Abstract
Kinetic studies of hydrolysis and deuteration of glycylglycine by dinuclear [BMXDCu 2]4+ complexes were following by NMR1H. Two parallel reactions were observed for the ternary system BMXD-Cu 2-Glycylglycine: peptide bond hydrolysis and NCH2 deuteration reactions. The reaction rates show the first-order behavior to the concentration of the ternary [BMXDCu2Glycylglycine] complex. The specific rate constants for the hydrolysis reaction are: KLCu2HGG4+ (L = BMXD and GG = glycylglycine) = 1,8 x 10-6 s-1; KLCu 2GG3+ = 2,3 x 10-6 s-1; KLCu2H-1GG2+, KLCu 2(OH)H-1GG+ and KLCu 2(OH) 2H-1GG = 0, and the specific deuteration rate constants for individual species are: KLCu 2HGG4+ = 3,9 x 10-6 s-1; KLCu 2GG3+ = 4,3 x 10-6 s-1; KLCu2H-1GG2+, KLCu2(OH)H-1GG+ and KLCu2(OH)2H-1GG = 0. The results show that the most active species toward hydrolysis and deuteration reactions are the protonated and non-protonated species, the former being the most reactive species. Semi-empirical calculations for energy minimization showed that the binuclear [BMXDCu 2]4+) complexes adopt the boat-type conformation, in order to accommodate the dipeptide glycylglycine.
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