Abstract

Several new mechanisms for enzyme-catalyzed breakdown of oligosaccharides have been uncovered in recent years. A common feature is the recruitment of elimination steps rather than direct displacements. Bond cleavage can proceed via E1 mechanisms with cationic transition states or E1(cb) mechanisms with anionic transition states, and can even involve NAD(+)-mediated redox steps. A common feature emerging from studies on disparate syn-eliminating enzymes is the use of a single catalytic residue, often tyrosine, as both general acid and base.

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