The crystal structure of rice (Oryza sativa L.) Os4BGlu12, an oligosaccharide and tuberonic acid glucoside-hydrolyzing β-glucosidase with significant thioglucohydrolase activity

► Os4BGlu12 has an extra disulfide bond compared to other plant family GH 1 enzymes. ► Os4BGlu12 stability is not correlated to the disulfide bond. ► Os4BGlu12 β-glucosidase intermediate with 2-F-glucoside is similar to myrosinase. ► The Os4BGlu12 thioglucosidase activity is higher than Os3BGlu6 and Os3BGlu7. ► Thioglucosidase activity and structural similarity support phylogenetic analysis.