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The biological chemistry of the elements : the inorganic chemistry of life / J. J. R. Fraústo da Silva, R. J. P. Williams

Main Author Silva, J. J. R. Fraústo da Coauthor Williams, R. J. P. Country Reino Unido. Publication Oxford : Clarendon Press, imp. 1994 Description XXI, 561 p. : il. ; 26 cm ISBN 0-19-855802-3 CDU 577.1
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Monografia Biblioteca Geral da Universidade do Minho
BGUMD 139447 Available 139135
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Enhanced descriptions from Syndetics:

The study of the chemistry of living processes has traditionally centred on the behaviour of organic compounds in water - together they account for 99 per cent of the matter in living systems. However, we also know that about twenty `inorganic' elements are also essential for life, and thatthey are found in similar amounts in most living systems. The authors' objective in this book is to examine and explain the importance of these elements by `bringing inorganic chemistry to life'.The authors commence with a survey of the chemical and physical factors controlling the elements of life; the essential functions of individual inorganic elements are then described in detail. A final section consolidates a major theme of the book - the cooperative interaction of elements in livingsystems. Chapters here examine the relationships between chemical activity and morphology and the effect that changes in the availability of elements have on life - not only in providing evolutionary pressures but also in the context of the use of medicines and the spread of pollutants.

Table of contents provided by Syndetics

  • General introduction (p. 1)
  • Part 1 The chemical and physical factors controlling the elements of life
  • 1 The chemical elements in biology (p. 7)
  • 1.1 The element content of living systems (p. 7)
  • 1.2 An aside: some biological chemistry of hydrogen (p. 11)
  • 1.3 The economical use of resources: abundance and availability (p. 12)
  • 1.4 Biological environment and element availability (p. 15)
  • 1.5 Sulphide chemistry in water (anaerobes) (p. 22)
  • 1.6 A note on homeostasis (p. 24)
  • 1.7 Survival and evolution (p. 26)
  • 1.8 Conclusion (p. 26)
  • 2 The principles of the uptake and chemical speciation of the elements in biology (p. 29)
  • 2.1 Introduction to chemical speciation (p. 30)
  • 2.2 The separations that biology can achieve (p. 33)
  • 2.3 The selective uptake of metal ions (p. 34)
  • 2.4 Effective stability constants (p. 38)
  • 2.5 Element uptake at equilibrium: the selectivity of the uptake (p. 39)
  • 2.6 Hydrolysis: hydroxides and oxenes (p. 51)
  • 2.7 Selective control of oxidation states of metals (p. 53)
  • 2.8 Selection by control of concentration of M and L (p. 54)
  • 2.9 Selection by transfer coefficients from water to proteins (or membranes) (p. 58)
  • 2.10 Selection at surfaces and in precipitates (p. 60)
  • 2.11 The selectivity of channels (p. 61)
  • 2.12 Kinetic effects and control (p. 62)
  • 2.13 Rejection of metal ions (p. 66)
  • 2.14 General aspects of the uptake of essential non-metals (p. 66)
  • 2.15 Mechanisms of selection of anions based on thermodynamic properties (p. 68)
  • 2.16 Redox incorporation of anions (p. 72)
  • 2.17 Coenzymes (p. 74)
  • 2.18 Precipitates in comparatments: cation and anion cooperativity (p. 74)
  • 2.19 The application of equilibria and equilibrium exchange to carriers, buffers, pumps, enzymes and gene regulation (p. 76)
  • 2.20 Genetic regulation-an introduction to control of ligand (protein) concentration (p. 79)
