Metabolic mechanism of lignin-derived aromatics in white-rot fungi.

White-rot fungi, such as Phanerochaete chrysosporium, play a crucial role in biodegrading lignocellulosic biomass including cellulose, hemicellulose, and lignin. These fungi utilise various extracellular and intracellular enzymes, such as lignin peroxidases, manganese peroxidases, versatile peroxidases, monooxygenases, and dioxygenases, to degrade lignin and lignin-derived aromatics, thereby significantly contributing to the global carbon cycle with potential applications in industrial bioprocessing and bioremediation. Although the metabolism of lignin fragments in P. chrysosporium has been studied extensively, the enzymes involved in fragment conversion remain largely unknown. This review provides an overview of the current knowledge regarding the metabolic pathways of lignin and its fragments by white-rot fungi. Recent studies have elucidated the intricate metabolic pathways and regulatory mechanisms of lignin-derived aromatic degradation by focusing on flavoprotein monooxygenases, intradiol dioxygenases, homogentisate dioxygenase-like proteins, and cytochrome P450 monooxygenases. Metabolic regulation of these enzymes demonstrates the adaptability of white-rot fungi in degrading lignin and lignin-derived aromatics. The interplay between the central metabolic pathways, haem biosynthesis, and haem-dependent NAD(P)H regeneration highlights the complexity of lignin degradation in white-rot fungi. These insights improve our understanding of fungal metabolism and pave the way for future studies aimed at leveraging these fungi for sustainable biotechnological applications. KEY POINTS: • White-rot fungi use enzymes to degrade lignin, and play a role in the carbon cycle. • Oxygenases are key enzymes for converting lignin-derived aromatics. • White-rot fungi adapt to metabolic changes by controlling the TCA/glyoxylate bicycle.