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Chemical Cross-Linking Gelatin with Natural Phenolic Compounds as Studied by High-Resolution NMR Spectroscopy

Cross-linking gelatin with natural phenolic compound caffeic acid (CA) or tannic acid (TA) above pH 9 resulted in formation of insoluble hydrogels. The cross-linking reactivity was controlled by variation of pH, the concentration of the gelatin solution, or the amount of CA or TA used in the reaction. The cross-linking chemistry was studied by high-resolution NMR technique in both solution and solid state via investigation on small molecular model systems or using (13)C enriched caffeic acid (LCA) in the reaction with gelatin. Direct evidence was obtained to confirm the chemical reactions occurring between the phenolic reactive sites of the phenolic compounds and the amino groups in gelatin to form C-N covalent bonds as cross-linking linkages in gelatin matrix. The cross-linked network was homogeneous on a scale of 2-3 nm. The cross-linking resulted in a significant decrease in the molecular mobility of the hydrogels, while the modulus of the films remained at high values at high temperatures.

Chemical modification of gelatin by a natural phenolic cross-linker, tannic acid.

Chemical modification of gelatin by a natural phenolic compound tannic acid (TA) at pH 8 was studied, and the properties of the modified gelatin materials were examined. The cross-linking effect was predominant when the TA content was lower, resulting in the formation of a partially insoluble cross-link network. The cross-linking structure was stable even under boiling, and the protein matrix became rigid, whereas the mechanical properties were enhanced. An effective cross-linking effect on gelatin matrix was achieved when the amount of TA was around 3 wt %. Further increase in the TA content enhanced the grafting and branching reactions between gelatin and TA in conjunction with the hydrogen bonding between gelatin and TA molecules. These effects produced an increase in molecular mobility of gelatin matrix, and the materials displayed a behavior similar to that of plasticized protein materials.

Wheat gluten-based renewable and biodegradable polymer materials with enhanced hydrophobicity by using epoxidized soybean oil as a modifier.

Epoxidized soybean oil (ESO) was applied as an additive for wheat gluten (WG) to modify the properties of the renewable and biodegradable natural polymer materials. Optimum intermolecular interactions and crosslinking between ESO chains and the WG matrix were achieved under alkaline conditions. The WGESO materials were heterogeneous on a scale of 20-30 nm, but the homogeneity was improved upon increasing the amount of glycerol as a plasticizer in the materials. The combination of plasticization and crosslinking effects derived from ESO resulted in good retention in mechanical strength for the plasticized WGESO materials as compared to those without 10 wt% of mobile ESO additives. The hydrophobicity of the plasticized WG materials was also enhanced significantly by using the ESO additives.

Plasticization and crosslinking effects of acetone-formaldehyde and tannin resins on wheat protein-based natural polymers

Efficient plasticization and sufficient crosslinking were achieved by using an acetone-formaldehyde (AF) resin as an additive in the thermal processing of wheat protein-based natural polymers. The mobile AF resin and its strong intermolecular interactions with a wheat protein matrix produced sufficient flexibility for the plastics, while the covalent bonds formed between AF and the protein chains also caused the water-soluble resin to be retained in the materials under wet conditions. The mechanical properties of the materials were also enhanced as an additional benefit due to the formation of crosslinked networks through the polymer matrix. Tensile strength was further enhanced when using AF in conjunction with tannin resin (AFTR) in the systems as rigid aromatic structures were formed in the crosslinking segments. Different components in wheat proteins (WPs) or wheat gluten (WG) (e.g., proteins, residual starch and lipids) displayed different capabilities in interaction and reaction with the AFTR additives, and thus resulted in different performances when the ratio of these components varied in the materials. The application of the AFTR additives provides a feasible methodology to thermally process wheat protein-based natural polymers with improved mechanical performance and water-resistant properties.