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| Preface | |
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| About the Author | |
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| Enzymes as Catalysts | |
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| What Are Enzymes, and How Do They Work? | |
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| Historical | |
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| Specificity of Enzyme-Catalyzed Reactions | |
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| Rate Acceleration | |
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| Mechanisms of Enzyme Catalysis | |
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| Approximation | |
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| Covalent Catalysis | |
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| General Acid/Base Catalysis | |
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| Electrostatic Catalysis | |
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| Desolvation | |
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| Strain or Distortion | |
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| Enzyme Catalysis in Organic Media | |
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| Enzyme Nomenclature | |
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| Epilogue | |
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| References | |
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| Group Transfer Reactions: Hydrolysis, Amination, Phosphorylation | |
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| Hydrolysis Reactions | |
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| Amide Hydrolysis: Peptidases | |
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| Ester Hydrolysis: Esterases and Lipases | |
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| Aminations | |
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| Glutamine-Dependent Enzymes | |
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| Aspartic Acid as a Source of Ammonia | |
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| Phosphorylations: Transfers of Phosphate and Phosphate Esters to Water or Other Acceptors | |
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| Phosphatases | |
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| Phosphodiesterases | |
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| Kinases | |
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| References | |
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| Reduction and Oxidation | |
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| General | |
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| Redox without a Coenzyme | |
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| Redox Reactions That Require Coenzymes | |
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| Nicotinamide Coenzymes (Pyridine Nucleotides) | |
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| Flavin Coenzymes | |
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| Quinone-Containing Coenzymes | |
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| Other Redox Enzymes | |
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| References | |
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| Monooxygenation | |
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| General | |
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| Flavin-Dependent Hydroxylases | |
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| No Reducing Agent Required | |
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| Hydroxylases Requiring an External Reducing Agent | |
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| Pterin-Dependent Hydroxylases | |
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| General | |
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| Mechanism | |
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| Heme-Dependent Monooxygenases | |
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| General | |
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| Molecular Oxygen Activation | |
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| Mechanistic Considerations | |
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| Nonheme Iron Oxygenation | |
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| Methane Monooxygenase | |
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| Copper-Dependent Oxygenation | |
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| Dopamine [beta]-Monooxygenase | |
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| References | |
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| Dioxygenation | |
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| General | |
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| Intramolecular Dioxygenases | |
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| Catechol Dioxygenases | |
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| Prostaglandin H Synthase (Cyclooxygenase) | |
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| Intermolecular Dioxygenases | |
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| [alpha]-Keto Acid-Dependent Dioxygenases | |
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| References | |
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| Substitutions | |
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| S[subscript N]1 | |
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| Farnesyl Diphosphate Synthase and Related Enzymes | |
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| S[subscript N]1/S[subscript N]2 | |
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| Disaccharide Phosphorylases | |
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| [beta]-Glycosidases | |
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| S[subscript N]2 | |
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| S[subscript N]2' | |
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| S[subscript N]Ar: Nucleophilic Aromatic Substitution | |
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| Electrophilic Substitution (Addition/Elimination) | |
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| Electrophilic Aromatic Substitution | |
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| References | |
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| Carboxylations | |
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| General Concepts | |
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| Carbon Dioxide as the Carboxylating Agent | |
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| Phosphoenolpyruvate (PEP) Carboxykinase | |
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| Phosphoenolpyruvate Carboxytransphosphorylase | |
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| Vitamin K-Dependent Carboxylation of Proteins | |
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| Bicarbonate as the Carboxylating Agent | |
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| Phosphoenolpyruvate Carboxylase | |
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| Biotin-Dependent Carboxylases | |
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| References | |
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| Decarboxylation | |
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| General | |
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| [beta]-Keto Acids | |
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| Schiff Base Mechanism | |
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| Metal Ion-Catalyzed Mechanism | |
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| [beta]-Hydroxy Acids | |
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| Isocitrate Dehydrogenase | |
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| 6-Phosphogluconate Dehydrogenase | |
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| [alpha]-Keto Acids | |
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| General | |
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| Chemistry and Properties of Thiamin Diphosphate | |
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| Mechanism of Thiamin Diphosphate-Dependent Enzymes | |
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| Amino Acids | |
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| Pyridoxal Phosphate-Dependent Decarboxylation | |
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| Pyruvoyl-Dependent Decarboxylation | |
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| Other Substrates | |
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| Orotidine 5'-Monophosphate | |
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| Mevalonate Diphosphate | |
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| References | |
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| Isomerizations | |
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| General | |
