The white rot basidiomycete Gelatoporia subvermispora produces fatty aldehydes that enable fungal manganese peroxidases to degrade recalcitrant lignin structures.

The ability of some white rot basidiomycetes to remove lignin selectively from wood indicates that low molecular weight oxidants have a role in ligninolysis. These oxidants are likely free radicals generated by fungal peroxidases from compounds in the biodegrading wood. Past work supports a role for manganese peroxidases (MnPs) in the production of ligninolytic oxidants from fungal membrane lipids. However, the fatty acid alkylperoxyl radicals initially formed during this process are not reactive enough to attack the major structures in lignin. Here, we evaluate the hypothesis that the peroxidation of fatty aldehydes might provide a source of more reactive acylperoxyl radicals. We found that Gelatoporia subvermispora produced trans-2-nonenal, trans-2-octenal, and n-hexanal (a likely metabolite of trans-2,4-decadienal) during the incipient decay of aspen wood. Fungal fatty aldehydes supported the in vitro oxidation by MnPs of a nonphenolic lignin model dimer, and also of the monomeric model veratryl alcohol. Experiments with the latter compound showed that the reactions were partially inhibited by oxalate, the chelator that white rot fungi employ to detach Mn3+ from the MnP active site, but nevertheless proceeded at its physiological concentration of 1 mM. The addition of catalase was inhibitory, which suggests that the standard MnP catalytic cycle is involved in the oxidation of aldehydes. MnP oxidized trans-2-nonenal quantitatively to trans-2-nonenoic acid with the consumption of one O2 equivalent. The data suggest that when Mn3+ remains associated with MnP, it can oxidize aldehydes to their acyl radicals, and the latter subsequently add O2 to become ligninolytic acylperoxyl radicals.IMPORTANCEThe biodegradation of lignin by white rot fungi is essential for the natural recycling of plant biomass and has useful applications in lignocellulose bioprocessing. Although fungal peroxidases have a key role in ligninolysis, past work indicates that biodegradation is initiated by smaller, as yet unidentified oxidants that can infiltrate the substrate. Here, we present evidence that the peroxidase-catalyzed oxidation of naturally occurring fungal aldehydes may provide a source of ligninolytic free radical oxidants.

The effect of ionising radiation on testosterone binding globulin characteristics: correction of the protein' parameters by lipid polyene complexes of fungus Laetiporus sulfureus.

PURPOSE: The aims of this work were: (i) To compare the effects of ionising radiation (IR) on testosterone binding globulin (TeBG) characteristics (serum concentration, cooperativity of androgen binding and affinity for hormone) in divergent mammalian species; (ii) to couple radiation effects with probable TeBG-parameter changes; and (iii) to investigate the prevention of these changes by fungal preparations (in particular - by lipid polyene complexes of Laetiporus sulphureus). MATERIALS AND METHODS: Characteristics of TeBG were investigated in microaliquots of rat and human serum samples using [(3)H]-5 alpha-dihydrotestosterone ([(3)H]-DHT) radioligand assays after in vivo exposures to IR (external gamma-sources, incorporation of (131)I-, (137)Cs-radionuclides) at experimental and post-Chernobyl radioecological conditions (doses 0.25-2.2 Gy). RESULTS: Species-specific changes of TeBG parameters were found depending on the type of IR, dose and time after irradiation. Specifically children living in radionuclide contaminated regions (near Chernobyl) were found to have a decrease of positive cooperativity for the TeBG-androgen binding, a drop of TeBG levels, and a decline in hormone affinity. Screening of natural substances (from phanerogams and fungi) detected that lipid polyene complexes of the basidiomycete L. sulphureus allowed recovery of the standard features of TeBG. CONCLUSIONS: IR induced a depletion of TeBG from blood simultaneously with species-specific changes of TeBG, which depend on the type of radiation, the dose of radiation (from 0.25 up to 2.2 Gy), and the time after radiation. The Hill coefficient of TeBG (indicating the degree of molecular cooperativity when hormone binding) appeared to be the most radiosensitive marker of the glycoprotein activity because of it is inversely to radiation dose. There are pharmacological possibilities to restore IR-induced "declines" of TeBG's affinity and cooperativity for androgen ligand binding.