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Recently, thermosensitive chitosan systems have attracted the interest of many researchers due to their growing application potential. Nevertheless, the mechanism of the sol-gel phase transition is still being discussed, and the glycerophosphate salt role is ambiguous. The aim of the work is to analyze the possibility of the exclusive use of a non-sodium glycerophosphate salt and to determine its impact on the gelation conditions determined by rheological and turbidimetric measurements as well as the stability of the systems by measuring changes in the Zeta potential value. It was found that ensuring the same proportions of glycerophosphate ions differing in cation to amino groups present in chitosan chains, leads to obtaining systems significantly different in viscoelastic properties and phase transition conditions. It was clearly shown that the systems with the calcium glycerophosphate, the insoluble form of which may constitute additional aggregation nuclei, undergo the gelation the fastest. The use of magnesium glycerophosphate salt delays the gelation due to the heat-induced dissolution of the salt. Thus, it was unequivocally demonstrated that the formulation of the gelation mechanism of thermosensitive chitosan systems based solely on the concentration of glycerophosphate without discussing its type is incorrect.

Polysaccharide matrices formed via thermoinduced sol–gel phase transition are promising systems used as drug carriers and minimally invasiveness scaffolds in tissue engineering. The strong shear field generated during injection may lead to changes in the conformation of polymer molecules and, consequently, affect the gelation conditions that have not been studied so far. Chitosan (CS) and hydroxypropyl cellulose (HPC) sols were injected through injection needles (14 G–25 G) or sheared directly in the rheometer measuring system. Then the sol–gel phase transition conditions were determined at 37 °C using rheometric, turbidimetric, and rheo-optical techniques. It was found that the use of low, respecting injection, shear rates accelerate the gelation, its increase extends the gelation time; applying the highest shear rates may significantly slow down (HPC) or accelerate gelation (CS) depending on thixotropic properties. From a practical point of view, the conducted research indicates that the use of thin needles without preliminary tests may lead to an extension of the gelation time and consequently the spilling of the polymeric carrier before gelation. Finally, an interpretation of the influence of an intensive shear field on the conformation of the molecules on a molecular scale was proposed.