510a Photosystem I Films at Nanoporous Gold Leaf Electrodes

G. Kane Jennings and Peter N. Ciesielski. Department of Chemical and Biomolecular Engineering, Vanderbilt University, Box 1604 Station B, Nashville, TN 37235

Plants and some types of bacteria demonstrate an elegant means to capitalize on the superabundance of solar energy that reaches our planet with their energy conversion process called photosynthesis. Seeking to take advantage of Nature's optimization of this process, we have devised a biomimetic photonic energy conversion system that makes use of the photoactive protein complex Photosystem I (PSI), immobilized on the surface of nanoporous gold leaf (NPGL) electrodes, to drive a photoinduced electric current through an electrochemical cell. In this presentation I will discuss how the additional PSI/electrode interfacial area provided by the NPGL allows for an increase in PSI-mediated electron transfer with respect to an analogous 2D system. Surface area enhancements provided by the NPGL electrodes over planar electrodes were obtained by the charge integration of peaks resulting from silver underpotential deposition (UPD) and revealed that enhancements of up to 14-fold were achieved. This enhancement of interfacial area is pertinent for other applications involving electron transfer between phases; thus, I will also describe the widely accessible and scalable method by which the NPGL electrode films used in this study are fabricated and attached to glass and Au/Si supports, and demonstrate their adaptability by modification with various self-assembled monolayers (SAMs). Exposing an aldehyde-terminated SAM to a buffered solution containing PSI resulted in covalent bonds between the SAM and exposed lysine residues on the protein complex. Photochronoamperometric measurements of the PSI-modified electrodes revealed that the protein complexes retained their photonic energy conversion functionality after attachment to the electrode surface. Finally, I will discuss the relationship between the magnitude of the PSI-catalyzed photocurrent enhancements provided by the NPGL electrode films and the dealloying times employed during the electrodes' fabrication, because the small pores achieved at relatively short times are inaccessible to PSI, while pores produced by dealloying times of 3 h and longer are of adequate dimensions to accommodate multiple PSI complexes.