Protein Nanobarrel for Integrating Chlorophyll a Molecules and Its Photochemical Performance.

Taking inspiration from biology's effectiveness in nanoscale organization of chlorophylls for photosynthesis, we describe here a design for chlorophyll-protein conjugates that exploits the central hydrophobic cavity of GroEL protein nanobarrel as a binding pocket for chlorophyll. We found water-soluble conjugates of chlorophyll with GroEL could be easily generated via detergent dialysis. The number of chlorophyll units bound to GroEL is tunable by varying the equilibrium concentration of chlorophyll during dialysis. Meanwhile, it is shown that an increase in the entrapped chlorophyll amount leads to an improvement of chlorophyll-GroEL photostability. Using methyl viologen as an electron acceptor, we demonstrate that chlorophyll-GroEL has photoreduction activity, which is also switchable in on/off illumination mode. Finally, it is shown that chlorophyll-GroEL-sensitized solar cells have good photoelectric properties, yielding a high photoelectric conversion efficiency of ∼0.9%. The current strategy may be adopted for integrating other photosensitizing dyes or for other photocatalytic reactions.