文摘
A 13-membered ring cyclic tetrapeptide was synthesized by thesolid-phase peptide synthesis method, and its copper(II) coordination properties were analyzed by optical spectroscopy, massspectrometry, and electrochemistry. All collected data stronglysupport the presence, at alkaline pH, of a stable peptide/copper(III) complex that is formed in solution by atmospheric dioxygenoxidation. On the basis of previous studies on cyclic peptide/coppersystems, we suggest that the copper(III) ion is at the center ofthe ligand's cavity being coordinated to four deprotonated amidenitrogen atoms. This donor set would greatly lower the redoxpotential for the CuIII/CuII couple, thus allowing easy oxidation ofthe coordinated copper(II) by atmospheric oxygen.