Supramolecular Structure and Mechanical Performance of κ-Carrageenan-Gelatin Gel.

In this work, by means of complex physicochemical methods the structural features of a composite κ-carrageenan-gelatin system were studied in comparison with initial protein gel. The correlation between the morphology of hydrogels and their mechanical properties was demonstrated through the example of changes in their rheological characteristics. The experiments carried out with PXRD, SAXS, AFM and rheology approaches gave new information on the structure and mechanical performance of κ-carrageenan-gelatin hydrogel. The combination of PXRD, SAXS and AFM results showed that the morphological structures of individual components were not observed in the composite protein-polysaccharide hydrogels. The results of the mechanical testing of initial gelatin and engineered κ-carrageenan-gelatin gel showed the substantially denser parking of polymer chains in the composite system due to a significant increase in intermolecular protein-polysaccharide contacts. Close results were indirectly followed from the SAXS estimations-the driving force for the formation of the common supramolecular structural arrangement of proteins and polysaccharides was the increase in the density of network of macromolecular chains entanglements; therefore, an increase in the energy costs was necessary to change the conformational rearrangements of the studied system. This increase in the macromolecular arrangement led to the growth of the supramolecular associate size and the growth of interchain physical bonds. This led to an increase in the composite gel plasticity, whereas the enlargement of scattering particles made the novel gel system not only more rigid, but also more fragile.

Modulation of Molecular Structure and Mechanical Properties of κ-Carrageenan-Gelatin Hydrogel with Multi-Walled Carbon Nanotubes.

Hydrogels, three-dimensional hydrophilic water-insoluble polymer networks having mechanical properties inherent for solids, have attracted continuous research attention over a long time period. Here, we studied the structure and properties of hydrogel based on gelatin, κ-carrageenan and CNTs using the combination of SAXS, PXRD, AFM microscopy, SEM and rheology methods. We have shown that the integration of polysaccharide and protein in the composite hydrogel leads to suppression of their individual structural features and homogenization of two macromolecular components into a single structural formation. According to obtained SAXS results, we observed the supramolecular complex, which includes both polysaccharide and protein components associated with each other. It was determined that hydrogel structure formed in the initial solution state (dispersion) retains hydrogel supramolecular structure under its cooling up to gel state. The sizes of dense cores of these polyelectrolyte complexes (PEC) slightly decrease in the gel state in comparison with PEC water dispersion. The introduction of CNTs to hydrogel does not principally change the type of supramolecular structure and common structural tendencies observed for dispersion and gel states of the system. It was shown that carbon nanotubes embedded in hydrogel act as the supplementary template for formation of the three-dimensional net, giving additional mechanical strengthening to the studied system.