Most of our effort during the past grant period has been directed towards investigating electron transfer processes involving redox proteins at lipid bilayer/aqueous interfaces. This theme, as was noted in our previous three year renewal proposal, is consistent with our goal of developing biomimetic solar energy conversion systems which utilize the unique properties of biological electron transfer molecules. Thus, small redox proteins such as cytochrome c, plastocyanin and ferredoxin function is biological photosynthesis as mediators of electron flow between the photochemical systems localized in the membrane, and more complex soluble or membrane-bound redox proteins which are designed to carry out specific biological tasks such as transbilayer proton gradient formation, dinitrogen fixation, ATP synthesis, dihydrogen synthesis, generation of strong reductants, etc. In these studies, we have utilized two principal experimental techniques, laser flash photolysis and cyclic voltammetry, both of which permit direct measurements of electron transfer processes.

Most of our effort during the past grant period has been directed towards investigating electron transfer processes involving redox proteins at lipid bilayer/aqueous interfaces. This theme, as was noted in our previous three year renewal proposal, is consistent with our goal of developing biomimetic solar energy conversion systems which utilize the unique properties of biological electron transfer molecules. Thus, small redox proteins such as cytochrome c, plastocyanin and ferredoxin function is biological photosynthesis as mediators of electron flow between the photochemical systems localized in the membrane, and more complex soluble or membrane-bound redox proteins which are designed to carry out specific biological tasks such as transbilayer proton gradient formation, dinitrogen fixation, ATP synthesis, dihydrogen synthesis, generation of strong reductants, etc. In these studies, we have utilized two principal experimental techniques, laser flash photolysis and cyclic voltammetry, both of which permit direct measurements of electron transfer processes.

This project has received DOE support since July 1, 1978. During this period, 40 papers have been published dealing predominantly with chlorophyll-photosensitized electron transfer reactions in a variety of media (solutions, polymer films, lipid bilayer membranes). The overall theme of this work has been to develop mechanistic strategies f or photochemical energy storage via chlorophyll, using the green plant photosynthetic system as a paradigm for designing in vitro systems. Microheterogeneous lipid vesicle suspensions allow ready application of time-resolved optical spectroscopy to follow the course of light-induced electron transfer processes. Both the yields and the lifetimes of electron transfer products were markedly improved in the vesicle systems. In subsequent studies, this compartmentalization was favorably manipulated by controlling the electrical charge on the membrane surface, by controlling the solubility properties of the acceptors, by varying the lipid composition, by using mediators to create a concentration gradient to carry electrons from within the bilayer to the aqueous medium, and by incorporating secondary electron acceptors into the aqueous phase.