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Some Radiation and Photochemical Studies in Aqueous Polysaccharide Gel Systems

The radiation and photochemistry of aqueous polysaccharide gel matrices have been investigated with a view to prolonging the lifetime of transient species, prior to storage of photochemical events. Our results indicate that with gels of kappa carrageenan and agarose, the rigid macroscopic gel structure is not reflected in the microscopic structure and reactions resemble closely those that would take place in aqueous solution under comparable conditions. This shows that the interior of the gel structure is essentially very fluid. Fluorescence probes were used in agarose gel systems incorporating neutral and anionic surfactants. Under such circumstances, there is strong evidence showing that a micellar-type environment exists, and also a gel-surfactant complex is formed with both neutral and anionic surfactants. The gel-surfactant complex appears on the basis of fluorescence quenching and fluorescence polarization studies, to have a more mobile interior than the interior of an ordinary surfactant micelle in the absence of the agarose. Studies on the stoichiometry of the complex indicate a much lower critical micelle concentration for the surfactant sodium dodecyl sulphate (SDS) in the presence of agarose. The agarose gel structure does not aid the micellar catalysed charge separation that occurs on photolysis of pyrene.