Biochemistry of the Elemental Halogens and Inorganic Halides, Softcover reprint of the original 1st ed. 1991
Biochemistry of the Elements Series, Vol. 9A+B

The elements in group 17 (VIlA) of the periodic table of elements-fluorine (F), chlorine (CI), bromine (Br), and iodine (I)-were designated by Berzelius as "halogens" (Greek hals, sea salt; gennao, I beget) because of their propensity to form salts. In this first of the two volumes of Bio­ chemistry of the Halogens, the biochemistry of the elemental halogens and inorganic halides is reviewed. Discovery, properties, and biochemistry of the elemental halogens are reviewed first (Chapter 1). This is followed by a review of the developments in the various areas of inorganic halide biochemistry (Chapters 2 through 5). The biochemistry of thyroid hor­ mones is considered in Chapter 6, while biohalogenation, an important link between inorganic and organic halogen biochemistry, is reviewed in Chapter 7. Chapter 8 covers the biochemistry of products produced by human-inspired halogenation, in particular, poly halogenated compounds that present environmental problems. In Chapter 9, the process is reversed and biodehalogenation is reviewed. In each subject, the attempt has been made to find an appropriate balance between depth and breadth of treatment, since a thorough, in­ depth review of this field would not be possible in a single volume. To provide readers not familiar with subjects with the necessary background to place subsequent discussions in perspective, brief historical develop­ ments of many of the topics are given.

1. The Halogens: Discovery, Occurrence, and Biochemistry of the Free Elements.- 1.1 Introduction.- 1.2 Fluorine.- 1.2.1 Isolation of Fluorine.- 1.2.2 Properties.- 1.2.3 Industrial Production and Uses of Fluorine.- 1.2.4 Biochemistry and Toxicology.- 1.3 Chlorine.- 1.3.1 Isolation of Chlorine.- 1.3.2 Properties.- 1.3.3 Industrial Production and Uses of Chlorine Gas.- 1.3.4 Biochemistry and Toxicology of Elemental Chlorine.- 1.3.5 Water Chlorination.- 1.4 Bromine.- 1.4.1 Isolation of Bromine.- 1.4.2 Industrial Production and Uses of Bromine.- 1.4.3 Biochemistry and Toxicology.- 1.5 Iodine.- 1.5.1 Isolation of Iodine.- 1.5.2 Industrial Production and Uses of Iodine.- 1.5.3 Biochemistry and Toxicology.- 1.6 Summary.- References.- 2. Biochemistry of Inorganic Fluoride.- 2.1 Introduction.- 2.2 Occurrence and Distribution of Inorganic Fluoride.- 2.3 Biological Uptake, Distribution, and Metabolism of Inorganic Fluoride.- 2.4 Overview of Effects of Fluoride on Enzyme Activity.- 2.5 Inhibition of 2-Phospho-D-Glycerate Hydrolase (Enolase).- 2.5.1 Properties of Enolase.- 2.5.2 Fluoride Inhibition of Enolase: Dependence on Inorganic Phosphate.- 2.5.3 Cation Requirements for Enolase.- 2.5.4 Interaction of Fluoride with Enzyme-Bound Metal.- 2.5.5 Synergistic Binding of Fluoride and Phosphate to the Enzyme–Metal Complex.- 2.5.6 Substrate-Dependent Inhibition of Yeast Enolase in the Absence of Pi.- 2.6 Inhibition of Inorganic Pyrophosphatase.