Novel Fatty Acid Chain-Shortening by Fungal Peroxygenases Yielding 2C-Shorter Dicarboxylic Acids
10 páginas.- 4 figuras.- referencias.-Data Availability Statement: All data underlying this article are available in the main publication and in its Supplementary Materials online. ; Unspecific peroxygenases (UPOs), the extracellular enzymes capable of oxygenating a potpourri of aliphatic and aromatic substrates with a peroxide as co-substrate, come out with a new reaction: carbon-chain shortening during the conversion of fatty acids with the well-known UPOs from Coprinopsis cinerea (rCciUPO) and Cyclocybe (Agrocybe) aegerita (AaeUPO). Although a pathway (Cα-oxidation) for shortening the hydrocarbon chain of saturated fatty acids has already been reported for the UPO from Marasmius rotula (MroUPO), it turned out that rCciUPO and AaeUPO shorten the chain length of both saturated and unsaturated fatty acids in a different way. Thus, the reaction sequence does not necessarily start at the Cα-carbon (adjacent to the carboxyl group), as in the case of MroUPO, but proceeds through the subterminal (ω-1 and ω-2) carbons of the chain via several oxygenations. This new type of shortening leads to the formation of a dicarboxylic fatty acid reduced in size by two carbon atoms in the first step, which can subsequently be further shortened, carbon by carbon, by the UPO Cα-oxidation mechanism. View Full-Text ; This research was funded by BioBased Industries Joint Undertaking under the European Union's Horizon 2020 Research and Innovation Programme, grant number 792063 (SusBind project; https://susbind.eu; to A.G., Á.T.M. and M.H.), the PID2020-118968RB-100 project by the Spanish MCIN/AEI/ 10.13039/501100011033 to A.G., and the CSIC projects PIE-202040E185 (to A.G.) and PIE-202120E019 (to Á.T.M.). ; Peer reviewed
