Genipin is increasingly used as a crosslinking agent for chitosans due to its low cytotoxicity as a naturally occurring extract of the plant Gardenia jasminoides. Genipin reacts with the primary amino groups of chitosan to form blue hydrogels. We studied the gelation kinetics of different chitosans varying in their properties (molar mass 34 000-213 000 g mol-1, degree of acetylation 9-20%) and genipin in detail. We found that critical sol-gel transition times obtained from dynamic light scattering were in good agreement with the results obtained by small deformation oscillatory rheometry and microviscosimetry at high concentrations of chitosan. However, at below critical concentrations, we found a second regime of gelation that followed the same Ross-Murphy's gelation kinetics. The macroscopic appearance of these samples was a suspension of weak gel-like particles that were sensitive to mechanical forces. We believe that the material is a mesoscopic gel, as described for other polymers. To the best of our knowledge, this is the first time that this phenomenon has been described for the gelling system of chitosan and genipin.
Engwer etal SI mesoscopic gelation