- 2.6.1 Bakers’ Yeast Pyrophosphatase: Mg2+ and Substrate-Dependent Inhibition by Fluoride.- 2.6.2 Metal Binding Sites and Fluoride Inhibition.- 2.6.3 Biological Significance of Inhibition of Inorganic Pyrophosphatase by Fluoride.- 2.7 Inhibition of Acetylcholinesterases and Butyrylcholinesterase.- 2.8 Inhibition of (Na+ + K+)-Dependent ATPase (ATP Phosphohydrolase) by Fluoride—Influence of Aluminum.- 2.9 Stimulation of ATP Pyrophosphate-Lyase (Cyclizing) (Adenylate Cyclase).- 2.9.1 Mechanism of Hormonal Activation of Adenylate Cyclase.- 2.9.2 Effects of Fluoride on Adenylate Cyclase Activation and Deactivation.- 2.10 Stimulation of Photoreceptor Phosphodiesterase I by Fluoride.- 2.10.1 G-Proteins and the Visual Process.- 2.10.2 Effect of GTP and of Fluoride on Subunit Dissociation and on Tranducin GTPase Activity.- 2.10.3 Mechanism of Fluoride-Induced Activation of cGMP Phosphodiesterase.- 2.11 Stimulation of Polyphosphoinositide Phosphodiesterase by Fluoride.- 2.11.1 GTP Analogues and Fluoride Stimulate PPI-pde Activity.- 2.11.2 Cellular Effects of Fluoride and PPI-pde Stimulation.- 2.12 Additional Regulatory Proteins That Interact with Fluoride.- 2.13 Effects of Fluoride on Cellular Function.- 2.13.1 Effect of Fluoride on Platelet Function.- 2.13.2 Effect of Fluoride on Neutrophil Function.- 2.13.3 Effect of Fluoride on Protein Synthesis.- 2.14 In Vivo Toxicity of Fluoride.- 2.15 Effects of Fluoride on Mineralized Tissue.- 2.15.1 Introduction.- 2.15.2 Biochemistry of Mineralized Tissue—An Overview.- 2.15.3 Uptake of Fluoride by Bone.- 2.15.4 Fluorosis.- 2.15.5 Fluoride in the Treatment of Osteoporosis.- 2.15.6 Fluoride in Dental Tissue.- 2.16 Biochemistry of Inorganic Fluoride—Summary.- References.- 3. Biochemistry of Inorganic Chloride.- 3.1 Introduction.- 3.2 Transport of Chloride Through Cell Membranes.- 3.2.1 Transmembrane Transport Mechanisms.- 3.2.2 Classification of Chloride Transport Mechanisms.- 3.3 Chloride Transport and Body Fluid Homeostasis.- 3.4 Chloride/Bicarbonate Cotransport in Erythrocyte Membrane.- 3.4.1 General Properties of Erythrocyte Anion Transport.- 3.4.2 Kinetics of Transport.- 3.4.3 Molecular Probes for the Erythrocyte Cl-/HCO3- Transport System.- 3.4.4 The Structure of Band 3 and Models for Anion Transport.- 3.4.5 Band 3 and Chloride Transport—Summary.- 3.5 Chloride/Cation Cotransport and Cell Volume Control.- 3.6 Chloride and Transepithelial Transport.- 3.6.1 Transepithelial Transport.- 3.6.2 Chloride Transport and Renal Function.- 3.7 Epithelial Chloride Secretion and Cystic Fibrosis.- 3.7.1 Altered Electrolyte Transport in Cystic Fibrosis.- 3.7.2 Mechanism of Secretion in Airway Epithelia.- 3.7.3 Regulation of the Apical Chloride Channel and Cystic Fibrosis.- 3.7.4 Chloride Secretion and Cystic Fibrosis—Summary.- 3.8 Hydrochloric Acid Secretion in the Stomach.- 3.9 Glycine- and Gaba-Gated Chloride Channels.- 3.9.1 Chloride Channels and Neural Hyperpolarization.- 3.9.2 Identification of a GABA/Benzodiazepine Receptor–Chloride Ionophore Complex.