title: A mechanistic study into the epoxidation of carboxylic acid and alkene in a mono, di-acylglycerol lipase.
abstract: More and more industrial chemistry reactions rely on green technologies. Enzymes are finding increasing use in diverse chemical processes. Epoxidized vegetable oils have recently found applications as plasticizers and additives for PVC production. We report here an unusual activity of the Malassezia globosa lipase (SMG1) that is able to catalyze epoxidation of alkenes. SMG1 catalyzes formation of peroxides from long chain carboxylic acids that subsequently react with double bonds of alkenes to produce epoxides. The SMG1 is selective towards carboxylic acids and active also as a mutant lacking hydrolase activity. Moreover we present previously unobserved mechanism of catalysis that does not rely on acyl-substrate complex nor tetrahedral intermediate. Since SMG1 lipase is activated by allosteric change upon binding to the lipophilic-hydrophilic phase interface we reason that it can be used to drive the epoxidation in the lipophilic phase exclusively.
authors.affiliation: College of Light Industry and Food Sciences, South China University of Technology, Guangzhou 510640, PR China.
authors.forename: Xuping
authors.initials: X
authors.lastname: Wang
authors.affiliation: College of Light Industry and Food Sciences, South China University of Technology, Guangzhou 510640, PR China.
authors.forename: Qingyun
authors.initials: Q
authors.lastname: Tang
authors.affiliation: Institute of Structural Biology, Helmholtz Zentrum München, Deutsches Forschungszentrum für Gesundheit und Umwelt (GmbH), Ingolstädter Landstraße 1, 85764 Neuherberg, Germany.
authors.forename: Grzegorz Maria
authors.initials: GM
authors.lastname: Popowicz
authors.affiliation: School of Bioscience and Bioengineering, South China University of Technology, Guangzhou 510006, PR China.
authors.forename: Bo
authors.initials: B
authors.lastname: Yang
authors.affiliation: College of Light Industry and Food Sciences, South China University of Technology, Guangzhou 510640, PR China. Electronic address: yonghw@scut.edu.cn.
authors.forename: Yonghua
authors.initials: Y
authors.lastname: Wang
mesh_terms: D000475:Alkenes / Q000378:metabolism*; D002264:Carboxylic Acids / Q000737:chemistry / Q000378:metabolism*; D004852:Epoxy Compounds / Q000378:metabolism*; D007700:Kinetics; D008071:Lipoprotein Lipase / Q000378:metabolism*; D008958:Models, Molecular; D013379:Substrate Specificity
chemical_list: D000475:Alkenes; D002264:Carboxylic Acids; D004852:Epoxy Compounds; D008071:Lipoprotein Lipase
keywords: Alkene; Carboxylic acid; Epoxidation; M. globosa lipase; Mechanism; Oil