Fatty Acid Chain Shortening by a Fungal Peroxygenase.

Autor: Olmedo A; Instituto de Recursos Naturales y Agrobiología de Sevilla, CSIC, Reina Mercedes 10, 41012, Seville, Spain., Río JCD; Instituto de Recursos Naturales y Agrobiología de Sevilla, CSIC, Reina Mercedes 10, 41012, Seville, Spain., Kiebist J; JenaBios GmbH, Löbstedter Str. 80, 07749, Jena, Germany., Ullrich R; TU Dresden, Markt 23, 02763, Zittau, Germany., Hofrichter M; TU Dresden, Markt 23, 02763, Zittau, Germany., Scheibner K; JenaBios GmbH, Löbstedter Str. 80, 07749, Jena, Germany., Martínez AT; Centro de Investigaciones Biológicas, CSIC, Ramiro de Maeztu 9, 28040, Madrid, Spain., Gutiérrez A; Instituto de Recursos Naturales y Agrobiología de Sevilla, CSIC, Reina Mercedes 10, 41012, Seville, Spain.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2017 Dec 01; Vol. 23 (67), pp. 16985-16989. Date of Electronic Publication: 2017 Nov 20.
DOI: 10.1002/chem.201704773
Abstrakt: A recently discovered peroxygenase from the fungus Marasmius rotula (MroUPO) is able to catalyze the progressive one-carbon shortening of medium and long-chain mono- and dicarboxylic acids by itself alone, in the presence of H 2 O 2 . The mechanism, analyzed using H 2 18 O 2 , starts with an α-oxidation catalyzed by MroUPO generating an α-hydroxy acid, which is further oxidized by the enzyme to a reactive α-keto intermediate whose decarboxylation yields the one-carbon shorter fatty acid. Compared with the previously characterized peroxygenase of Agrocybe aegerita, a wider heme access channel, enabling fatty acid positioning with the carboxylic end near the heme cofactor (as seen in one of the crystal structures available) could be at the origin of the unique ability of MroUPO shortening carboxylic acid chains.
(© 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)
Databáze: MEDLINE