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Titration and Assignment of Residues that Regulate the Enantioselectivity of Phenylacetone Monooxygenase
Author(s) -
Zambianchi Francesca,
Fraaije Marco W.,
Carrea Giacomo,
de Gonzalo Gonzalo,
Rodríguez Cristina,
Gotor Vicente,
Ottolina Gianluca
Publication year - 2007
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200600598
Subject(s) - chemistry , thioanisole , protonation , monooxygenase , stereochemistry , peroxide , biocatalysis , titration , enantioselective synthesis , organic chemistry , catalysis , enzyme , cytochrome p450 , reaction mechanism , ion
Phenylacetone monooxygense (PAMO) from Thermobifida fusca was employed for the asymmetric oxidation of thioanisole (sulfooxidation) and of racemic 2‐phenylpropionaldehyde (Baeyer–Villiger oxidation). A pH dependence of enantioselectivity was observed in both cases. Two different residues, with p K a values of 7.8±0.2 and 9.2±0.2, appeared to be responsible for the pH effects on PAMO enantioselectivity. The protonation of Arg337 and the FAD:C4a‐hydroperoxide/FAD:C4a‐peroxide equilibrium were identified as the major factors responsible for the fine‐tuning of PAMO enantioselectivity in Baeyer–Villiger oxidation and sulfooxidation, respectively.