Enzymatic transition state structures constrained by experimental kinetic isotope effects: Experimental measurement of transition state variability

An individual kinetic isotope effect (KIE) provides bond vibrational and geometric information for the differences in atomic environment between an atom in a reactant and its transition state. The magnitude of KIEs measured at every atom surrounding the sites of bond-making and bond-breaking in a reaction places tight experimental constraints on calculations to determine the geometry of the transition state structure. Interpretation of …