MARKED DEPENDENCE OF ENZYME PROCHIRAL SELECTIVITY ON THE SOLVENT

被引:85
作者
TERRADAS, F [1 ]
TESTONHENRY, M [1 ]
FITZPATRICK, PA [1 ]
KLIBANOV, AM [1 ]
机构
[1] MIT,DEPT CHEM,CAMBRIDGE,MA 02139
关键词
D O I
10.1021/ja00055a004
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Prochiral selectivity of various hydrolytic enzymes (lipases and proteases) in organic solvents was investigated in transformations involving a 2-substituted 1,3-propanediol or its diester. In two instances, a significant dependence of enzyme prochiral selectivity on the solvent was found: transesterification of diol 1 with vinyl butyrate catalyzed by Aspergillus oryzae protease in anhydrous solvents and hydrolysis of diester 3 catalyzed by Pseudomonas sp. lipase in hydrated organic solvents (monoester 2 was a product in both reactions). The latter process, where the pro-S selectivity of the enzyme varied from around 3 in some solvents to greater than 30 in others, was examined in more detail. A mechanistic model was proposed that predicted an inverse correlation between lipase's prochiral selectivity and solvent hydrophobicity, as well as particular effects of substrate structure variation and an additive on the prochiral selectivity; all these predictions were confirmed experimentally. Subtilisin Carlsberg lacked appreciable prochiral selectivity in either transesterification or hydrolysis reactions regardless of the solvent; this was rationalized by means of interactive computer modeling based on the X-ray crystal structure of this serine protease.
引用
收藏
页码:390 / 396
页数:7
相关论文
共 54 条
[1]   KINETIC ISOTOPE EFFECT INVESTIGATION OF ENZYME MECHANISM IN ORGANIC-SOLVENTS [J].
ADAMS, KAH ;
CHUNG, SH ;
KLIBANOV, AM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (25) :9418-9419
[2]   SOLVENT DIELECTRIC EFFECTS ON PROTEIN DYNAMICS [J].
AFFLECK, R ;
HAYNES, CA ;
CLARK, DS .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1992, 89 (11) :5167-5170
[3]   AN EFFICIENT ENANTIOSELECTIVE PREPARATION OF 2-SUBSTITUTED-3-HYDROXYPROPIONIC ACIDS VIA CHEMOENZYMATIC REACTION [J].
ATSUUMI, S ;
NAKANO, M ;
KOIKE, Y ;
TANAKA, S ;
OHKUBO, M ;
YONEZAWA, T ;
FUNABASHI, H ;
HASHIMOTO, J ;
MORISHIMA, H .
TETRAHEDRON LETTERS, 1990, 31 (11) :1601-1604
[4]   ENZYMOLOGY - MORE OF THE CATALYTIC TRIAD [J].
BLOW, D .
NATURE, 1990, 343 (6260) :694-695
[5]   THE HIGH-RESOLUTION X-RAY CRYSTAL-STRUCTURE OF THE COMPLEX FORMED BETWEEN SUBTILISIN CARLSBERG AND EGLIN-C, AN ELASTASE INHIBITOR FROM THE LEECH HIRUDO-MEDICINALIS - STRUCTURAL-ANALYSIS, SUBTILISIN STRUCTURE AND INTERFACE GEOMETRY .2. [J].
BODE, W ;
PAPAMOKOS, E ;
MUSIL, D .
EUROPEAN JOURNAL OF BIOCHEMISTRY, 1987, 166 (03) :673-692
[6]   RESOLUTION OF (+/-)-TRANS-SOBREROL BY LIPASE PS-CATALYZED TRANSESTERIFICATION AND EFFECTS OF ORGANIC-SOLVENTS ON ENANTIOSELECTIVITY [J].
BOVARA, R ;
CARREA, G ;
FERRARA, L ;
RIVA, S .
TETRAHEDRON-ASYMMETRY, 1991, 2 (09) :931-938
[7]   THE CHEMISTRY OF THE TRITERPENES AND RELATED COMPOUNDS .18. ELUCIDATION OF THE STRUCTURE OF POLYPORENIC ACID-C [J].
BOWERS, A ;
HALSALL, TG ;
JONES, ERH ;
LEMIN, AJ .
JOURNAL OF THE CHEMICAL SOCIETY, 1953, (SEP) :2548-2560
[8]   A SERINE PROTEASE TRIAD FORMS THE CATALYTIC CENTER OF A TRIACYLGLYCEROL LIPASE [J].
BRADY, L ;
BRZOZOWSKI, AM ;
DEREWENDA, ZS ;
DODSON, E ;
DODSON, G ;
TOLLEY, S ;
TURKENBURG, JP ;
CHRISTIANSEN, L ;
HUGEJENSEN, B ;
NORSKOV, L ;
THIM, L ;
MENGE, U .
NATURE, 1990, 343 (6260) :767-770
[9]   DEMONSTRATION OF STRUCTURAL INTEGRITY OF AN ENZYME IN ORGANIC-SOLVENTS BY SOLID-STATE NMR [J].
BURKE, PA ;
SMITH, SO ;
BACHOVCHIN, WW ;
KLIBANOV, AM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (21) :8290-8291
[10]   ACTIVITY OF THIOLSUBTILISIN IN ORGANIC-SOLVENTS [J].
CHATTERJEE, S ;
RUSSELL, AJ .
BIOTECHNOLOGY PROGRESS, 1992, 8 (03) :256-258