HPAEC-PAD and Q-TOF-MS/MS analysis reveal a novel mode of action of endo-β-1,3(4)-<ce:small-caps>d</ce:small-caps>-glucanase Eng16A from <ce:italic>coprinopsis cinerea</ce:italic> on barley β-glucan

• Q-TOF-MS/MS analysis reveals a novel mode of Eng16A action on barley β-glucan. • Eng16A can cleave (1 → 4)-β-linkages adjacent to two sides of the (1 → 3)-β-linkage. • Insertion of a (1 → 3)-β-linkage makes (1 → 4)-β-linkages prone to cleavage by Eng16A.