- 3.9.3 Structure of the GABA/Benzodiazepine Receptor–Chloride Ionophore Complex.- 3.9.4 Physiological Relevance of Modulation of the GABA-Gated Chloride Channel.- 3.10 Stimulation and Inhibition of Enzymes by Chloride.- 3.10.1 Chloride and the Photosynthetic Formation of Oxygen.- 3.10.2 Activation of ?-Amylase.- 3.10.3 Inhibition of [Glu1]Plasminogen Activation.- 3.10.4 Stimulation of Angiotensin Converting Enzyme (ACE).- 3.10.5 Regulation of GTP-Dependent Regulatory Proteins by Chloride.- 3.11 Chloride and Neutrophil Function.- 3.11.1 Chloride Transport and Neutrophil Activation.- 3.11.2 Role of Chloride in the Microbicidal Action of Neutrophils.- 3.11.3 Chloride and the Pathogenesis of Inflammation.- 3.12 Biochemistry of Chloride—Summary.- References.- 4. Biochemistry of Inorganic Bromide.- 4.1 Introduction.- 4.2 Occurrence and Biodistribution of Bromide.- 4.3 Pharmacology and Toxicology of Bromide.- 4.3.1 Historical Background.- 4.3.2 “Bromism”—Chronic Bromide Toxicity.- 4.3.3 Effects of Bromide on the Central Nervous System.- 4.3.4 Bromide and Thyroid Function.- 4.4 Bromide and Anion Transport Mechanisms.- 4.4.1 Theoretical Basis for Anion Selectivity.- 4.4.2 Examples of Selectivity in Halide Transport.- 4.5 Inhibition and Stimulation of Enzymes by Bromide.- 4.6 Bromide and Eosinophil Function.- 4.6.1 Eosinophil Function and Host Defense.- 4.6.2 Brominating Oxidants from Human Eosinophils.- 4.6.3 Bromide and the Biological Production of Singlet Oxygen.- 4.7 Biochemistry of Bromide—Summary.- References.- 5. Biochemistry of Inorganic Iodide.- 5.1 Introduction.- 5.2 Occurrence, Uptake, and Biodistribution of Iodide.- 5.3 Iodide Transport into Thyroid and Other Iodide-Concentrating Tissues.- 5.3.1 The Thyroid Gland.- 5.3.2 The Iodide Pump.- 5.3.3 Regulation of Iodide Uptake: Thyroid-Stimulating Hormone (TSH).- 5.3.4 Autoregulation of Iodide Uptake.- 5.3.5 Additional Thyroid Ion Transport Mechanisms.- 5.3.6 Iodide Transport and Thyroglobulin Iodination.- 5.3.7 Additional Iodine-Concentrating Organs.- 5.4 Stimulation and Inhibition of Enzymes by Iodide.- 5.4.1 The Hofmeister Lyotropic Series and “Thyroid-Like” Systems.- 5.4.2 Carbonic Anhydrase Inhibition.- 5.4.3 Inhibition of Thyroid Adenylate Cyclase Activity.- 5.5 Biochemistry of Inorganic Iodide—Summary.- References.- 6. Iodotyrosine, Iodothyronines, and Thyroid Function.- 6.1 Iodotyrosine as a Biological Tracer.- 6.2 Iodothyronines and Thyroid Function.- 6.2.1 A Brief Historical Perspective.- 6.2.2 Biosynthesis of Thyroid Hormones.- 6.2.3 Release and Biological Transport of Thyroid Hormones.- 6.2.4 Thyroid Hormone Receptors and Biological Response.- 6.2.5 Regulation of Thyroid Hormone Synthesis and Release.- 6.2.6 Metabolism and Deactivation of Thyroid Hormones.- 6.2.7 Conclusion.- References.- 7. Biohalogenation.- 7.1 Introduction.- 7.2 Naturally Occurring Halometabolites.- 7.2.1 Chlorometabolites Produced by Fungi and Lichens.- 7.2.2 Halometabolites Produced by Bacteria.