Utilization of dyes particularly in conjunction with organic polymers, is of interest in a number of contexts, including solar photochemistry, the operation of dye lasers, and the functionalization of biopolymers and proteins. In another context, investigation of biopolymer-bound dyes is important in understanding the fate of commercial dyestuffs as environmental pollutants in aquatic media. Arrays of chromophores in polymers are also of potential use in the development of photonic devices (e.g., molecular electronics). Novel effects induced by binding organic dyes to amphiphilic or water-soluble polymers (including peptides and proteins) are of particular interest to our group. Flash illumination, fluorescence, circular dichroism, and molecular modeling techniques are employed in the investigation of the properties of polymer-bound dye systems. Synthetic work is directed to judicious placement of chromophores and electron transfer groups in peptides or proteins. Investigations include the effect of polymer conformation (e.g., the presence of a-helices in peptides) in controlling photochemical behavior fordye-biopolymer assemblies. These studies are directed to a number of objectives, including the advance of theories dealing with long-range electron transfer, the development of new dye-polymer (drug-carrier) conjugates, and characterization of the photochemistry of dyestuffs bound to biopolymers such as humic acids in natural aquatic media. In this project, a series of peptides arebeing synthesized with covalently attached dye moieties attached to the N-terminus. These arethen allowed to self-assemble into structures that incorporate defined features (e.g., beta sheets and helices) that place the dyes in fixed spatial relationships to one another. The efficiency of electron transfers within the structures are then followed using various physical techniques.
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