Spin-labelling studies of the agarose gelling-system

Rates of tumbling and exchange of free nitroxides in aqueous solution are unaffected by the presence of quite high concentrations of agarose gel. Low-level, covalent attachment of labels to the polysaccharide by means of stable, acetamido ether linkages, however, causes considerable diminution in their rate of reorientation. Dissolution of this material to form a gel and melting and setting of the gel cause further changes in the e.s.r. spectrum. Experimental correlation-times for reorientation of label may be decomposed into contributions from rotation about bonds in the linking group and from polysaccharide motions. This allows information to be obtained about the microscopic characteristics of the gel state, which is found to vary greatly depending on its history.