G these, vegetable oils represent a great proportion of the present consumption by the chemical

G these, vegetable oils represent a great proportion of the present consumption by the chemical market. Nevertheless, the chemical possibilities of renewable oils and fats are nonetheless incredibly far from getting completely exploited. Indeed, most of oleochemical reactions have been those MMP-10 Accession occurring at theFrontiers in Bioengineering and Biotechnology | www.frontiersin.orgJanuary 2021 | Volume 8 | ArticleGonz ez-Benjumea et al.Biobased Epoxides by Fungal Peroxygenasesfatty acid carboxy group, while only a very minor proportion of them have involved transformations from the alkyl chain. Nonetheless, the latter reactions have great potential for extending the selection of compounds accessible from oils and fats. In this context, the epoxidation of vegetable oils is being studied because of the current and prospective industrial applications in the products PAK5 manufacturer obtained. Oil epoxides are utilised as stabilizers and plasticizers (Kandula et al., 2014; Jia et al., 2016), and are also promising intermediates for the production of polyols (Zhang et al., 2014a), polyurethanes (Zhang et al., 2014b), biolubricants (Borugadda and Goud, 2014), and epoxy resins (Xia and Larock, 2010), among other uses. Furthermore, by basic industrial procedures, fatty acids are accessible from vegetable oils in such purity that they may be used for further chemical transformations. Their conversion to fatty-acid methyl esters (FAMEs) can be a well-known application, largely investigated for biodiesel production. In addition, unsaturated fatty acids and FAMEs is usually additional epoxidized, and made use of in industrial syntheses of chemical substances and intermediates. Industrial epoxidation of unsaturated fatty-acid compounds is frequently performed by the Prileschajew (1909) reaction by way of percarboxylic acids. Even so, this technique, which consists of strong mineral acids as catalysts for the “in situ” generation of peracids, suffers from numerous drawbacks including the low selectivity for epoxide formation, as a result of oxirane ring opening in acidic medium, the corrosive nature of acids, as well as the unstable character of peracids (Danov et al., 2017). New procedures have already been investigated aimed at browsing an alternative, including the chemo-enzymatic synthesis with lipases catalyzing carboxylic acid reaction with H2 O2 yielding the reactive peracids (Bj kling et al., 1992; Tiran et al., 2008). However, direct enzymatic processes emerge as a resolution for additional selective and environmentally friendly epoxidation of unsaturated lipids. Quite a few enzymes are recognized to catalyze epoxidation directly, for example some cytochrome P450 monooxygenases (P450), diiron-center oxygenases, and plant peroxygenases (Ruettinger and Fulco, 1981; Oliw, 1994; Piazza et al., 2003). Having said that, they typically present some drawbacks, for instance their intracellular nature and frequent association to membranes (in the case of plant peroxygenases and some P450s), and the requirement for pricey cosubstrates or FADcontaining auxiliary enzymes or domains (within the case of P450s and diiron oxygenases). Phylogenetically distant fungal unspecific peroxygenases (UPOs, EC 1.11.two.1) are associated to P450s within the sense that they also contain a heme prosthetic group coordinated by a cysteine ligand, but they usually do not depend on the reductive activation of molecular oxygen but catalyze the transfer of an oxygen atom from peroxides to reducing substrates (Hofrichter et al., 2015). The very first UPO was described within the basidiomycete Agrocybe aegerita (AaeUPO) (Ullrich et al., 2004) and considering that then, UPO enzymes.