Nuclear magnetic resonance studies of the acid–base chemistry of amino acids and peptides. III. Determination of the microscopic and macroscopic acid dissociation constants of α,ω-diaminocarboxylic acids

Abstract

The acid–base chemistry of 2,3-diaminopropionic acid (dap), 2,4-diaminobutyric acid (dab), ornithine (orn), and lysine (lys) has been studied by 13C and proton nmr spectroscopy. Macroscopic acid dissociation constants for titration of the two ammonium groups of each molecule have been calculated from the 13C chemical shift titration curves for the alkyl carbon atoms by nonlinear least squares curve fitting methods. Microscopic acid dissociation constants for the simultaneous titration of the two ammonium groups of protonated orn and lys have been obtained from their proton chemical shift titration curves and from the 13C titration curves for orn and dap. The results indicate that the α-ammonium group of each of these α,ω-diaminocarboxylic acids is more acidic than its ω-ammonium group, but that the difference decreases as the number of carbons separating the ammonium groups decreases so that the acidities of the two ammonium groups of dap are almost identical. Results of pmr studies of the acid–base chemistry of glycyl-L-lysine and L-lysylglycine also are reported.