Ionic Aggregation of Macromolecules as the Cause of the Kinetic (Non)Stability of Physicochemical Properties of Chitosan Solutions
Hydrodynamic, optical, colloid-flocculating, film-forming and structural morphological properties of diluted chitosan solutions (50–640 kDa) in acetate buffer (0.33 М СН3СООН + 0.2 М СН3СOONa), both initial ones and stored for ~1,850 days, were studied. It has been established that the decrease in the intrinsic viscosity of solutions over time is manifested for the reprecipitated and high-molecular-weight samples of chitosan to a greater degree. The viscosity drop effect is not affected by the use of untreated or sterile degassed distilled water to dissolve the polymer. A decrease in the values of the self-diffusion coefficient of macromolecules and an increase in the refractive index increment of solutions were also observed in the course of storage. At the same time, optical, electrochemical and flocculating properties of the polymer system showed a very slight change. A diagram of the kinetics of physicochemical properties of the chitosan–acetate buffer system is proposed, which includes three time stages with different patterns of structure formation. It is suggested that features of the properties of acid-salt solutions over time are controlled by the formation of ion pairs of the polycation with acetate anions, their multiplets, followed by ionic aggregation of the structures formed and liquid-crystal phase separation of the polymer system. It was found that the spontaneously separated phase is represented by a highly crystalline polymorphic modification of the polymer with characteristic features of an «anhydrous » crystal lattice.
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