For biomedical applications, gelatin is usually modified with methacryloyl groups to obtain gelatin methacryloyl (GelMA), which can be crosslinked by a radical reaction induced by low wavelength light to form mechanically stable hydrogels. The potential of GelMA hydrogels for tissue engineering has been well established, however, one of the main disadvantages of mammalian-origin gelatins is that their sol-gel transitions are close to room temperature, resulting in significant variations in viscosity that can be a problem for biofabrication applications. For these applications, cold-water fish-derived gelatins, such as salmon gelatin, are a good alternative due to their lower viscosity, viscoelastic and mechanical properties, as well as lower sol-gel transition temperatures, when compared with mammalian gelatins. However, information regarding GelMA (with special focus on salmon GelMA as a model for cold-water species) molecular conformation and the effect of pH prior to crosslinking, which is key for fabrication purposes since it will determine final hydrogel’s structure, remains scarce. The aim of this work is to characterize salmon gelatin (SGel) and salmon methacryloyl gelatin (SGelMA) molecular configuration at two different acidic pHs (3.6 and 4.8) and to compare them to commercial porcine gelatin (PGel) and methacryloyl porcine gelatin (PGelMA), usually used for biomedical applications. Specifically, we evaluated gelatin and GelMA samples’ molecular weight, isoelectric point (IEP), their molecular configuration by circular dichroism (CD), and determined their rheological and thermophysical properties. Results showed that functionalization affected gelatin molecular weight and IEP. Additionally, functionalization and pH affected gelatin molecular structure and rheological and thermal properties. Interestingly, the SGel and SGelMA molecular structure was more sensitive to pH changes, showing differences in gelation temperatures and triple helix formation than PGelMA. This work suggests that SGelMA presents high tunability as a biomaterial for biofabrication, highlighting the importance of a proper GelMA molecular configuration characterization prior to hydrogel fabrication.

Gelatin is a natural hydrocolloid with excellent film-forming properties, high processability, and tremendous potential in the field of edible coatings and food packaging. However, its reinforcing by materials such as cellulose nanocrystals (CNC) is often necessary to improve its mechanical behavior, including shape memory properties. Since the interaction between these polymers is complex and its mechanism still remains unclear, this work aimed to study the effect of low concentrations of CNC (2, 6, and 10 weight%) on the molecular organization, thermomechanical, and shape memory properties in mammalian gelatin-based composite films at low moisture content (~10 weight% dry base). The results showed that the presence of CNCs (with type I and type II crystals) interfered with the formation of the gelatin triple helix, with a decrease from 21.7% crystallinity to 12% in samples with 10% CNC but increasing the overall crystallinity (from 21.7% to 22.6% in samples with 10% CNC), which produced a decrease in the water monolayer in the composites. These changes in crystallinity also impacted significantly their mechanical properties, with higher E’ values (from 1 × 10⁴ to 1.3 × 10⁴ Pa at 20 °C) and improved thermal stability at higher CNC content. Additionally, the evaluation of their shape memory properties indicated that while molecular interactions between the two components occur, CNCs negatively impacted the magnitude and kinetics of the shape recovery of the composites (more particularly at 10 weight% CNC, reducing shape recovery from 90% to 70%) by reducing the netting point associated with the lower crystallinity of the gelatin. We believe that our results contribute in elucidating the interactions of gelatin–CNC composites at various structural levels and highlights that even though CNC acts as a reinforcement material on gelatin matrices, their interaction are complex and do not imply synergism in their properties. Further investigation is, however, needed to understand CNC–gelatin interfacial interactions with the aim of modulating their interactions depending on their desired application.