THE NONEXISTENCE OF SPECIALLY STABILIZED HYDROGEN-BONDS IN ENZYMES

被引:133
作者
SCHEINER, S
KAR, T
机构
[1] Department of Chemistry, Southern Illinois University, Carbondale
关键词
D O I
10.1021/ja00131a020
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Ab initio calculations are used to test a recent suggestion that enzymic catalysis can be aided by strengthening of a hydrogen bond in a key intermediate, occurring when this bond is shortened and the pK(a)'s of the two groups are equalized. The requisite amount of energy is not available in electrically neutral H-bonds; no additional strengthening can be accomplished by shortening such a bond. Interaction energies where one subunit is charged, on the other hand, can be very high. These bonds are intrinsically very short, and the proton transfer profile contains a very low energy barrier. There is no special stabilization associated with the disappearance of the transfer barrier or equalization of the pK(a)'s.
引用
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页码:6970 / 6975
页数:6
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共 35 条
[1]  
[Anonymous], 1990, ADV PHYS ORG CHEM, DOI DOI 10.1016/S0065-3160(08)60047-7
[2]   HYDROGEN-BONDING IN GLOBULAR-PROTEINS [J].
BAKER, EN ;
HUBBARD, RE .
PROGRESS IN BIOPHYSICS & MOLECULAR BIOLOGY, 1984, 44 (02) :97-179
[3]   MOLLER-PLESSET THEORY FOR ATOMIC GROUND-STATE ENERGIES [J].
BINKLEY, JS ;
POPLE, JA .
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 1975, 9 (02) :229-236
[4]   EXTENDED GAUSSIAN-TYPE VALENCE BASIS-SETS FOR CALCULATIONS INVOLVING NON-EMPIRICAL CORE PSEUDOPOTENTIALS [J].
BOUTEILLER, Y ;
MIJOULE, C ;
NIZAM, M ;
BARTHELAT, JC ;
DAUDEY, JP ;
PELISSIER, M ;
SILVI, B .
MOLECULAR PHYSICS, 1988, 65 (02) :295-312
[5]   LOW-BARRIER HYDROGEN-BONDS AND ENZYMATIC CATALYSIS [J].
CLELAND, WW ;
KREEVOY, MM .
SCIENCE, 1994, 264 (5167) :1887-1890
[6]   HYDROGEN-BONDING AND PROTON TRANSFERS INVOLVING THE CARBOXYLATE GROUP [J].
CYBULSKI, SM ;
SCHEINER, S .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (01) :23-31
[7]   HYDROGEN-BONDING AND PROTON TRANSFERS INVOLVING TRIPLY BONDED ATOMS - HC=CH AND HC=N [J].
CYBULSKI, SM ;
SCHEINER, S .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (14) :4199-4206
[8]   MOLECULAR-ORBITAL STUDY OF THE COMPLEXES (AHN)2H+ FORMED FROM NH3, OH2, FH, PH3, SH2, AND CIH [J].
DELBENE, JE ;
FRISCH, MJ ;
POPLE, JA .
JOURNAL OF PHYSICAL CHEMISTRY, 1985, 89 (17) :3669-3674
[9]  
DELBENE JE, 1994, J MOL STRUC-THEOCHEM, V307, P27
[10]   EVIDENCE FOR A BOUND WATER MOLECULE NEXT TO THE RETINAL SCHIFF-BASE IN BACTERIORHODOPSIN AND RHODOPSIN - A RESONANCE RAMAN-STUDY OF THE SCHIFF-BASE HYDROGEN/DEUTERIUM EXCHANGE [J].
DENG, H ;
HUANG, LW ;
CALLENDER, R ;
EBREY, T .
BIOPHYSICAL JOURNAL, 1994, 66 (04) :1129-1136