Analysis of Enzyme Reaction Kinetics

• Type: Book
• Date: 2023

Authors

Francisco Xavier Malcata (Author) FEUP

Publisher

John Wiley & Sons

Indexing

ISI Web of Knowledge

ISI Web of Science

Scientific classification

CORDIS: Technological sciences

FOS: Engineering and technology

Other information

DOI: 10.1002/9781119490258

Abstract (EN): Analysis of Enzyme Reaction Kinetics is the second set in a unique 11-volume collection on Enzyme Reactor Engineering. This two-volume set comprehensively describes rate equations pertaining to enzymatic reactions, including modulation by physicochemical factors – as tools for prediction and control of how fast substrate(s) will be transformed to products, an essential element of mass balances to, and practical operation of (enzyme) reactors. Therefore, rate expressions are mathematically derived from mech- anistic postulates, and complemented by appropriate statistical approaches, in attempts to fit them to experimental data (first volume); physical and chemical modulation of reaction rate is discussed next, upon both enzyme-catalyzed and enzyme deactivation reactions (second volume). Introductory concepts – including such key issues as molecular mechanism of a given chemical reaction, derivation of kinetic expression from elementary steps, definition of reaction order, and difference between uni- and multisubstrate reactions are taken as starting point for the first volume. For reactions catalyzed by a single enzyme, the basic Michaelis and Menten’s postulates are reviewed, and the analytical form of the associated rate expression is produced and graphically interpreted – by resorting to semilogarith- mic, Eisenthal and Cornish-Bowden’s, and Dixon’s plots; the concentrations of free enzyme and enzyme – substrate complex are accordingly retrieved, while overparame- terization is reduced as much as possible. Alternative derivations of the basic rate expression are then provided – namely based on van Slyke and Culen’s, or Briggs and Haldane’s postulates; the accompanying relative errors are estimated, and the underlying biochemical rationale is explored. Said rate expressions are meanwhile discussed in terms of absolute sensitivity to lumped parameters and relative sensitivity to intrinsic parameters – and their derivatives duly calculated. With regard to reactions catalyzed by multiple enzymes, independent attention is dedicated to two, several or (asymptotically) infinite number of isozymes; a brief tour is taken through autocatalytic reactions – where enzyme serves as both substrate and catalyst; as well as through multiphasic reactions – where substrate(s)/product(s) are contributed by distinct, immmiscible phases. A more in-depth treatment of single enzyme, homogeneous reactions is then devel- oped, following Morrison’s general algebraic derivation, and Kim’s even more general differential approach; graphical interpretations are provided in both cases, limiting cases considered, and absolute sensitivity to intrinsic kinetic parameters ascertained. Dedicated techniques for accurate modeling of initial and final transients are reported – under both batch and flow stirred configurations. In attempts to make Michaelis and Menten’s rate expression simpler to use, Lambert’s solution and Taylor’s expansion are utilized to generate explicit forms useful for integrated mass balances; and several possibi- lities for linearization are introduced and discussed, applicable to both differential and inte- gral forms of such mass balances. Finally, general techniques for systematic derivation of multisubstrate rate expres- sions, under pseudo steady-state, are made available – based on King and Altman’s method and Cha’s approximation, complemented with Cleland’s nomenclature. Illustra- tions of their use are conveyed for selected (relevant) mechanisms, e.g. Uni Uni and ordered Bi Bi, as well as Uni Bi and other Bi Bi possibilities; ...

Language: English

Type (Professor's evaluation): Scientific

ISBN: 9781119490241