Early stages of gelation in gelatin solution detected by dynamic oscillating rheology and nuclear magnetic spectroscopy

This study focuses on the early stages of the gelation of an aqueous type A (pig skin) gelatin solution. The thermo-reversible mono and triple helix formation was observed by rheology and proton NMR relaxation measurements. At high temperatures (T > 330 K), gelatin molecules form flexible random coils of small hydrodynamic radius, the elastic modulus of the solution is relatively low. On decreasing the temperature (330-320 K), mono helix formation begins, connected with an increase of the storage modulus and the hydrodynamic radius. The absence of a significant concentration dependence of this early variation of the modulus indicates the intramolecular nature of this structural change. The simultaneous decrease of the spin-spin relaxation times of the ¹H signals of certain aminoacids confirms its effect on the molecular mobility. As this affects especially the signals of arginine and lysine, we conclude that these basic aminoacids play a significant role in forming the intramolecular interactions. The formation of a three-dimensional network occurs at a point at which the viscosity begins to increase rapidly near the gel point (T < 320 K). This process is clearly dominated by intermolecular interactions, as the slope as well as the starting point of the rapid increase significantly depends on the concentration.