- 7.2.3 Halometabolites Produced by Marine Organisms.- 7.2.4 Halometabolites Produced by Higher Plants.- 7.2.5 Iodometabolites.- 7.2.6 Fluorometabolites.- 7.3 Haloperoxidases.- 7.3.1 Occurrence.- 7.3.2 Structure.- 7.3.3 Formation of the Halogenating Intermediate.- 7.3.4 The Halogenating Intermediate.- 7.3.5 Glycoprotein Structure and Reactivity.- 7.3.6 pH Dependence on Rates of Halogenation.- 7.3.7 Substrate Specificity and Scope of Reaction.- 7.4 Biosynthesis of Halometabolites in Marine Organisms.- 7.4.1 Acetogenin Biosynthesis.- 7.4.2 Terpene Biosynthesis.- 7.4.3 Formation of Mixed Halides.- 7.5 Biological Fluorination.- 7.6 Biohalogenation—Summary.- References.- 8. Persistent Polyhalogenated Compounds: Biochemistry, Toxicology, Medical Applications and Associated Environmental Issues.- 8.1 Introduction.- 8.2 Biochemistry and Toxicology of Chlorinated Insecticides.- 8.2.1 2,2-Bis (p-chlorophenyl)-1,1,1-trichloroethane (DDT) and Analogues.- 8.2.2 Chlorinated Cyclodiene, Hexachlorocyclohexane, and Polychloronorbornane Insecticides.- 8.3 Biochemistry and Toxicology of Halogenated Biphenyls, Terphenyls, Naphthalenes, Dibenzodioxins, and Related Compounds.- 8.3.1 Industrial Applications of Halogenated Aromatic Compounds and the Environmental Consequences of Their Use.- 8.3.2 Toxic Manifestations of Halogenated Aromatic Hydrocarbons.- 8.3.3 The TCDD (Ah) Receptor and Enzyme Induction.- 8.3.4 The Aromatic Hydrocarbon (Ah) Receptor, AHH Induction, and TCDD Toxicity.- 8.3.5 Halogenated Aromatic Hydrocarbons and Thyroid Function.- 8.4 Medical Applications of Halogenated Hydrocarbons.- 8.4.1 Halogenated Volatile Anesthetics.- 8.4.2 Perfluorocarbons as Artificial Oxygen Transporters.- 8.5 Summary.- References.- 9. Metabolism of Halogenated Compounds—Biodehalogenation.- 9.1 Biodehalogenation—Introduction.- 9.1.1 Cytochrome P-450-Linked Monooxygenases.- 9.1.2 Glutathione S-Transferases.- 9.2 Metabolism of Halogenated Alkanes.- 9.2.1 Monooxygenase-Catalyzed Oxidations of Halogenated Alkanes.- 9.2.2 GSH-Dependent Metabolism of Haloalkanes.- 9.2.3 Metabolism of Environmentally Persistent Compounds Having Aliphatic Halogen–Carbon Bonds.- 9.3 Metabolism of Halogenated Alkenes.- 9.3.1 Vinyl Halides.- 9.3.2 1,1-Dichloroethylene (Vinylidene Chloride).- 9.3.3 cis- and trans-1,2-Dichloroethylene.- 9.3.4 Trichloroethylene.- 9.3.5 Tetrachloroethylene.- 9.3.6 Halogenated Allylic Compounds.- 9.4 GSH-Dependent Metabolism and Toxicity of Halogenated Alkenes.- 9.4.1 Renal ?-Lyase and Nephrotoxicity.- 9.4.2 Molecular Mechanism of ?-Lyase-Dependent Toxicity.- 9.4.3 Metabolism of Cyclodiene Insecticides.- 9.5 Metabolism of Halogenated Aromatic Compounds.- 9.5.1 Haloaromatic Compounds and the NIH Shift.- 9.5.2 Reductive Dehalogenation of Iodothyronines.- 9.5.3 Metabolism of Fluorinated Polycyclic Hydrocarbons—Modulation of Carcinogenicity.- 9.5.4 Metabolism of Environmentally Persistent Polyhalogenated Aromatic Compounds.- 9.6 Biodehalogenation Mediated by Microorganisms.- 9.7 Metabolism and Biodehalogenation—Summary.- References.