Fatty Acid Chain Shortening by a Fungal Peroxygenase. Issue 67 (20th November 2017)

• Record Type: Journal Article
• Authors: Olmedo, Andrés; Río, José C. del; Kiebist, Jan; Ullrich, René; Hofrichter, Martin; Scheibner, Katrin; Martínez, Angel T.; Gutiérrez, Ana
• Is Part Of: Chemistry. Volume 23:Issue 67(2017)
• Page Start: 16985
• Page End: 16989
• Publication Date: 2017-11-20
• Subjects: carboxylic acids -- chain shortening -- enzymes -- hydrogen peroxide -- oxidation; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201704773
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A recently discovered peroxygenase from the fungus Marasmius rotula ( Mro UPO) 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 H2 O2 . The mechanism, analyzed using H2 18 O2, starts with an α‐oxidation catalyzed by Mro UPO 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 Mro UPO shortening carboxylic acid chains. Abstract : Magic from a mushroom : A peroxygenase from the fungus Marasmius rotula catalyzes the stepwise chain shortening of carboxylic acids by one carbon atom, in the presence of H2 O2 as the sole co‐substrate.