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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.
MILS-16 provides an up-to-date review of the impact of alkali metal ions on life. Their bioinorganic chemistry and analytical determination, the solid state structures of bio-ligand complexes and the properties of alkali metal ions in solution in the context of all kinds of biologically relevant ligands are covered, this includes proteins (enzymes) and nucleic acids (G-quadruplexes). Minerals containing sodium (Na+) and potassium (K+) are abundant in the Earth's crust, making Na+ and K+ easily available. In contrast, the alkali elements lithium (Li+), rubidium, and cesium are rare and the radioactive francium occurs only in traces. Since the intra- and extracellular, as well as the compartmental concentrations of Na+ and K+ differ significantly, homeostasis and active transport of these ions are important; this involves transporters/carriers and pore-forming ion channel proteins. Systems like Na+/K+-ATPases, H+/K+-ATPases or Na+/H+ antiporters are thoroughly discussed. The role of K+ in photosynthesis and the role of Na+ in charging the "battery of life" are pointed out. Also, the relationships between alkali metal ions and diseases (e.g., Parkinson or traumatic brain injury) are covered and the relevance of Li+ salts in medicine (pharmacology and mechanism) is reviewed. This and more is treated in an authoritative and timely manner in the 16 stimulating chapters of Volume 16, The Alkali Metal Ions: Their Role for Life, which are written by 44 internationally recognized experts from 12 nations. The impact of this vibrant research area is manifested in nearly 3000 references, over 30 tables and more than 150 illustrations (two thirds in color). MILS-16 also provides excellent information for teaching. Astrid Sigel, Helmut Sigel, and Roland K. O. Sigel have long-standing interests in Biological Inorganic Chemistry. Their research focuses on metal ion interactions with nucleotides and nucleic acids and on related topics. They edited previously 44 volumes in the series Metal Ions in Biological Systems.
Emphasises on contemporary applications and an intuitive problem-solving approach that helps students discover the exciting potential of chemical science. This book incorporates fresh applications from the three major areas of modern research: materials, environmental chemistry, and biological science.
Endlich ein Fachbuch, das die Theorie, Methoden und die verschiedenen Arten von Metall-Ionen-Komplexen in Wasser (Hydrolyse) umfassend behandelt. Geschrieben wurde dieses Referenzwerk von einem Kernchemiker aus dem Hochschulbereich und einem Geochemiker aus der Industrie. Behandelt werden Kationen- und Anionen-Komplexe sowie die Metall-Ionen-Hydrolyse, zu der zunächst Hintergrundinformationen geliefert werden, bevor eine Beschreibung der Dissoziation von Wasser, aller verschiedenen Hydrolysekomplexe und Verbindungen von Metall und Wasser folgt. Ein Muss für Wissenschaftler im universitären Umfeld und in der Industrie, die sich mit diesem interdisziplinären Thema beschäftigen.
This outline of the principles and chemical interactions in inorganic solution chemistry delivers a course module in an area of considerable complexity. Problems with solutions and tutorial hints to test comprehension have been added as a feature to check readers' understanding and assist self-study. Exercises and projects are also provided to help readers deepen and extend their knowledge and understanding. - Inorganic solution chemistry is treated thoroughly - Emphasis is placed upon NMR, UV-VIS, IR Raman spectroscopy, X-ray diffraction, and such topics as acid-base behaviour, stability constants and kinetics
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The importance of metals in biology, the environment and medicine has become increasingly evident over the last twenty five years. The study of the multiple roles of metal ions in biological systems, the rapidly expanding interface between inorganic chemistry and biology constitutes the subject called Biological Inorganic Chemistry. The present text, written by a biochemist, with a long career experience in the field (particularly iron and copper) presents an introduction to this exciting and dynamic field. The book begins with introductory chapters, which together constitute an overview of the concepts, both chemical and biological, which are required to equip the reader for the detailed analysis which follows. Pathways of metal assimilation, storage and transport, as well as metal homeostasis are dealt with next. Thereafter, individual chapters discuss the roles of sodium and potassium, magnesium, calcium, zinc, iron, copper, nickel and cobalt, manganese, and finally molybdenum, vanadium, tungsten and chromium. The final three chapters provide a tantalising view of the roles of metals in brain function, biomineralization and a brief illustration of their importance in both medicine and the environment.Relaxed and agreeable writing style. The reader will not only fiind the book easy to read, the fascinating anecdotes and footnotes will give him pegs to hang important ideas on.Written by a biochemist. Will enable the reader to more readily grasp the biological and clinical relevance of the subject.Many colour illustrations. Enables easier visualization of molecular mechanismsWritten by a single author. Ensures homgeneity of style and effective cross referencing between chapters
