Controlling the chiral inversion reaction of the metallopeptide Ni-asparagine-cysteine-cysteine with dioxygen.

ABSTRACT: Synthetically generated metallopeptides have the potential to serve a variety of roles in biotechnology applications, but the use of such systems is often hampered by the inability to control secondary reactions. We have previously reported that the Ni(II) complex of the tripeptide LLL-asparagine-cysteine-cysteine, LLL-Ni(II)-NCC, undergoes metal-facilitated chiral inversion to dld-Ni(II)-NCC, which increases the observed superoxide scavenging activity. However, the mechanism for this process remained unexplored. Electronic absorption and circular dichroism studies of the chiral inversion reaction of Ni(II)-NCC reveal a unique dependence on dioxygen. Specifically, in the absence of dioxygen, the chiral inversion is not observed, even at elevated pH, whereas the addition of O(2) initiates t

SUBMITTER: Glass AM 

PROVIDER: S-EPMC3939776 | biostudies-literature | 2012 Sep

REPOSITORIES: biostudies-literature