Enantioselectivity of Pseudomonas cepacia lipase towards 2-methyl-3(or 4)-arylalkanols: An approach based on the stereoelectronic theory and molecular modeling

Tomić, Sanja; Dobovičnik, Vladimir; Šunjić, Vitomir; Kojić-Prodić, Biserka (2001) Enantioselectivity of Pseudomonas cepacia lipase towards 2-methyl-3(or 4)-arylalkanols: An approach based on the stereoelectronic theory and molecular modeling. Croatica Chemica Acta, 74 (2). pp. 343-357. ISSN 0011-1643

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Abstract

For a better understanding of the previously reported enantioselectivity of Pseudomonas cepacia lipase (PCL) in acylation of racemic primary alcohols, 2-methyl-3(or 4)-arylalkanols, molecular modeling of tetrahedral intermediates (TIs) at the active site was performed. The most probable conformers of TIs were elucidated and their interactions with the amino acid residues of the binding pockets at the enzyme active site were studied. The free energy difference between TIs of two enantiomers was approximated by the differences in potential energy and the solvent accesible surface area. Correlation between the HE(His286). . .O gamma (Ser87) hydrogen bond differences of diastereomeric, low energy gauche-TIs, and experimentally determined enantiomeric ratios was found. In agreement with the stereoelectronic theory, the gauche-TI precedes ester release.

Item Type:	Article
Uncontrolled Keywords:	Pseudomonas cepacia lipase; kinetic resolution; primary alcohols; enantioselectivity; molecular modeling; stereoelectronic theory; candida-rugosa lipase; secondary alcohols; structural basis; catalyzed transesterification; kinetic resolution; rhizomucor-miehei; substrate-binding; microbial lipases; open conformation; sec-alcohols
Subjects:	NATURAL SCIENCES > Chemistry
Divisions:	Division of Physical Chemistry
Projects:	Project title Project leader Project code Project type Struktura i svojstva (bio)molekula Biserka Kojić-Prodić 00980608 MZOS Steroselektivni katalitički i biokatalitički procesi Vitomir Šunjić 00980701 MZOS
Depositing User:	Sanja Tomić
Date Deposited:	20 Nov 2013 09:46
URI:	http://fulir.irb.hr/id/eprint/991

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