Enzyme Kinetics and Mechanism

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1 Methods in Enzymology Volume 87 Enzyme Kinetics and Mechanism Part C Intermediates, Stereochemistry, and Rate Studie s Daniel L. Purich

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3 CONTRIBUTO RS TO VOLUME ix PREFACE VOLUMES IN SERIES xi xiii Section I. Enzyme Intermediate s 1. Criteria for Evaluating the Catalytic Competenc e of Enzyme-Substrate Covalent Compounds DANIEL L. PURICH 3 2. Galactose-l-Phosphate Uridylyltransferase : De- PERRY A. FREY, LEE-JUN tection, Isolation, and Characterization of the WONG, KWAN-FU SHEU, Uridylyl Enzyme AND SUE-LEIN YANG The Trimethylacetyl-Transglutaminase Complex J. E. FOLK Intermediates in the Phosphoglycerate Mutase and Bisphosphoglycerate Synthase Reactions ZELDA B. ROSE Covalent Chemistry of Pyruvate, Orthophosphate NEIL H. Goss AN D Dikinase HARLAND G. WOOD Preparation and Properties of Covalent Com- R. J. CoLL, P. D. COMPTON, pounds and Intermediates of Serine Proteases AND A. L. FINK Covalent Reaction of Substrates and Antimetabolites with Formylglycinamide Ribonucleotide Amidotransferase JOHN M. BUCHANAN Enzymology of Enol Intermediates IRWIN A. ROSE 84 Section II. Stereochemistr y 9. Stereospecificities of the Pyridine Nucleotide- Linked Enzymes KWAN-SA YOU Preparation, Analysis, and Biochemical Applications of Chiral Methyl Groups HEINZ G. FLOSS Preparation of Chromium(III) and Cobalt(III) Nucleotides as Chirality Probes and Inhibitors W. WALLACE CLELAND NMR and EPR Studies of Chromium and Cobal t Nucleotides and Their Interactions with Enzymes JOSEPH J. VILLAFRANCA Stereochemistry of Enzymic Phosphoryl and Nu- FRITZ ECKSTEIN, cleotidyl Transfer PAUL J. ROMANIUK, AN D BERNARD A. CONNOLLY 197

4 14. Stereochemistry of Selected Phosphotransferases PERRY A. FREY, JOHN P. and Nucleotidyltransferase RICHARD, Hsu-Tso Ho, RICHARD S. BRODY, R. DOUGLAS SAMMONS, AN D KWAN-FU SHEU Use of 31 P(160) 31 P( 17 0), and 170 NMR Method s to Study Enzyme Mechanisms Involving Phosphorus MING-DAW TSAI Chiral [16 0, 170, 16O]Phosphoric Monoesters as STEPHEN L. BUCHWALD, Stereochemical Probes of Phosphotransferases DAVID E. HANSEN, ANNEMARIE HASSETT, AN D JEREMY R. KNOWLES The Stereochemical Course of Nucleoside Triphosphatase Reactions MARTIN R. WEBB 30 1 Section III. Initial Rate and Inhibitor Methods 18. Kinetic Examination of Enzyme Mechanisms Involving Branched Reaction Pathways-A Detaile d Consideration of Multifunctional Glucose-6- phosphatase ROBERT C. NORDLIE Initial Velocity Analysis for Terreactant Mech- RONALD E. VIOLA AN D anisms W. WALLACE CLELAND An Analysis of Haldane Relationships W. WALLACE CLELAND Regression Analysis, Experimental Error, and Statistical Criteria in the Design and Analysis of Experiments for Discrimination between Rival Kinetic Models BENGT MANNERVIK The Use of ph Studies to Determine Chemical Mechanisms of Enzyme-Catalyzed Reactions W. WALLACE CLELAND Buffers of Constant Ionic Strength for Studying KEITH J. ELLIS AN D ph-dependent Processes JOHN F. MORRISON Two-Protonic-State Electrophiles as Probes of Enzyme Mechanism KEITH BROCKLEHURST Application of Affinity Labeling for Studyin g Structure and Function of Enzymes BRYCE V. PLAPP The Yonetani-Theorell Graphical Method fo r Examining Overlapping Subsites of Enzyme Active Centers TAKASHI YONETANI Determination of Binding Stoichiometry by th e Continuous Variation Method : The Job Plot CHARLES Y. HUANG The Mechanism of Action of Yeast Inorgani c Pyrophosphatase BARRY S. COOPERMAN 526

5 Section IV. Isotopes as Mechanistic Probe s 29. Solvent Isotope Effects on Enzyme Systems K. BARBARA SCHOWE N AND RICHARD L. SCHOWEN Deuterium and Tritium Kinetic Isotope Effect s on Initial Rates DEXTER B. NORTHROP The Use of Isotope Effects to Determine Transition- State Structure for Enzymic Reactions W. WALLACE CLELAND Determination of Equilibrium Isotope Effects b y the Equilibrium Perturbation Method W. WALLACE CLELAND Isotope Exchange Studies of Regulatory Enzymes : "Fingerprint" Kinetic Patterns for Modifier FREDERICK C. WEDLE R Action AND WILLIAM H. SHALONGO Deduction of Kinetic Mechanisms from Primary Hydrogen Isotope Effects : Dopamine ß-Monooxy- SUSAN M. MILLER AN D genase-a Case History JUDITH P. KLINMAN Carbonic Anhydrase : Oxygen-18 Exchange Catalyzed by an Enzyme with Rate-Contributin g Proton-Transfer Steps DAVID N. SILVERMAN 73 2 AUTHOR INDEX 75 3 SUBJECT INDEX 777

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