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| [1,1]-Hydrogen Shift | |
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| Amino Acid Racemases That Require No Cofactors | |
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| Amino Acid Racemases That Require Pyridoxal 5'-Phosphate | |
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| Other Racemases | |
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| Epimerases | |
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| [1,2]-Hydrogen Shift | |
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| Aldose-Ketose Isomerases | |
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| [1,3]-Hydrogen Shift | |
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| Enolization | |
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| Allylic Isomerizations | |
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| Aza-Allylic Isomerizations | |
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| Cis/Trans Isomerizations | |
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| Maleylacetoacetate Isomerase | |
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| Retinol Isomerase | |
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| Catalytic Antibody-Catalyzed Cis/Trans Isomerization | |
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| Phosphate Isomerization | |
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| References | |
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| Eliminations and Additions | |
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| Anti Eliminations and Additions | |
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| Dehydratases and Hydratases | |
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| Elimination of Phosphate | |
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| Ammonia Lyases: Elimination of Ammonia | |
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| Syn Eliminations and Additions | |
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| Schiff Base Mechanism | |
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| Pyridoxal 5'-Phosphate-Dependent Eliminations | |
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| Pyridoxamine 5'-Phosphate and Iron-Sulfur Cluster-Dependent Reactions | |
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| A Catalytic Antibody-Catalyzed Syn Elimination | |
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| References | |
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| Aldol and Claisen Reactions and Retroreactions | |
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| Aldol Reactions | |
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| General Chemical Considerations | |
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| Aldolases | |
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| Porphobilinogen Synthase (5-Aminolevulinate Dehydratase) | |
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| ATP Citrate-Lyase | |
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| Transketolase | |
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| Dehydroquinate Synthase | |
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| Claisen Reactions | |
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| General | |
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| Thiolase | |
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| Kynureninase | |
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| References | |
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| Formylations, Hydroxymethylations, and Methylations | |
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| Tetrahydrofolate-Dependent Enzymes: The Transfer of One-Carbon Units | |
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| Formation of the Active Coenzyme | |
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| Transfer of One-Carbon Units | |
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| S-Adenosylmethionine-Dependent Enzymes: The Transfer of Methyl Groups | |
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| References | |
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| Rearrangements | |
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| Pericyclic Reactions | |
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| Sigmatropic Rearrangements | |
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| Cycloaddition Reactions | |
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| Rearrangements That Proceed via Carbenium Ion Intermediates | |
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| Acyloin Rearrangement | |
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| Cyclizations | |
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| Rearrangements That Proceed via Radical Intermediates | |
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| DNA Photolyase, Formally a [2+2] Cycloreversion Reaction | |
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| Coenzyme B[subscript 12]-Dependent and Related Rearrangements | |
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| Epilogue | |
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| References | |
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| Enzyme Kinetics | |
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| Substrate Kinetics | |
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| Michaelis-Menten Equation | |
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| Graphical Representations | |
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| Kinetics of Enzyme Inhibition | |
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| Reversible Enzyme Inhibition | |
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| Irreversible Enzyme Inhibition | |
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| Substrate Inhibition | |
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| Nonproductive Binding | |
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| Competing Substrates | |
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| Multisubstrate Systems | |
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| Sequential Mechanisms | |
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| Allosterism and Cooperativity | |
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| General | |
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| Monod-Wyman-Changeux (MWC) Concerted Model | |
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| Koshland-Nemethy-Filmer (KNF) Sequential Model | |
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| General References | |
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| References | |
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| Problems and Solutions | |
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| Problems | |
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| Chapter 1 | |
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| Chapter 2 | |
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| Chapter 3 | |
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| Chapter 4 | |
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| Chapter 5 | |
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| Chapter 6 | |
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| Chapter 7 | |
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| Chapter 8 | |
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| Chapter 9 | |
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| Chapter 10 | |
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| Chapter 11 | |
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| Chapter 12 | |
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| Chapter 13 | |
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| Biosynthetic Pathways | |
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| Solutions to Problems | |
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| Chapter 1 | |
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| Chapter 2 | |
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| Chapter 3 | |
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| Chapter 4 | |
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| Chapter 5 | |
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| Chapter 6 | |
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| Chapter 7 | |
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| Chapter 8 | |
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| Chapter 9 | |
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| Chapter 10 | |
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| Chapter 11 | |
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| Chapter 12 | |
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| Chapter 13 | |
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| Biosynthetic Pathways | |
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| Index | |