Abstract
A cyclic hexapeptide, cyclo(D-Leu-L-Glu-L-His)2 was synthesized and its catalytic activity for the hydrolysis of various carboxylic acid p-nitrophenyl esters was investigated. Cyclo(D-Leu-L-Glu-L-His)2 was 3 to 20 times as effective as imidazole as a catalyst for the hydrolysis of CH3(CH2)8COOPh(NO2) and CH3(CH2)10COOPh(NO2) in 20% dioxane/H2O mixture at pH 7.8 (phosphate buffer). Cyclo(D-Leu-L-Glu-L-His)2 showed neither higher catalytic activity than imidazole nor enantiomer-selective catalysis in the hydrolysis of Val-OPh(NO2)·HCl and Leu-OPh(NO2)·HCl in aqueous solution at pH 6.95 (phosphate buffer). When Cu(ClO4)2 was added to an aqueous solution of cyclo(D-Leu-L-Glu-L-His)2 at pH 6.05 (phosphate buffer), a 40—150 time increase in the second-order rate constant of both the above a-amino acid active ester hydrochlorides was observed and the L-enantiomers were hydrolyzed slightly faster than the D-enantiomers. The addition of Cu(ClO4)2 to an aqueous solution containing the cyclic hexapeptide at pH 6.01 (citrate buffer) did not lead to peptide-metal ion interaction and an enhanced rate of enantiomer-selective hydrolysis. It was made clear that cyclo(D-Leu-L-Glu-L-His)2 is a highly efficient and weakly enantiomer-selective catalyst in the hydrolysis of α-amino acid active ester hydrochlorides only when it forms a complex with copper ion.
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Tanihara, M., Imanishi, Y. Highly Efficient and Enantiomer-Selective Hydrolysis of α-Amino Acid Active Ester Hydrochlorides by a Cyclic Hexapeptide Containing Histidines. Polym J 15, 499–507 (1983). https://doi.org/10.1295/polymj.15.499
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DOI: https://doi.org/10.1295/polymj.15.499