alpha-Oxidative decarboxylation of fatty acids catalysed by cytochrome P450 peroxygenases yielding shorter-alkyl-chain fatty acids

作者：Onoda Hiroki; Shoji Osami^*; Suzuki Kazuto; Sugimoto Hiroshi; Shiro Yoshitsugu; Watanabe Yoshihito^*

来源：Catalysis Science & Technology, 2018, 8(2): 434-442.

DOI：10.1039/c7cy02263h

Cytochrome P450 peroxygenases belonging to the CYP152 family catalyse the oxidation of fatty acids using H2O2. CYP152N1 isolated from Exiguobacterium sp. AT1b exclusively catalyses the a-selective hydroxylation of myristic acid at physiological H2O2 concentration. However, a series of shorter-alkyl-chain fatty acids such as tridecanoic acid were produced from myristic acid by increasing the concentration of H2O2 (1-10 mM). The yield of tridecanoic acid from myristic acid reached 17%. An O-18-labeled oxidant study suggested that CYP152N1 catalysed the overoxidation of alpha-hydroxymyristic acid to form alpha-ketomyristic acid, which in turn was spontaneously decomposed by H2O2 to yield tridecanoic acid. Crystal structure analysis of CYP152N1 revealed its high similarity to other CYP152 family enzymes, such as CYP152A1 and CYP152B1. MD simulations of alpha-hydroxymyristic acid accommodated in CYP152N1 proposed a possible pre-oxidation conformation of alpha-hydroxymyristic acid for the decarboxylation reaction.

• 出版日期2018-1-21
• 单位RIKEN