  • 2.21 Concluding remarks: element handling in biological systems (p. 80)
  • 3 Physical separations of elements: compartments and zones in biology (p. 83)
  • 3.1 General aspects (p. 84)
  • 3.2 The nature of compartments (p. 85)
  • 3.3 The chemical solutions and physical states of compartments (p. 86)
  • 3.4 The role and nature of membranes (p. 89)
  • 3.5 Different types of membrane (p. 90)
  • 3.6 Special solution conditions in vesicles (p. 98)
  • 3.7 Cooperativity of separations and localizations (p. 100)
  • 3.8 Summary of metal ion positioning (p. 100)
  • 3.9 Symbiosis and multicellular systems (p. 101)
  • 3.10 Spatial distribution of bulk non-metals (p. 101)
  • 3.11 The spatial transfer of H, C, N, S: mobile and fixed coenzymes (p. 103)
  • 3.12 Summary of non-metal transport (p. 105)
  • 3.13 Evolution of compartments and organization: summary (p. 106)
  • 4 Kinetic considerations of chemical reactions, catalysis, and control (p. 108)
  • 4.1 Introduction (p. 108)
  • 4.2 Chemical transformations (p. 108)
  • 4.3 The nature of acid-base reactions: hydrolysis and condensation (p. 109)
  • 4.4 The hydrolysis of proteins, RNA, DNA, and other polymers (p. 113)
  • 4.5 The nature of ion flow (p. 114)
  • 4.6 On/off reactions: control systems (p. 117)
  • 4.7 Electron-transfer reactions: electronics (p. 118)
  • 4.8 Redox potentials of complexes (p. 122)
  • 4.9 Atom transfer reactions (p. 123)
  • 4.10 Group transfer (p. 125)
  • 4.11 The nature of transition-metal centres in catalysis (p. 125)
  • 4.12 Free radical reactions (p. 127)
  • 4.13 Sizes of atoms, stereochemistry, and reaction paths (p. 128)
  • 4.14 The creation of local small spaces: mechanical devices for transfer reactions (p. 130)
  • 4.15 Networks: kinetic circuits (p. 132)
  • 4.16 Summary (p. 133)
  • 5 Energy in biological systems and hydrogen biochemistry (p. 135)
  • 5.1 Introduction (p. 135)
  • 5.2 Biological systems and light (p. 136)
  • 5.3 Oxidative energy: mitochondria (p. 139)
  • 5.4 Proton migration coupled to redox reactions (p. 141)
  • 5.5 The coupling of gradients to ATP formation (p. 142)
  • 5.6 Anaerobes in the dark (p. 144)
  • 5.7 Compartments, energy, and metabolism (p. 147)
  • 5.8 Organization and tension (p. 148)
  • 5.9 Motion of organisms (p. 148)
  • 5.10 Local storage of elements and energy (p. 148)
  • 5.11 Primitive sources of energy (p. 150)
  • 5.12 Energy networks and summary (p. 151)
  • 6 The role of biological macromolecules and polymers (p. 154)
  • A Proteins and nucleic acids (p. 155)
  • 6.1 Introduction (p. 155)
  • 6.2 Protein composition and basic structure (p. 156)
  • 6.3 The protein fold and the internal motions in solution (p. 161)
  • 6.4 The amino-acid composition of specific proteins (p. 164)
  • 6.5 Structural proteins and mechanical devices (p. 169)
  • 6.6 Matching of proteins and organic and inorganic ions (p. 170)
  • 6.7 Enzymes (p. 171)
  • 6.8 States of metal ions in proteins (p. 173)
  • 6.9 Summary of proteins: the proteome (p. 179)
  • 6.10 Nucleic-acid composition and outline structure (p. 180)
  • 6.11 Metal-ion binding to polynucleotides (p. 182)
  • 6.12 Nucleic acids and proteins (p. 185)
  • 6.13 Controlled synthesis and degradation of biopolymers (p. 186)
  • 6.14 Genetic control (p. 186)
  • 6.15 Summary of genetic control and regulation at 'equilibrium' (p. 194)
  • B Polysaccharides and lipids (p. 196)
  • 6.16 Introduction (p. 196)
  • 6.17 Introduction to polysaccharides (p. 196)
  • 6.18 The backbones and sidechains of polysaccharides (p. 197)
  • 6.19 Glycoproteins and cell surface packing (p. 198)
