On the hydrolysis mechanisms of amides and peptides

摘要

Here the possibility is raised that peptide hydrolysis, in the absence of catalysis by proteases or buffers, may still have a self-catalyzing mechanism that differs from ordinary amide hydrolysis. Second, an attempt is made to clarify the ongoing confusion in the computational chemistry literature regarding the rate-limiting step in ordinary amide hydrolysis. Third, Gibbs activation energies (free-energy barriers) for formamide hydrolysis are derived from rate constants and presented under different concentration conventions, for ease of comparison to values from computational chemistry predictions past and future.