Metabolomics Analysis Reveals Major Differential Metabolites and Metabolic Alterations in Tea Plant Leaves (Camellia sinensis L.) Under Different Fluorine Conditions

Tea plant (Camellia sinensis L.) is capable of accumulating a large amount of fluorine (F) in leaves without showing toxicity symptoms and thus offers a good model for exploring F tolerance mechanisms. Here, gas chromatography time-of-flight mass spectrometry (GC-TOF–MS) was used to investigate metabolic changes in leaves of tea seedlings under control (0 mM), low F (0.2 mM) and high F (0.8 mM) conditions. Differentially changed metabolites such as galacturonic acid, lactose, fructose, malic acid, alanine were identified by the comparison among the three F treatment groups. A pathway map depicted based on the KEGG database reflected the involvement of pectin biosynthesis metabolism in F stress response. The gene expression and enzyme activity of key enzymes involved in pectin biosynthesis pathway and the content of pectic polysaccharides were increased by exogenous F treatments, indicating the promotion effect of F on the pectin biosynthesis. Pectin was also immunochemically stained in vivo using monoclonal antibody (2F4), which confirmed the increment. The increased pectin might contribute to combining the exogenous F in tea leaves. This research provided some novel insights into further research on F detoxification of plants.