Further perspectives on the charge transfer transitions of blue copper proteins and the ligand moieties in stellacyanin

Abstract

The charge transfer spectra of plastocyanin and azurin are analyzed in detail, taking into account the structural information that is available. The number and relative energies of the low-lying charge transfer bands attributable to cysteine and methionine sulfur are considered with reference to the energy levels associated with the donor centers and to experimental work on relevant complexes. Two cysteine --> Cu(II) charge transfer transitions are assigned to bands that occur near 620 nm and near 770 nm. Energy considerations suggest that the methionine --> Cu(II) transition occurs in the vicinity of 550 nm for both plastocyanin and azurin. The existence of a disulfide linkage in stellacyanin is established by thiol titrations, and the possibility exists that the fourth ligand in stellacyanin may involve disulfide sulfur. If so, the cystine --> Cu(II) transition is also expected to appear around 550 nm.