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The environment of the N-terminal amino groups of glycophorins AM and AN has been studied using 13C-NMR spectroscopy and pyrylium salts as amino-blocking agents. The extent of amino blocking was monitored by 13C-reductive methylation of the residual free amino groups. The pyrylium ions reacted with the N-terminal amino groups of the two glycophorins at almost identical rates, which is thought to indicate that the overriding steric bulk of the pyrylium salt may determine the rate of the reaction. The difference in the rates of modification of lysine residues of glycophorins AM) and AN by the pyrylium ions did indicate that there may exist an environmental difference around the lysine residues between the two glycophorins. This environmental difference may result from solution aggregation of the glycophorin A molecules or from some differences in the pKa values of the five lysine residues found in glycophorins AM and AN.