Catalytic hydrogenolysis of larix bark proanthocyanidins in ionic liquids produces UV blockers with potential for use in cosmetics

The bark of larix, a major tree species in the coniferous forests of China's Greater Khingan Mountains, is typically treated as waste. The bark is, however, rich in flavonoids, known as proanthocyanidins, although their high degree of polymerization and high molecular weight reduce their biological activity and potential applications. Ionic liquids, a new type of "green solvent", characterized by low vapor pressure and good stability, have been developed and used as new solvents for naturally occurring macromolecules. Here, we used 1-butyl-3-methylimidazole chloride ([BMIM]Cl) as the ionic solvent to reduce the degree of polymerization of larix bark proanthocyanidins by Pd/C-catalyzed hydrogenolysis. The optimal reaction conditions, determined using an orthogonal experimental design, were: reaction temperature, 90 degrees C; reaction time, 1.5 h; catalyst loading, 4 g L-1 (Pd/C: [BMIM]Cl); and hydrogen pressure, 2.5 MPa. Characterization of the reaction products by UV-Vis and IR spectroscopy and gel permeation chromatographys showed that they retained the proanthocyanidin structure. We showed that whilst both the native and depolymerized proanthocyanidins were able to block UV light when added to commercially available skin creams and sunscreens, the depolymerized proanthocyanidins were more effective at a given concentration. This study expands the applications of a new "green" ionic liquid solvent, provides a technical foundation for the low-cost depolymerization of larix bark proanthocyanidins, and also explores a potential high-value use for waste larix bark as the source of a UV-blocking additive for cosmetics.