by guest editors, for example forthcoming issues will address the following topics: in vivo magnetic resonance (P. Robitaille and L. J. Berliner, eds. ) Modern techniques in proton NMR ofproteins (R. Krishna and L. J. Berliner, eds. ) Instrumental techniques of EPR (C. Bender and L. J. Berliner, eds. ) Thecurrent volume, Spin Labeling: The NextMillennium, presents an excellent collection of techniques and applications that evolved during the past decade since the last volume, volume 8 (1989). Someobvious omissions, such as multiquantum EPR and very high-frequency FT-ESR were unfortunately not possible for this volume. Perhaps they will appear in Spin Labeling: 2001. Lastly it is a pleasure to honor two scientists whose contributions were both pioneering and pivotal to the spin label technique: Professor Eduard G. Rozantsev (Moscow), whose synthetic feats in nitroxyl chemistry set the broad stage for a versatile catalog of labels; and Professor Harden M. McConnell, last year's Int- national ESR (EPR) Society Gold Medalist, who conceived and developed the spin label technique to address many biological problems (proteins, enzymes, m- branes, cells, immune response, etc. ). Lawrence J.