  • 6.20 Interaction of polysaccharides with metal ions (p. 199)
  • 6.21 Properties of lipids (p. 200)
  • 6.22 Ion association with lipid surfaces (p. 201)
  • 6.23 Essential fatty acids (p. 202)
  • 6.24 Summary of biopolymers (p. 202)
  • 7 The functional value of the chemical elements in biological systems (p. 206)
  • 7.1 Introduction (p. 206)
  • 7.2 Major chemical properties of elements in aqueous solutions (p. 208)
  • 7.3 Biochemical functions of the chemical elements (p. 210)
  • 7.4 The living process (p. 214)
  • 7.5 The chemical flow in biology (p. 217)
  • 7.6 The integration of activity (p. 224)
  • 7.7 Conclusion (p. 226)
  • Part 2 The roles of individual elements in biology
  • 8 Sodium, potassium, and chlorine: osmotic control, electrolytic equilibria, and currents
  • 8.1 Introduction (p. 231)
  • 8.2 Passive diffusion (p. 232)
  • 8.3 Gated channels (p. 235)
  • 8.4 Channel selectivity and possible constructions (p. 236)
  • 8.5 Active transport: pumps (p. 238)
  • 8.6 The nature of selective pumps (p. 242)
  • 8.7 Building electrolytic circuits (p. 242)
  • 8.8 Simple salts and the conditions of polyelectrolytes (p. 245)
  • 8.9 Enzymes requiring potassium (p. 246)
  • 8.10 Ion genetics and networks (p. 246)
  • 8.11 Summary (p. 248)
  • 9 The biological chemistry of magnesium: phosphate metabolism
  • 9.1 Introduction (p. 251)
  • 9.2 The spatial distribution of magnesium (p. 251)
  • 9.3 Magnesium chemistry (p. 252)
  • 9.4 Magnesium pumping in cells (p. 255)
  • 9.5 Very strong binding of magnesium (p. 257)
  • 9.6 Magnesium in walls and membranes (p. 257)
  • 9.7 Magnesium enzymes: magnesium and phosphates (p. 257)
  • 9.8 Magnesium and muscle cells (p. 262)
  • 9.9 Magnesium and polynucleotides (p. 264)
  • 9.10 Competition with polyamines (p. 265)
  • 9.11 Polymeric equilibria: tubulins, DNA, and the cell cycle (p. 268)
  • 9.12 Magnesium outside cells (p. 268)
  • 9.13 Magnesium and lipids (p. 269)
  • 9.14 Magnesium and chlorophyll (p. 269)
  • 9.15 The use of manganese as a magnesium probe (p. 272)
  • 9.16 Interference of other metal ions with Mg[superscript 2+] biochemistry (p. 274)
  • 9.17 Lithium and magnesium (p. 274)
  • 9.18 Evolution and genetics of Mg[superscript 2+] proteins and networks (p. 274)
  • 9.19 Conclusion (p. 276)
  • 10 Calcium: controls and triggers
  • 10.1 Introduction (p. 279)
  • 10.2 Free calcium ion levels (p. 280)
  • 10.3 The calcium ion (p. 282)
  • 10.4 Protein ligands for calcium (p. 284)
  • 10.5 Magnesium/calcium competition (p. 286)
  • 10.6 The resting state of calcium in cells (p. 287)
  • 10.7 Calcium triggering: calmodulins (p. 288)
  • 10.8 The calcium trigger proteins (p. 289)
  • 10.9 S-100 proteins (p. 291)
  • 10.10 Other triggering modes: annexins and C-domains (p. 292)
  • 10.11 Calcium and protein phosphorylation (p. 294)
  • 10.12 Calcium buffering and calcium transport in cells (p. 295)
  • 10.13 Calcium currents: movement through membranes, channels, gates, and pumps (p. 296)
  • 10.14 Calcium exchangers (p. 298)
  • 10.15 Internal calcium-induced proteases: apoptosis (p. 298)
  • 10.16 General remarks concerning control systems in cells (p. 298)
  • 10.17 Extracytoplasmic calcium in vesicles (p. 300)
  • 10.18 Extracellular calcium in circulating fluids (p. 301)
  • 10.19 Calcium proteins of biominerals (p. 305)
  • 10.20 Calcium biominerals (p. 305)
  • 10.21 Intra- and extracytoplasmic calcium balances (p. 308)
  • 10.22 The calcium network today (p. 309)
  • 10.23 The genetic controls of calcium-binding proteins (p. 312)
  • 10.24 Summary of calcium biological chemistry (p. 312)
  • 11 Zinc: Lewis acid catalysis and regulation
