This study explored the substrate scope and regio-selectivity of Gliocladium deliquescens NRRL 1086 on hydroxylated benzophenones (HBPs), which was the follow-up investigation on the glycosylation of phenolic hydroxyl compounds by this unique microbe. Five HBPs substrates were used and three glycosylated metabolites, iriflophenone 2- O - β - d -glycopyranoside ( 6 , 40%), riflophenone 4- O - β - d -glycopyranoside( 7 , 21%) and 2,6,4′-trihydroxy-4-methoxybenzophenone-2- O - β - d -glycopyranoside ( 8 , 65%) were isolated and structurally identified unambiguously by ESI-MS, 1 H NMR, 13 C NMR, and 2D NMR spectroscopy. The versatile glycosylation ability of G. deliquescens NRRL 1086 on phenolic hydroxyl compounds may provide an alternative and convenient method to enable high-efficiency synthesis of various HBPs glycosides.
Abstract Environmental bisphenol F (BPF) has a cyclic endocrine disruption effect, seriously threatening animal and human health. It is frequently detected in environmental samples worldwide. For BPF remediation, biological methods are more environmentally friendly than physicochemical methods. White-rot fungi have been increasingly studied due to their potential capability to degrade environmental pollutants. Phanerochaete sordida YK-624 has been shown to degrade BPF by ligninolytic enzymes under ligninolytic conditions. In the present study, degradation of BPF under non-ligninolytic conditions (no production of ligninolytic enzymes) was investigated. Our results showed that BPF could be completely removed after 7-d incubation. A metabolite of BPF, 4,4’-dihydroxybenzophenone (DHBP) was identified by mass spectrometry and nuclear magnetic resonance, and DHBP was further degraded by this fungus to form 4-hydroxyphenyl 4-hydroxybenzoate (HPHB). DHBP and HPHB were the intermediate metabolites of BPF and would be further degraded by P. sordida YK-624. We also found that cytochrome P450s played an important role in BPF degradation. Additionally, transcriptomic analysis further supported the involvement of these enzymes in the action of BPF degradation. Therefore, BPF is transformed to DHBP and then to HPHB likely oxidized by cytochrome P450s in P. sordida YK-624. Furthermore, the toxicological studies demonstrated that the order of endocrine-disrupting activity for BPF and its metabolites was HPHB > BPF > DHBP. Key points
• White-rot fungus Phanerochaete sordida YK-624 could degrade BPF.
• Cytochrome P450s were involved in the BPF degradation.
• The order of endocrine disrupting activity was: HPHB > BPF > DHBP.
Graphical abstract
危险品化学品经营许可证（带存储）