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• W2023677223 abstract "Lipid peroxidation by managanese peroxidase (MnP) is reported to decompose recalcitrant polycyclic aromatic hydrocabon (PAH) and nonphenolic lignin models. To elucidate the oxidative process, linoleic acid and 13( S )‐hydroperoxy‐9 Z ,11 E ‐octadecadienoic acid [13( S )‐HPODE] were reacted with MnPs from Ceriporiopsis subvermispora and Bjerkandera adusta and the free radicals produced were analyzed by ESR. When the MnPs were reacted with 13( S )‐HPODE in the presence of Mn(II), H 2 O 2 and tert ‐nitrosobutane ( t ‐NB), the ESR spectrum contained a sharp triplet of acyl radical (a N = 0.81 mT). Formation of acyl radical was also observed in the reactions of Mn(III)‐tartrate with 13( S )‐HPODE and with linoleic acid, but the latter reaction occurred explosively after an induction period of around 30 min. Reactions of MnP with linoleic acid in the presence of Mn(II), H 2 O 2 and t ‐NB gave no spin adducts while addition of t ‐NB after preincubation of linoleic acid with MnP/Mn(II)/H 2 O 2 for 2 h gave spin adducts of carbon‐centered (a N = 1.53 mT, a H = 0.21 mT) and acyl (a N = 0.81 mT) radicals. In contrast to linoleic acid, methyl linoleate and oleic acid were not peroxidized by MnP and chelated Mn(III) within a few hours, indicating that structures containing both the 1,4‐pentadienyl moiety and a free carboxyl group are necessary for inducing the peroxidation in a short reaction time. These results indicate that MnP‐dependent lipid peroxidation is not initiated by direct abstraction of hydrogen from the bis ‐allylic position during turnover but proceeds by a Mn(III)‐dependent hydrogen abstraction from enols and subsequent propagation reactions involving the formation of acyl radical from lipid hydroperoxide. This finding expands the role of chelated Mn(III) from a phenol oxidant to a strong generator of free radicals from lipids and lipid hydroperoxides in lignin biodegradation." @default.
• W2023677223 created "2016-06-24" @default.
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• W2023677223 date "2000-07-01" @default.
• W2023677223 modified "2023-09-29" @default.
• W2023677223 title "Formation of acyl radical in lipid peroxidation of linoleic acid by manganese-dependent peroxidase from<i>Ceriporiopsis subvermispora</i>and<i>Bjerkandera adusta</i>" @default.
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• W2023677223 doi "https://doi.org/10.1046/j.1432-1033.2000.01469.x" @default.
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