Coordination of divalent metal cation to amide group to form adduct ion in FAB mass spectrometry: implication of Zn2+ in enzymatic hydrolysis of amide bond

The structures of complexes between amides and metal ions were examined by FAB mass spectrometry and collision-induced dissociation (CID). Zn2+ was coordinated by the amide carbonyl oxygen atom of N-tetradecylacetamide (1). In contrast, Ca2+ and Mg2+ were coordinated by the amide group of 1 in both the keto and enol forms. The catalytic role of Zn2+ at the active site of the hydrolases might partly be explained by the effective attack of Zn2+ on carbonyl oxygen atom of the scissile amide group.