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P450 Jα : A New, Robust and α‐Selective Fatty Acid Hydroxylase Displaying Unexpected 1‐Alkene Formation
Author(s) -
Armbruster Julia,
Steinmassl Mathilde,
Müller Bogotá Christina A.,
Berg Gabriele,
Nidetzky Bernd,
Dennig Alexander
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201905511
Subject(s) - lauric acid , chemistry , yield (engineering) , hydroxylation , alkene , regioselectivity , substrate (aquarium) , oleic acid , decarboxylation , fatty acid , oxidative decarboxylation , enzyme , organic chemistry , selectivity , stereochemistry , biochemistry , catalysis , materials science , oceanography , metallurgy , geology
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 Jα ) which catalyses the selective conversion of a broad range of FAs (C6:0‐C16:0) and oleic acid (C18:1) with H 2 O 2 as oxidant. Under optimized reaction conditions P450 Jα 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 H 2 O 2 in fed‐batch mode. Under similar conditions P450 Jα 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 Jα 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.