Improving Photostability of Photosystem I-Based Nanodevice by Plasmonic Interactions with Planar Silver Nanostructures.

One of the crucial challenges for science is the development of alternative pollution-free and renewable energy sources. One of the most promising inexhaustible sources of energy is solar energy, and in this field, solar fuel cells employing naturally evolved solar energy converting biocomplexes-photosynthetic reaction centers, such as photosystem I-are of growing interest due to their highly efficient photo-powered operation, resulting in the production of chemical potential, enabling synthesis of simple fuels. However, application of the biomolecules in such a context is strongly limited by the progressing photobleaching thereof during illumination. In the current work, we investigated the excitation wavelength dependence of the photosystem I photodamage dynamics. Moreover, we aimed to correlate the PSI-LHCI photostability dependence on the excitation wavelength with significant (ca. 50-fold) plasmonic enhancement of fluorescence due to the utilization of planar metallic nanostructure as a substrate. Finally, we present a rational approach for the significant improvement in the photostability of PSI in anoxic conditions. We find that photobleaching rates for 5 min long blue excitation are reduced from nearly 100% to 20% and 70% for substrates of bare glass and plasmonically active substrate, respectively. Our results pave promising ways for optimization of the biomimetic solar fuel cells due to synergy of the plasmon-induced absorption enhancement together with improved photostability of the molecular machinery of the solar-to-fuel conversion.