  • 11.1 Introduction to Lewis acids (p. 315)
  • 11.2 Zinc in biological space (p. 317)
  • 11.3 Availability and concentration of free Zn[superscript 2+] ions (p. 318)
  • 11.4 Types of protein associated with zinc (p. 319)
  • 11.5 Zinc exchange rates (p. 324)
  • 11.6 The number and selectivity of ligands to zinc (p. 324)
  • 11.7 Zinc as a catalytic group in enzymes (p. 325)
  • 11.8 Summary of zinc proteins (p. 329)
  • 11.9 Regulatory and control roles of zinc (p. 330)
  • 11.10 The export of zinc enzymes: digestion and peptide messages (p. 331)
  • 11.11 Zinc enzymes and peptide hormones (p. 332)
  • 11.12 Other functions of zinc outside cells (p. 333)
  • 11.13 Zinc genetics (p. 334)
  • 11.14 Zinc and evolution (p. 334)
  • 11.15 Summary: is zinc today a master hormone? (p. 335)
  • 12 Non-haem iron: redox reactions and controls
  • 12.1 General introduction to transition metals (p. 341)
  • 12.2 Introduction to iron biological chemistry (p. 344)
  • 12.3 Iron uptake (p. 345)
  • 12.4 The non-haem iron proteins (p. 348)
  • 12.5 The iron/sulphur proteins (p. 348)
  • 12.6 Fe/S centres active as enzymes (p. 351)
  • 12.7 Location of Fe/S proteins (p. 353)
  • 12.8 Why are there Fe[subscript n] S[subscript n] clusters in cells? (p. 353)
  • 12.9 The organization and selectivity of ferredoxins (p. 355)
  • 12.10 The Fe-O-Fe cluster (p. 357)
  • 12.11 Mononuclear non-haem/non-Fe/S iron and oxidative enzymes (p. 359)
  • 12.12 Iron and secondary metabolism (p. 362)
  • 12.13 Binding ligands in non-haem/non-Fe/S proteins (p. 363)
  • 12.14 Extracellular iron as an acid catalyst (p. 363)
  • 12.15 Summary of non-haem iron/non-Fe/S enzymes (p. 363)
  • 12.16 Iron buffering and carriers (p. 364)
  • 12.17 Iron controls of metabolism (p. 365)
  • 12.18 Iron regulation: relationship to genes and evolution (p. 366)
  • 13 Haem iron: coupled redox reactions
  • 13.1 Iron in porphyrins (p. 370)
  • 13.2 Properties of isolated haem units (p. 370)
  • 13.3 Classification of haem proteins by iron properties (p. 373)
  • 13.4 Classification of haem proteins by secondary structure (p. 375)
  • 13.5 Where are haem proteins in cells? (p. 378)
  • 13.6 Haem protein functions I: electron-transfer (p. 379)
  • 13.7 The surfaces of haem proteins (p. 384)
  • 13.8 Haem-protein functions II: storage and transport (p. 385)
  • 13.9 Haem-protein functions III: oxidases and dioxygenases (p. 388)
  • 13.10 Substrates of haem enzymes and secondary metabolism (p. 392)
  • 13.11 Haem in controls (p. 394)
  • 13.12 The synthesis of haem and its genes (p. 394)
  • 13.13 Summary of haem-iron functions (p. 397)
  • 14 Manganese: dioxygen evolution and glycosylation
  • 14.1 Introduction (p. 400)
  • 14.2 Manganese chemistry (p. 400)
  • 14.3 Monomeric Mn(II) and Mn(IV) chemistry (p. 405)
  • 14.4 The biological chemistry of manganese (p. 408)
  • 14.5 The production of dioxygen (p. 409)
  • 14.6 Manganese and peroxide metabolism (p. 411)
  • 14.7 Manganese and hydrolytic reactions (p. 412)
  • 14.8 Manganese precipitates (p. 413)
  • 14.9 Manganese control systems and genetics (p. 414)
  • 14.10 The evolution of manganese functions (p. 415)
  • 14.11 Summary (p. 416)
  • 15 Copper: extracytoplasmic oxidases and matrix formation
  • 15.1 Introduction (p. 418)
  • 15.2 Copper and electron-transfer (p. 419)
  • 15.3 Copper and dioxygen (p. 420)
  • 15.4 Copper enzymes and nitrogen oxides (p. 426)
  • 15.5 Superoxide dismutase (p. 426)
  • 15.6 The transport and homeostasis of copper (p. 428)
  • 15.7 The overall functions of copper (p. 432)
  • 16 Nickel and cobalt: remnants of early life?
