title: From Alkanes to Carboxylic Acids: Terminal Oxygenation by a Fungal Peroxygenase.
abstract: A new heme-thiolate peroxidase catalyzes the hydroxylation of n-alkanes at the terminal position-a challenging reaction in organic chemistry-with H2 O2 as the only cosubstrate. Besides the primary product, 1-dodecanol, the conversion of dodecane yielded dodecanoic, 12-hydroxydodecanoic, and 1,12-dodecanedioic acids, as identified by GC-MS. Dodecanal could be detected only in trace amounts, and 1,12-dodecanediol was not observed, thus suggesting that dodecanoic acid is the branch point between mono- and diterminal hydroxylation. Simultaneously, oxygenation was observed at other hydrocarbon chain positions (preferentially C2 and C11). Similar results were observed in reactions of tetradecane. The pattern of products formed, together with data on the incorporation of (18) O from the cosubstrate H2 (18) O2 , demonstrate that the enzyme acts as a peroxygenase that is able to catalyze a cascade of mono- and diterminal oxidation reactions of long-chain n-alkanes to give carboxylic acids.
authors: Instituto de Recursos Naturales y Agrobiología de Sevilla, CSIC, Reina Mercedes 10, 41012, Seville, Spain.
authors: Andrés
authors: A
authors: Olmedo
authors: Instituto de Recursos Naturales y Agrobiología de Sevilla, CSIC, Reina Mercedes 10, 41012, Seville, Spain.
authors: Carmen
authors: C
authors: Aranda
authors: Instituto de Recursos Naturales y Agrobiología de Sevilla, CSIC, Reina Mercedes 10, 41012, Seville, Spain.
authors: José C
authors: 0000-0002-3040-6787
authors: JC
authors: Del Río
authors: JenaBios GmbH, Orlaweg 2, 00743, Jena, Germany.
authors: Jan
authors: J
authors: Kiebist
authors: JenaBios GmbH, Orlaweg 2, 00743, Jena, Germany.
authors: Katrin
authors: K
authors: Scheibner
authors: Centro de Investigaciones Biológicas, CSIC, Ramiro de Maeztu 9, 28040, Madrid, Spain.
authors: Angel T
authors: 0000-0002-1584-2863
authors: AT
authors: Martínez
authors: Instituto de Recursos Naturales y Agrobiología de Sevilla, CSIC, Reina Mercedes 10, 41012, Seville, Spain. anagu@irnase.csic.es.
authors: Ana
authors: 0000-0002-8823-9029
authors: A
authors: Gutiérrez
mesh_terms: D000473:Alkanes / Q000737:chemistry / Q000378:metabolism*; D055162:Biocatalysis; D002264:Carboxylic Acids / Q000737:chemistry / Q000378:metabolism*; D003998:Dicarboxylic Acids / Q000032:analysis; D007851:Dodecanol / Q000032:analysis; D005658:Fungi / Q000201:enzymology*; D008401:Gas Chromatography-Mass Spectrometry; D006861:Hydrogen Peroxide / Q000737:chemistry; D006900:Hydroxylation; D006899:Mixed Function Oxygenases / Q000378:metabolism*; D010084:Oxidation-Reduction
chemical_list: D000473:Alkanes; D002264:Carboxylic Acids; D003998:Dicarboxylic Acids; C007548:n-dodecane; D007851:Dodecanol; C036836:dodecanedioic acid; D006861:Hydrogen Peroxide; D006899:Mixed Function Oxygenases; C022333:peroxygenase
keywords: alkanes; carboxylic acids; oxidoreductases; peroxygenase; terminal hydroxylation