P450: A New, Robust and α-Selective Fatty Acid Hydroxylase Displaying Unexpected 1-Alkene Formation

Julia Armbruster, Mathilde Steinmassl, Christina A. Müller Bogotá, Gabriele Berg, Bernd Nidetzky, Alexander Dennig*

*Corresponding author for this work

Research output: Contribution to journalArticle

Abstract

Oxyfunctionalization of fatty acids (FAs) is a key step in the design of novel synthetic pathways for biobased/biodegradable polymers, surfactants and fuels. Here, we show the isolation and characterization of a robust FA α-hydroxylase (P450) which catalyses the selective conversion of a broad range of FAs (C6:0-C16:0) and oleic acid (C18:1) with H2O2 as oxidant. Under optimized reaction conditions P450 yields α-hydroxy acids all with >95 % regioselectivity, high specific activity (up to 15.2 U mg−1) and efficient coupling of oxidant to product (up to 85 %). Lauric acid (C12:0) turned out to be an excellent substrate with respect to productivity (TON=394 min−1). On preparative scale, conversion of C12:0 reached 83 % (0.9 g L−1) when supplementing H2O2 in fed-batch mode. Under similar conditions P450 allowed further the first biocatalytic α-hydroxylation of oleic acid (88 % conversion on 100 mL scale) at high selectivity and in good yields (1.1 g L−1; 79 % isolated yield). Unexpectedly, P450 displayed also 1-alkene formation from shorter chain FAs (≤C10:0) showing that oxidative decarboxylation is more widely distributed across this enzyme family than reported previously.

Original languageEnglish
Pages (from-to)15910-15921
Number of pages12
JournalChemistry - a European Journal
Volume26
Issue number68
DOIs
Publication statusPublished - 4 Dec 2020

Keywords

  • alpha-hydroxylation
  • biocatalysis
  • fatty acids
  • oleic acid
  • P450 peroxygenases

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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