Effects of Distance and Driving Force on Photoinduced Electron Transfer between Photosynthetic Reaction Centers and Gold Electrodes

Abstract

The electron-transfer (ET) parameters for oriented and aligned monolayers of the bacterial photosynthetic reaction center (RC) from Rhodobacter sphaeroides formed on the top of self-assembled monolayers (SAMs) of alkanethiols of various lengths immobilized on gold electrode are estimated using cyclic voltammetry and photoelectrochemistry. Utilization of the unique polyHis tag in the protein and the Ni−NTA chelator complex in SAMs allows for specific protein orientation with the RC primary donor facing the electrode. To improve the efficiency of ET between the RC special pair and the electrode, an RC-Cyt complex was formed (J. Am. Chem. Soc. 2006, 128, 12044−12045). The results are analyzed in terms of integrated Marcus formalism, taking into account the density of electronic states in the metal. The dependence of the ET rate on the distance between RC and electrode demonstrates an adiabatic region up to 10 A, typical for other proteins, followed by a nonadiabatic area of electron tunneling with a β-factor...