Metabolomics reveals dopa melanin involved in the enzymatic browning of the yellow cultivars of East Asian golden needle mushroom (Flammulina filiformis)

Browning seriously causes postharvest deterioration of the yellow cultivars of Flammulina filiformis, yet the browning process and its mechanism have not been described. Changes of L*, a*, b* values, the browning and whiteness index during air contacted storage were evaluated, uncovering the great loss of brightness and meanwhile the accumulation of yellowness and redness. Browning tissue showed an increase of malondialdehyde, total phenolics, and browning-related enzyme activities of polyphenol oxidase and peroxidase, in contrast to the decrease of bioprotective catalase, superoxide, and dismutase. Non-targeted metabolomics revealed an upregulation of melanin synthesis under oxidation stress, and targeted LC-MS/MS verified the upregulation of l-dopa (3,4-dihydroxy-l-phenylalanine) during browning. Pyrrole-2,3,5-tricarboxylic acid was identified in the degradation products of browning pigments after alkaline hydrogen peroxide by LC-MS/MS, suggesting the existence of 5,6-dihydroxyindole-2-carboxylic acid derived units of eumelanin. Therefore, the biosynthesis of eumelanin via l-dopa pathway could participate in the enzymatic browning of postharvest F. filiformis.