Insights into the mechanisms underlying the degradation of xylooligosaccharides in UV/H2O2 system

UV/H2O2 process is increasingly used to degrade carbohydrates, though the underlying mechanisms remain unclear. This study aimed to fill this knowledge gap, focusing on mechanisms and energy consumption involved in hydroxyl radical (•OH)-mediated degradation of xylooligosaccharides (XOSs) in UV/H2O2 system. Results showed that UV photolysis of H2O2 generated large amounts of •OH radicals, and degradation kinetics of XOSs fitted with a pseudo-first-order model. Xylobiose (X2) and xylotriose (X3), main oligomers in XOSs, were attacked easier by •OH radicals. Their hydroxyl groups were largely converted to carbonyl groups and then carboxy groups. The cleavage rate of glucosidic bonds was slightly higher than that of pyranose ring, and exo-site glucosidic bonds were more easily cleaved than endo-site bonds. The terminal hydroxyl groups of xylitol were more efficiently oxidized than other hydroxyl groups of it, causing an initial accumulation of xylose. Oxidation products from xylitol and xylose included ketoses, aldoses, hydroxy acids and aldonic acids, indicating the complexity of •OH radical-induced XOSs degradation. Quantum chemistry calculations revealed 18 energetically viable reaction mechanisms, with the conversion of hydroxy-alkoxyl radicals to hydroxy acids being the most energetically favorable (energy barriers <0.90 kcal/mol). This study will provide more understanding of •OH radicals-mediated degradation of carbohydrates.