Competition among physical, chemical, and hybrid gelation mechanisms in biopolymers.

Depending on how they form their linkages, biopolymer gelatin gels are commonly classified as physical, chemical, or hybrid; in gelatin hybrid gels, the physical and chemical crosslinking mechanisms occur simultaneously. The viscoelastic behavior of gels following different gelation processes was determined around the gel point. Their gel fractal dimensions were obtained using the BST-scaling model from large amplitude oscillatory shear results. The fractal dimension of hybrid gels is between 1.46 and 1.60, depending on the dominant crosslinking process. The main features of the Lissajous-Bowditch curves were determined for maturated gels that follow different gelation processes, and it is possible to observe the dominant gelation mechanism. The gelation kinetics process is followed by measuring the mean squared displacement (MSD) of microspheres embedded in gelatin solutions using diffusion wave spectroscopy, which in turn allows evaluating G '( ω ) and G ''( ω ), the persistence length, and the mesh size as a function of time throughout the gelation process. The MSD, as a function of elapsed time from the start of the gelation process, follows a behavior that depends on the gelation processes. As time elapses after gelation starts, the persistence length of the unstructured, non-bonded flexible polymer sections decreases due to the formation of bonds. In the hybrid case, it is not a mixture of both processes; they are not independent when occurring simultaneously. The time evolution of the gel network's mesh size roughly follows an exponential decay.