Origin of the regioselective fatty acid hydroxylation versus decarboxylation by a cytochrome P450 peroxygenase: What drives the reaction to biofuel production?

Faponle, A. S, Quesne, Matthew and De Visser, S. P 2016. Origin of the regioselective fatty acid hydroxylation versus decarboxylation by a cytochrome P450 peroxygenase: What drives the reaction to biofuel production? Chemistry - a European Journal 22 (16) , pp. 5478-5483. 10.1002/chem.201600739

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Abstract

The cytochromes P450 are heme based monoxygenases or peroxygenases involved in vital reaction processes for human health. A recently described P450 peroxygenase, OleTJE, converts long chain fatty acids to terminal olefins and as such may have biotechnological relevance in biodiesel production. The reaction, however, produces significant amounts of α- and β-hydroxylation by-products and their origin are poorly understood. In this work we elucidate through a QM/MM study on the bifurcation pathways how the three possible products are generated and show how the enzyme can be further engineered for optimum desaturase activity. The studies show that the polarity and the solvent accessibility of the substrate in the binding pocket destabilize the OH rebound pathways and kinetically enable a thermodynamically otherwise unfavorable decarboxylation reaction. The origins of the bifurcation pathways are analyzed with valence bond models and highlight the differences in reaction mechanism.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Subjects:	Q Science > QD Chemistry
Publisher:	WileyBlackwell
ISSN:	0947-6539
Date of Acceptance:	25 February 2016
Last Modified:	03 Jul 2017 09:58
URI:	https://orca.cardiff.ac.uk/id/eprint/88669

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