Dramatic Electronic Perturbations of Cu_A Centers via Subtle Geometric Changes.

ABSTRACT: Cu_A is a binuclear copper site acting as electron entry port in terminal heme-copper oxidases. In the oxidized form, Cu_A is a mixed valence pair whose electronic structure can be described using a potential energy surface with two minima, σ_u* and π_u, that are variably populated at room temperature. We report that mutations in the first and second coordination spheres of the binuclear metallocofactor can be combined in an additive manner to tune the energy gap and, thus, the relative populations of the two lowest-lying states. A series of designed mutants span σ_u*/π_u energy gaps ranging from 900 to 13 cm^-1. The smallest gap corresponds to a variant with an effectively degenerate ground state. All engineered sites p

SUBMITTER: Leguto AJ 

PROVIDER: S-EPMC6576268 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature