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Titolo:
Structural basis of stereoselectivity in Candida rugosa lipase-catalyzed hydrolysis of secondary alcohols
Autore:
Schulz, T; Schmid, RD; Pleiss, J;
Indirizzi:
Univ Stuttgart, Inst Tech Biochem, D-70569 Stuttgart, Germany Univ Stuttgart Stuttgart Germany D-70569 hem, D-70569 Stuttgart, Germany
Titolo Testata:
JOURNAL OF MOLECULAR MODELING
fascicolo: 7, volume: 7, anno: 2001,
pagine: 265 - 270
SICI:
1610-2940(2001)7:7<265:SBOSIC>2.0.ZU;2-C
Fonte:
ISI
Lingua:
ENG
Soggetto:
PSEUDOMONAS-CEPACIA LIPASE; RHIZOPUS-ORYZAE LIPASE; INTERFACIAL ACTIVATION; PANCREATIC LIPASE; MECHANISM; TRANSESTERIFICATION; ENANTIOSELECTIVITY; TRIRADYLGLYCEROLS; ESTERS;
Keywords:
Candida rugosa lipase; enantioselectivity; diastereoselectivity; molecular modeling; secondary alcohol;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Life Sciences
Physical, Chemical & Earth Sciences
Citazioni:
24
Recensione:
Indirizzi per estratti:
Indirizzo: Pleiss, J Univ Stuttgart, Inst Tech Biochem, Allmandring 31, D-70569 Stuttgart, Germany Univ Stuttgart Allmandring 31 Stuttgart Germany D-70569 Germany
Citazione:
T. Schulz et al., "Structural basis of stereoselectivity in Candida rugosa lipase-catalyzed hydrolysis of secondary alcohols", J MOL MODEL, 7(7), 2001, pp. 265-270

Abstract

Lipases are widely used catalysts for highly enantioselective resolution of chiral secondary alcohols. While stereopreference is determined predominantly by the substrate structure, stereoselectivity (enantioselectivity and diastereoselectivity) depends on the atomic details of interactions betweensubstrate and lipase. Experimentally obtained stereoselectivity and activity in the hydrolysis of butanoic acid esters of two secondary alcohols withtwo neighboring stereocenters by Candida rugosa lipase have been investigated by computer-aided molecular modeling of tetrahedral substrate intermediates in complex with the lipase. Breakdown of these intermediates is considered to be the rate-limiting step. Steric interactions of stereoisomers with the side chain of catalytic histidine led to different orientations of the imidazole. The distance d(HNepsilon-O-alc) between H-N epsilon of the imidazole side chain of catalytic histidine and the alcohol oxygen of the substrate was identified to correlate with the experimentally determined reactivity order of the four stereoisomers. Modeled distances d(H-N epsilon-O-alc) were short (= 1.8 Angstrom) for RR stereoisomers, which were also found to be hydrolyzed most rapidly experimentally; distances d(H-N epsilon-O-alc)were about 2 Angstrom for SS and SR stereoisomers, which were converted atsimilar rates but at a lower rate than RR stereoisomers; finally, distances d(H-N epsilon-O-alc) for SR stereoisomers were greater than 4 Angstrom, in accordance with very slow conversion of SR stereoisomers.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 25/11/20 alle ore 15:53:36