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SynopsisDielectric dispersion measurements on poly-y-benzyl-L-glutamate (PBLG) in dioxane and dioxane-dichloroacetic acid (DCA) mixtures in the frequency range 203 Hz-2 MHz were made in order to study the structure of molecular aggregates. The structure of aggregates is explained on the basis of the variation of dipole moment and relaxation time with degree of aggregation. PBLG was found to form linear head-to-tail-type aggregates in dioxane. These aggregates gradually reduce in size without loosing their a-helical structure during the process of disaggregation obtained by either adding DCA to the solution in dioxane or by heating. J t was confirmed that the addition of 30 wt ' % DCA completely destroys the aggregation of PBLG in dioxane at 30°C. Thermal disaggregation, however, was not complete even at a temperature approaching the boiling point of the solvent. A reaction scheme for aggregation is proposed and equilibrium constants are calculated a t various stages of aggregation. The enthalpy of aggregate formation is found to be -3 kcal/mol. Results of optical rotatory dispersion measurements of the helixcoil transition in this system are also presented.

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