A new model for the origin of kinetic hydrogen isotope effects

被引:42
作者
Klinman, Judith P. [1 ,2 ]
机构
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
[2] Univ Calif Berkeley, Dept Mol & Cell Biol, Berkeley, CA 94720 USA
关键词
C-H activation; enzymes; heavy atom motions; isotope effects; tunneling; TRANSITION-STATE THEORY; TEMPERATURE-DEPENDENCE; HYDRIDE-TRANSFER; SOYBEAN LIPOXYGENASE-1; THEORETICAL-ANALYSIS; ENZYME-KINETICS; PROTON; MECHANISM; DYNAMICS; REACTIVITY;
D O I
10.1002/poc.1661
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Measurements of kinetic hydrogen isotope effects in enzymatic C-H bond cleavage reactions have generated a body of data that is inconsistent with either a semi-classical formalism for the origin of the isotope effects or a semi-classical formalism together with a modest degree of hydrogen tunneling. A model that treats the movement of hydrogen as a wave, and whose behavior is dictated by the heavy atom environment, is presented and discussed. A list of unanswered questions and challenges is given at the end of this paper. Copyright (C) 2010 John Wiley & Sons, Ltd.
引用
收藏
页码:606 / 612
页数:7
相关论文
共 64 条
[1]   Canonical variational theory for enzyme kinetics with the protein mean force and multidimensional quantum mechanical tunneling dynamics.: Theory and application to liver alcohol dehydrogenase [J].
Alhambra, C ;
Corchado, J ;
Sánchez, ML ;
Garcia-Viloca, M ;
Gao, J ;
Truhlar, DG .
JOURNAL OF PHYSICAL CHEMISTRY B, 2001, 105 (45) :11326-11340
[2]  
[Anonymous], 1980, TUNNELING EFFECT CHE
[3]   A link between protein structure and enzyme catalyzed hydrogen tunneling [J].
Bahnson, BJ ;
Colby, TD ;
Chin, JK ;
Goldstein, BM ;
Klinman, JP .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1997, 94 (24) :12797-12802
[4]   UNMASKING OF HYDROGEN TUNNELING IN THE HORSE LIVER ALCOHOL-DEHYDROGENASE REACTION BY SITE-DIRECTED MUTAGENESIS [J].
BAHNSON, BJ ;
PARK, DH ;
KIM, K ;
PLAPP, BV ;
KLINMAN, JP .
BIOCHEMISTRY, 1993, 32 (21) :5503-5507
[5]   Enzymatic H-transfer requires vibration-driven extreme tunneling [J].
Basran, J ;
Sutcliffe, MJ ;
Scrutton, NS .
BIOCHEMISTRY, 1999, 38 (10) :3218-3222
[6]  
BASSHAN JA, 1957, PATH CARBON PHOTOSYN, V49, P24
[7]   DEUTERIUM ISOTOPE EFFECT IN THE REACTION OF HYDROGEN MOLECULES WITH CHLORINE ATOMS AND THE POTENTIAL ENERGY OF THE H2CL TRANSITION COMPLEX [J].
BIGELEISEN, J ;
KLEIN, FS ;
WESTON, RE ;
WOLFSBERG, M .
JOURNAL OF CHEMICAL PHYSICS, 1959, 30 (05) :1340-1351
[8]   CALCULATION OF EQUILIBRIUM CONSTANTS FOR ISOTOPIC EXCHANGE REACTIONS [J].
BIGELEISEN, J ;
MAYER, MG .
JOURNAL OF CHEMICAL PHYSICS, 1947, 15 (05) :261-267
[9]   VIBRATIONALLY ENHANCED TUNNELING AS A MECHANISM FOR ENZYMATIC HYDROGEN TRANSFER [J].
BRUNO, WJ ;
BIALEK, W .
BIOPHYSICAL JOURNAL, 1992, 63 (03) :689-699
[10]   HYDROGEN TUNNELING IN ENZYME-REACTIONS [J].
CHA, Y ;
MURRAY, CJ ;
KLINMAN, JP .
SCIENCE, 1989, 243 (4896) :1325-1330