Excited States of the Inactive and Active Forms of the Orange Carotenoid Protein

The orange carotenoid protein (OCP) is a crucial player in the process of nonphotochemical quenching in a large number of cyanobacteria. This water-soluble protein binds one pigment only, the keto carotenoid 3'-hydroxyechinenone, and needs to be photoactivated by strong (blue-green) light in order to induce energy dissipation within or from the phycobilisome, the main light harvesting system of these organisms. We performed transient-absorption spectroscopy on OCP samples frozen in the inactive and active forms at 77 K. By making use of target analysis we determined the excited state properties of the active form. Our results show that OCP photoactivation modifies the carotenoid excited state energy landscape. More specifically the photoactivated OCP is characterized by one state with predominantly ICT character (ICT/S1) and a lifetime of 2.3 ps, and another state with mainly S1 character (S1/ICT) with a lifetime of 7.6 ps. We also show that the kinetic model is fully consistent with the RT data obtained earlier (Berera et al., J. Phys. Chem. B 2012, 116, 2568-2574). We propose that this ICT/S1 state acts as the quencher in the OCP mediated nonphotochemical quenching.