62839 20210121114505.0 doi 10.1111/febs.13177 sideral 89931 ART-2015-89931 eng Carro, Juan 5-hydroxymethylfurfural conversion by fungal aryl-alcohol oxidase and unspecific peroxygenase 2015 Access copy available to the general public Unrestricted Oxidative conversion of 5-hydroxymethylfurfural (HMF) is of biotechnological interest for the production of renewable (lignocellulose-based) platform chemicals, such as 2,5-furandicarboxylic acid (FDCA). To the best of our knowledge, the ability of fungal aryl-alcohol oxidase (AAO) to oxidize HMF is reported here for the first time, resulting in almost complete conversion into 2,5-formylfurancarboxylic acid (FFCA) in a few hours. The reaction starts with alcohol oxidation, yielding 2,5-diformylfuran (DFF), which is rapidly converted into FFCA by carbonyl oxidation, most probably without leaving the enzyme active site. This agrees with the similar catalytic efficiencies of the enzyme with respect to oxidization of HMF and DFF, and its very low activity on 2,5-hydroxymethylfurancarboxylic acid (which was not detected by GC-MS). However, AAO was found to be unable to directly oxidize the carbonyl group in FFCA, and only modest amounts of FDCA are formed from HMF (most probably by chemical oxidation of FFCA by the H2O2 previously generated by AAO). As aldehyde oxidation by AAO proceeds via the corresponding geminal diols (aldehyde hydrates), the various carbonyl oxidation rates may be related to the low degree of hydration of FFCA compared with DFF. The conversion of HMF was completed by introducing a fungal unspecific heme peroxygenase that uses the H2O2 generated by AAO to transform FFCA into FDCA, albeit more slowly than the previous AAO reactions. By adding this peroxygenase when FFCA production by AAO has been completed, transformation of HMF into FDCA may be achieved in a reaction cascade in which O2 is the only co-substrate required, and water is the only by-product formed. info:eu-repo/grantAgreement/ES/MICINN/BIO2011-26694 info:eu-repo/grantAgreement/EC/FP7/613549/EU/Optimized oxidoreductases for medium and large scale industrial biotransformations/INDOX info:eu-repo/semantics/openAccess by-nc-nd http://creativecommons.org/licenses/by-nc-nd/3.0/es/ 4.237 2015 BIOCHEMISTRY & MOLECULAR BIOLOGY 72 / 289 = 0.249 2015 Q1 T1 2.152 2015 Biochemistry 2015 Q1 Molecular Biology 2015 Q1 Cell Biology 2015 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion (orcid)0000-0003-4076-6118 Ferreira, Patricia Universidad de Zaragoza Rodríguez, Leonor Prieto, Alicia Serrano, Ana Balcells, Beatriz Ardá, Ana Jiménez-Barbero, Jesús Gutiérrez, Ana Ullrich, René Hofrichter, Martín Martínez, Ángel T. 1002 060 Universidad de Zaragoza Dpto. Bioq.Biolog.Mol. Celular Área Bioquímica y Biolog.Mole. 282, 16 (2015), 3218–3229 FEBS J. FEBS JOURNAL 1742-464X 887273 http://zaguan.unizar.es/record/62839/files/texto_completo.pdf Versión publicada 98314 http://zaguan.unizar.es/record/62839/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:62839 articulos driver 2021-01-21-10:53:57 ARTICLE