Wood decay fungi have complex detoxification systems that enable them to cope with secondary metabolites produced by plants. Although the number of genes encoding for glutathione transferases is especially expanded in lignolytic fungi, little is known about their target molecules. In this study, by combining biochemical, enzymatic and structural approaches, interactions between polyphenols and six glutathione transferases from the white-rot fungus Trametes versicolor have been demonstrated. Two isoforms, named TvGSTO3S and TvGSTO6S have been deeply studied at the structural level. Each isoform shows two distinct ligand-binding sites, a narrow L-site at the dimer interface and a peculiar deep hydrophobic H-site. In TvGSTO3S, the latter appears optimized for aromatic ligand binding such as hydroxybenzophenones. Affinity crystallography revealed that this H-site retains the flavonoid dihydrowogonin from a partially purified wild-cherry extract. Besides, TvGSTO6S binds two molecules of the flavonoid naringenin in the L-site. These data suggest that TvGSTO isoforms could interact with plant polyphenols released during wood degradation.

White-rot fungi possess the unique ability to degrade and mineralize all the different components of wood. In other respects, wood durability, among other factors, is due to the presence of extractives that are potential antimicrobial molecules. To cope with these molecules, wood decay fungi have developed a complex detoxification network including glutathione transferases (GST). The interactions between GSTs from two white-rot fungi, Trametes versicolor and Phanerochaete chrysosporium, and an environmental library of wood extracts have been studied. The results demonstrate that the specificity of these interactions is closely related to the chemical composition of the extracts in accordance with the tree species and their localization inside the wood (sapwood vs heartwood vs knotwood). These data suggest that the fungal GSTome could reflect the chemical environment encountered by these fungi during wood degradation and could be a way to study their adaptation to their way of life.

The natural durability of wood is linked to its chemical composition and in particular the presence of metabolites called extractives that often possess chemical reactivity. For dealing with these compounds, wood degraders have developed detoxification systems usually involving enzyme families. Among these enzymes, glutathione transferases (GSTs) are involved in the decrease of the reactivity of toxic compounds. In this study, the hypothesis that the detoxification systems of wood decaying fungi could be indicators of the chemical reactivity of wood extracts has been tested. This approach has been evaluated using 32 wood extracts coming from French Guiana species, testing their antimicrobial ability, antioxidative properties, and reactivity against six GSTs from the white rot Trametes versicolor. From the obtained data, a significant correlation between the antimicrobial and antioxidative properties of the tested wood extracts and GST interactions was established. In addition, the chemical analysis performed on one of the most reactive extracts (an acetonic extract of Bagassa guianensis) has demonstrated oxyresveratrol as a major constituent. We were able to cocrystallize one GST with this commercially interesting compound. Taken together, the presented data support the hypothesis that detoxifying enzymes could be used to identify the presence of molecules of industrial interest in wood extracts.