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 Encyclopedia of Physical Science and Technology  EN005G-231  June 15, 2001  20:46




















                                                           Enzyme Mechanisms






              Stephen J. Benkovic
              Ann M. Valentine
              Pennsylvania State University



               I. Introduction to Enzymes as Catalysts
              II. Enzyme Kinetics
              III. Illustrative Examples
              IV. Origins of the Catalytic Efficiency of Enzymes








              GLOSSARY                                          noninclusive article describes a small number of enzyme-
                                                                catalyzed reactions from the viewpoint of protein struc-
              Inhibitor A molecule that by binding to the enzyme low-  ture, reaction kinetics, and probable chemical identity of
                ers its activity (i.e., its ability to process the substrate).  intermediates along the reaction pathway. It concludes
              Intermediate A molecular species usually bound to the  with our musings as to the chemical origins of the unusual
                enzyme that exists transiently in the course of convert-  catalytic properties of enzymes.
                ing the substrate of the enzyme to its product.
              Product Amoleculethatresultsfromachemicaltransfor-
                mation of its precursor substrate at an enzyme’s active  I. INTRODUCTION TO ENZYMES
                site.                                             AS CATALYSTS
              Substrate A molecule that binds to an enzyme’s active
                site and is chemically transformed.             Enzymes are biological molecules which accelerate the
                                                                rate, and often direct the specificity, of a chemical reac-
                                                                tion. Like all catalysts, they are not themselves consumed
              THE IMPETUS for understanding how enzymes function  in the reactions in which they participate but are regen-
              is inspired by their enormous catalytic efficiency and their  erated to take part in multiple cycles. Transformations
              exquisite substrate stereospecificity. With the advent of  which are very slow, such as the breakdown of DNA, can
              the determination of enzyme structure and the application  be accelerated by many orders of magnitude by an appro-
              of physical organic tools to examine the reaction coor-  priate enzyme. Enzymes cannot catalyze reactions that are
              dinate for the enzymatic transformation of the substrate,  not thermodynamically favorable, but they can facilitate
              penetrating insights have been gained as to the number  and accelerate those that are favorable but slow and can
              and magnitude of the kinetic steps in the catalytic cycle,  couple unfavorable reactions to even more favorable ones.
              the chemical nature of intermediates, and the function of  Most enzymes are proteins and thus are made up of amino
              the active site residues contributed by the enzyme. This  acids. Recently it was discovered that RNA molecules can




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