An advanced-level textbook of inorganic chemistry for the graduate (B.Sc) and postgraduate (M.Sc) students of Indian and foreign universities. This book is a part of four volume series, entitled "A Textbook of Inorganic Chemistry – Volume I, II, III, IV". CONTENTS: Chapter 1. Stereochemistry and Bonding in Main Group Compounds: VSEPR theory; dπ -pπ bonds; Bent rule and energetic of hybridization. Chapter 2. Metal-Ligand Equilibria in Solution: Stepwise and overall formation constants and their interactions; Trends in stepwise constants; Factors affecting stability of metal complexes with reference to the nature of metal ion and ligand; Chelate effect and its thermodynamic origin; Determination of binary formation constants by pH-metry and spectrophotometry. Chapter 3. Reaction Mechanism of Transition Metal Complexes – I: Inert and labile complexes; Mechanisms for ligand replacement reactions; Formation of complexes from aquo ions; Ligand displacement reactions in octahedral complexes- acid hydrolysis, base hydrolysis; Racemization of tris chelate complexes; Electrophilic attack on ligands. Chapter 4. Reaction Mechanism of Transition Metal Complexes – II: Mechanism of ligand displacement reactions in square planar complexes; The trans effect; Theories of trans effect; Mechanism of electron transfer reactions – types; outer sphere electron transfer mechanism and inner sphere electron transfer mechanism; Electron exchange. Chapter 5. Isopoly and Heteropoly Acids and Salts: Isopoly and Heteropoly acids and salts of Mo and W: structures of isopoly and heteropoly anions. Chapter 6. Crystal Structures: Structures of some binary and ternary compounds such as fluorite, antifluorite, rutile, antirutile, crystobalite, layer lattices- CdI2, BiI3; ReO3, Mn2O3, corundum, pervoskite, Ilmenite and Calcite. Chapter 7. Metal-Ligand Bonding: Limitation of crystal field theory; Molecular orbital theory: octahedral, tetrahedral or square planar complexes; π-bonding and molecular orbital theory. Chapter 8. Electronic Spectra of Transition Metal Complexes: Spectroscopic ground states, Correlation and spin-orbit coupling in free ions for Ist series of transition metals; Orgel and Tanabe-Sugano diagrams for transition metal complexes (d1 – d9 states); Calculation of Dq, B and β parameters; Effect of distortion on the d-orbital energy levels; Structural evidence from electronic spectrum; John-Tellar effect; Spectrochemical and nephalauxetic series; Charge transfer spectra; Electronic spectra of molecular addition compounds. Chapter 9. Magantic Properties of Transition Metal Complexes: Elementary theory of magneto - chemistry; Guoy’s method for determination of magnetic susceptibility; Calculation of magnetic moments; Magnetic properties of free ions; Orbital contribution, effect of ligand-field; Application of magneto-chemistry in structure determination; Magnetic exchange coupling and spin state cross over. Chapter 10. Metal Clusters: Structure and bonding in higher boranes; Wade’s rules; Carboranes; Metal carbonyl clusters - low nuclearity carbonyl clusters; Total electron count (TEC). Chapter 11. Metal-π Complexes: Metal carbonyls: structure and bonding; Vibrational spectra of metal carbonyls for bonding and structure elucidation; Important reactions of metal carbonyls; Preparation, bonding, structure and important reactions of transition metal nitrosyl, dinitrogen and dioxygen complexes; Tertiary phosphine as ligand.
This book is intended as a practical manual for chemists, biologists and others whose work requires the use of pH or metal-ion buffers. Much information on buffers is scattered throughout the literature and it has been our endeavour to select data and instructions likely to be helpful in the choice of suitable buffer substances and for the preparation of appropriate solutions. For details of pH measurement and the preparation of standard acid and alkali solutions the reader is referred to a companion volume, A. Albert and E. P. Serjeant's The Determination of Ionization Constants (1971). Although the aims of the book are essentially practical, it also deals in some detail with those theoretical aspects considered most helpful to an understanding of buffer applications. We have cast our net widely to include pH buffers for particular purposes and for measurements in non-aqueous and mixed solvent systems. In recent years there has been a significant expansion in the range of available buffers, particularly for biological studies, largely in conse quence of the development of many zwiUerionic buffers by Good et al. (1966). These are described in Chapter 3.