  • 16.1 Introduction (p. 436)
  • 16.2 The chemistry of cobalt and nickel (p. 438)
  • 16.3 Hydrogenases (p. 441)
  • 16.4 The reactions of vitamin B[subscript 12] (p. 442)
  • 16.5 The organometallic chemistry of life (p. 444)
  • 16.6 Hydrolytic catalysis by nickel and cobalt (p. 444)
  • 16.7 Nickel and cobalt uptake (p. 447)
  • 16.8 Cobalt and nickel genes in E. coli (p. 448)
  • 16.9 Conclusion (p. 448)
  • 17 Molybdenum, tungsten, vanadium, and chromium
  • 17.1 Introduction (p. 450)
  • 17.2 The availabilities of molybdenum, tungsten, vanadium, and chromium (p. 450)
  • 17.3 The molybdenum enzymes: a first overview (p. 451)
  • 17.4 Biological chemistry of molybdenum (p. 453)
  • 17.5 The structure and function of the molybdenum enzymes (p. 455)
  • 17.6 Molybdenum genetics (p. 458)
  • 17.7 Molybdenum: conclusions (p. 459)
  • 17.8 Tungsten biological chemistry (p. 459)
  • 17.9 Vanadium chemistry and biochemistry (p. 461)
  • 17.10 Molybdenum, vanadium, and tungsten in evolution (p. 466)
  • 17.11 The biological chemistry of chromium (p. 468)
  • 18 Phosphate, silica, and chloride: acid-base non-metals
  • 18.1 Introduction to the non-metals (p. 471)
  • 18.2 Phosphate chemistry (p. 472)
  • 18.3 The forms and energies of bound phosphate (p. 473)
  • 18.4 Summary of phosphate functions (p. 480)
  • 18.5 Chloride channels, pumps, and exchangers (p. 481)
  • 18.6 Anion balance: chloride, phosphate, sulphate, and carboxylates (p. 481)
  • 18.7 Silicon biochemistry (p. 482)
  • 18.8 Boron in biology (p. 487)
  • 18.9 Halides and other non-metal trace elements (p. 487)
  • 19 Sulphur, selenium, and halogens: redox non-metals
  • 19.1 Introduction (p. 489)
  • 19.2 Sulphur biochemistry (p. 490)
  • 19.3 Summary of sulphur chemistry (p. 496)
  • 19.4 The biochemistry of selenium (p. 497)
  • 19.5 Evolution and selenium (p. 499)
  • 19.6 Notes on the use of the halogens (p. 499)
  • 19.7 The cellular content of sulphur, selenium, and iodine (the metallome) (p. 500)
  • 20 Integrated living systems of elements
  • 20.1 Introduction (p. 503)
  • 20.2 The nature of systems (p. 505)
  • 20.3 The detailed steps in the evolution of earth's surface (p. 511)
  • 20.4 Macromolecules and systems (p. 517)
  • 20.5 The beginnings of life (p. 519)
  • 20.6 Survival, reproduction and the need for a coded molecule (p. 523)
  • 20.7 Evolution: introduction and morphological changes (p. 523)
  • 20.8 Evolution and the metallome (p. 528)
  • 20.9 Changes of elements in prokaryotes (p. 532)
  • 20.10 Eukaryotes: the development of new membrane components: new lipids (p. 534)
  • 20.11 Carriers (p. 540)
  • 20.12 The metallome of extracellular and vesicular fluids of mulicellular organisms (p. 542)
  • 20.13 The metallome of brain extracellular fluid (p. 543)
  • 20.14 Summary of metallome content (p. 544)
  • 20.15 Changing non-metals in the proteome and in small organic molecules (p. 544)
  • 20.16 Extracellular communication networks (p. 548)
  • 20.17 Survival of systems: summary of the value of the elements (p. 552)
  • Index (p. 557)

Author notes provided by Syndetics

J.J.R. Frausto da Silva is Professor of Analytical Chemistry, Instituto Superior Tecnico de Lisboa, Portugal
R.J.P. Williams is Emeritus Professor of Chemistry, University of Oxford

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