Catalysis in Chemistry and Biochemistry Theory and Experiment

The 12th JerusaLem'Symposium was devoted to the exciting sub ject of CataLysis in Chemistry and Biochemistry. As usuaL in these Sym posia Theory and Experiment have been considered simuLtaneousLy in dis cussions invoLving renowned experts from many countries. We wish to thank aLL those who made this meeting possibLe and contributed to its success: the Baron de RothschiLd whose continuous generosity is at the source of these gatherings, the IsraeL Academy of Sciences and Humanities which offers us the cordiaL hospitaLity of its impressive and beautifuL buiLding and gardens and the Hebrew University of JerusaLem, faithfuL cosponsor of the Symposia. THE MACROMOLECULAR ELECTROSTATIC EFFECT IN BIOCHEMICAL ~EACTIVITY OF THE NUCLEIC ACIDS. BERNARD PULUIAN Institut de BioLogie Physico-Chimique, Laboratoire de Biochimie Theorique, aSSOCle au C. N. R. S. , 13, rue P. et M. Curie, Paris 75005, France. 1. INTRODUCTION The roLe of the macromoLecuLe and of its overaLL structure upon the reactivity of its reaction site(s) represents one of the fundamentaL probLems in the theory of cataLysis. The most impressive and most fre quentLy considered exampLes occur in the fieLd of proteins where the probLem generaLLy consists of accounting for the enhancement of the reaction rate at the active site or at the coenzyme with respect to modeL systems, devoid of the macromoLecuLar superstructure. Different effects have been considered as possibLy responsibLe for the infLuence of the macromoLecuLe on such LocaLized-site reactions. I do not have the time to summarize or discuss them here.

Klappentext

The 12th JerusaLem'Symposium was devoted to the exciting sub­ ject of CataLysis in Chemistry and Biochemistry. As usuaL in these Sym­ posia Theory and Experiment have been considered simuLtaneousLy in dis­ cussions> invoLving renowned experts from many countries. We wish to thank aLL those who made this meeting possibLe and contributed to its success: the Baron de RothschiLd whose continuous generosity is at the source of these gatherings, the IsraeL Academy of Sciences and Humanities which offers us the cordiaL hospitaLity of its impressive and beautifuL buiLding and gardens and the Hebrew University of JerusaLem, faithfuL cosponsor of the Symposia. THE MACROMOLECULAR ELECTROSTATIC EFFECT IN BIOCHEMICAL ~EACTIVITY OF THE NUCLEIC ACIDS. BERNARD PULUIAN Institut de BioLogie Physico-Chimique, Laboratoire de Biochimie Theorique, aSSOCle au C. N. R. S. , 13, rue P. et M. Curie, Paris 75005, France. 1. INTRODUCTION The roLe of the macromoLecuLe and of its overaLL structure upon the reactivity of its reaction site(s) represents one of the fundamentaL probLems in the theory of cataLysis. The most impressive and most fre­ quentLy considered exampLes occur in the fieLd of proteins where the probLem generaLLy consists of accounting for the enhancement of the reaction rate at the active site or at the coenzyme with respect to modeL systems, devoid of the macromoLecuLar superstructure. Different effects have been considered as possibLy responsibLe for the infLuence of the macromoLecuLe on such LocaLized-site reactions. I do not have the time to summarize or discuss them here.

Inhalt
The Macromolecular Electrostatic Effect in Biochemical Reactivity of the Nucleic Acids.- Dynamic and Statistical Aspects of Enzyme Action.- Efficiency and Mechanism in Intramolecular Catalysis.- Cryoenzymology in Reverse Micelles.- Theoretical Studies on Models of the Active Site of Carbonic Anhydrase.- The Mechanism of Carbonic Anhydrase A Solvation Problem?.- A Comparison of the Energetics of Proton Transfer in the Serine and Cysteine 'Charge Relay' Systems and the Role of the Protein Electrostatic Potential on the Proton Transfer Energetics.- Hydrolysis by Acetylcholinesterase. Trimethyl and Methyl Subsites.- Creatine Kinase: An Asymmetric Dimer operating by a 'One-at-a-Time' Mechanism.- Studies on the Mechanism of Catalysis by Thiamin: Progress and Problems.- The Conformation of Cocarboxylase (Thiamine-Pyrophosphate).- Probing the Mechanism of Binding of the Thiamin Pyrophosphate Co-Enzyme on Yeast Pyruvate Decarboxylase.- Ab Initio Orbital Studies of the Flavins.- Flavin Catalysis, the Experimental Approach.- Molecular Orbital Calculations of Metal Microcluster Properties.- Structure Sensitivity and Supported Platinum Catalysts.- Relation Between Catalytic and Electronic Properties of Transition Metals.- Basic Parameters in Metal-Catalysed Processes: Method of Inverse Titration.- The Chemisorption of Acetylene on the Pt(III) Surface. Extended Hückel Results.- Asymmetric Homogeneous Hydrogenation of Prochiral Olefins and Control of the Metal Configuration in Labile Optically Active Organotransition Metal Complexes.- Homogeneous and Heterogeneous Hydrogen Transfer in Carbinols by Group VIII Metal Catalysts.- The Cooperate Effect of Organomagnesium and Nickel Compounds in the Catalytic Oligomerization of 1,3-Dienes.- Trimethylphosphine Cobaltatescontaining Monoolefin and Dinitrogen Ligands Model Compounds for Homogeneous Catalysis.- Conformational Transitions of the Membrane-Bound Cholinergic Receptor.- The Catalytic Effect of Hydrogen Bonding upon Epoxide Ring-Opening.- A Comparison of Dioxygen Activation by Biochemical and Synthetic Polymeric Chemical Systems.- Surface and End Effects in the Electronic Structure of Crystals and Polymers.- Some Aspects of Asymmetric Induction in Addition Reactions to Olefins.- The Catalytic Function of Anthraquinones in the Photooxidation of Chloride to Chlorine.- Tetraphenylporphyrin Complexes as Chemical, Photo- and Electro-Catalysts.- Index of Subjects.- Index of Names.