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Preface | |
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Representation of Protein Three-Dimensional Structures | |
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From Jack Beans to Designer Genes | |
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Introduction | |
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The discovery of enzymes | |
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The discovery of coenzymes | |
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The commercial importance of enzymes in biosynthesis and biotechnology | |
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The importance of enzymes as targets for drug discovery | |
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All Enzymes Are Proteins | |
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Introduction | |
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The structures of the L-�-amino acids | |
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The primary structure of polypeptides | |
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Alignment of amino acid sequences | |
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Secondary structures found in proteins | |
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The folded tertiary structure of proteins | |
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Enzyme structure and function | |
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Metallo-enzymes | |
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Membrane-associated enzymes | |
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Glycoproteins | |
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Enzymes Are Wonderful Catalysts | |
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Introduction | |
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A thermodynamic model of catalysis | |
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Proximity effects | |
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The importance of transition state stabilization | |
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Acid/base catalysis in enzymatic reactions | |
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Nucleophilic catalysis in enzymatic reactions | |
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The use of strain energy in enzyme catalysis | |
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Desolvation of substrate and active site nucleophiles | |
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Catalytic perfection | |
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The involvement of protein dynamics in enzyme catalysis | |
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Methods for Studying Enzymatic Reactions | |
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Introduction | |
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Enzyme purification | |
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Enzyme kinetics | |
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The stereochemical course of an enzymatic reaction | |
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The existence of intermediates in enzymatic reactions | |
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Analysis of transition states in enzymatic reactions | |
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Determination of active site catalytic groups | |
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Hydrolytic and Group Transfer Enzymes | |
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Introduction | |
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The peptidases | |
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CASE STUDY: HIV-1 protease | |
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Esterases and lipases | |
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Acyl transfer reactions in biosynthesis (coenzyme A) | |
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Enzymatic phosphoryl transfer reactions | |
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Adenosine 5'-triphosphate (ATP) | |
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Enzymatic glycosyl transfer reactions | |
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Methyl group transfer: use of S-adenosyl methionine and tetrahydrofolate coenzymes for one-carbon transfers | |
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Enzymatic Redox Chemistry | |
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Introduction | |
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Nicotinamide adenine dinucleotide-dependent dehydrogenases | |
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Flavin-dependent dehydrogenases and oxidases | |
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Flavin-dependent mono-oxygenases | |
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CASE STUDY: Glutathione and trypanothione reductases | |
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Deazaflavins and pterins | |
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Iron-sulphur clusters | |
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Metal-dependent mono-oxygenases | |
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�-Ketoglutarate-dependent dioxygenases | |
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Non-heme iron-dependent dioxygenases | |
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Enzymatic Carbon-Carbon Bond Formation | |
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Introduction | |
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Carbon-carbon bond formation via carbanion equivalents | |
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Aldolases | |
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CASE STUDY: Fructose 1,6-bisphosphate aldolase | |
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Claisen enzymes | |
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Assembly of fatty acids and polyketides | |
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Carboxylases: Use of biotin | |
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Ribulose bisphosphate carboxylase/oxygenase (Rubisco) | |
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Vitamin K-dependent carboxylase | |
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Thiamine pyrophosphate-dependent enzymes | |
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Carbon-carbon bond formation via carbocation intermediates | |
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Terpene cyclases | |
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Carbon-carbon formation through radical intermediates | |
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Phenolic radical couplings | |
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Enzymatic Addition/Elimination Reactions | |
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Introduction | |
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Hydratases and dehydratases | |
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Ammonia lyases | |
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Elimination of phosphate and pyrophosphate | |
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CASE STUDY: 5-Enolpyravyl shikimate 3-phosphate (EPSP) synthase | |
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Enzymatic Transformations of Amino Acids | |
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Introduction | |
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Pyridoxal 5'-phosphate-dependent reactions at the �-position | |
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CASE STUDY: Aspartate aminotransferase | |
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Reactions at the �-and �-positions of amino acids | |
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Serine hydroxymethyltransferase | |
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N-Pyruvoyl-dependent amino acid decarboxylases | |
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Imines and enamines in alkaloid biosynthesis | |
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Isomerases | |
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Introduction | |
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Cofactor-independent racemases and epimerases | |
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Keto-enol tautomerases | |
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Allylic isomerases | |
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CASE STUDY: Chorisrnate mutase | |
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Radicals in Enzyme Catalysis | |
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Introduction | |
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Vitamin B<sub>12</sub>-dependent rearrangements | |
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The involvement of protein radicals in enzyme catalysis | |
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S-adenosyl-methionine-dependent radical reactions | |
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Biotin synthase and sulphur insertion reactions | |
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Radical chemistry in DNA repair enzymes | |
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Oxidised amino acid cofactors and quinoproteins | |
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Non-Enzymatic Biological Catalysis | |
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Introduction | |
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Catalytic RNA | |
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Catalytic antibodies | |
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Synthetic enzyme models | |
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Cahn-Ingold-Prelog Rule for Stereochemical Nomenclature | |
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Amino Acid Abbreviations | |
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A Simple Demonstration of Enzyme Catalysis | |
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Answers to Problems | |
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Index | |