Intermolecular Interactions in the Formation of Polysaccharide-Gelatin Complexes: A Spectroscopic Study.

Gelatin, due to its gelling and stabilizing properties, is one of the widely used biopolymers in biotechnology, medicine, pharmaceuticals, and the food industry. One way to modify the characteristics of gelatin is molecular modification by forming non-covalent polyelectrolyte complexes with polysaccharides based on the self-organization of supramolecular structures. This review summarizes recent advances in the study of various types and the role of intermolecular interactions in the formation of polysaccharide-gelatin complexes, and conformational changes in gelatin, with the main focus on data obtained by spectroscopic methods: UV, FT-IR, and 1H NMR spectroscopy. In the discussion, the main focus is on the complexing polysaccharides of marine origin-sodium alginate, κ-carrageenan, and chitosan. The prospects for creating polysaccharide-gelatin complexes with desired physicochemical properties are outlined.

Rheological Properties of Fish Gelatin Modified with Sodium Alginate.

Polyelectrolyte complexes of sodium alginate and gelatin obtained from cold-blooded fish were studied for potential application as structure-forming agents in food hydrogels. The mass ratio of sodium alginate to gelatin plays a decisive role in the sol-gel transition and rheological behavior of the complexes. Differences in the sol-gel transition temperature were observed upon heating and cooling, as is typical for such materials. We investigated the characteristics of this transition by measuring the isothermal changes in the elastic modulus over time at a constant frequency and the transition temperature at a range of frequencies. The kinetic nature of this transition depends on the composition of the complexes. A characteristic alginate-gelatin mass ratio is the ratio at which maximum transition temperature as well as elastic modulus and viscosity (rheological parameters) values are obtained; the characteristic mass ratio for these complexes was found to be 0.06. Calculation of the ionic group ratios in the biopolymers that form complexes and comparison of these data with the turbidimetric titration results clarified the origin of these maxima. Measuring the viscoelastic properties and the creep-elastic recoil of the samples allowed us to characterize these materials as viscoelastic media with a viscosity in the order of 103-104 Pa·s and an elastic modulus in the order of 102-103 Pa. These values drastically decrease at a certain stress threshold, which can be treated as the gel strength limit. Therefore, the observed rheological behavior of gels formed by fish gelatin modified with sodium alginate characterizes them as typical viscoelastic soft matter.

Modified Fish Gelatin as an Alternative to Mammalian Gelatin in Modern Food Technologies.

This review considers the main properties of fish gelatin that determine its use in food technologies. A comparative analysis of the amino acid composition of gelatin from cold-water and warm-water fish species, in comparison with gelatin from mammals, which is traditionally used in the food industry, is presented. Fish gelatin is characterized by a reduced content of proline and hydroxyproline which are responsible for the formation of collagen-like triple helices. For this reason, fish gelatin gels are less durable and have lower gelation and melting temperatures than mammalian gelatin. These properties impose significant restrictions on the use of fish gelatin in the technology of gelled food as an alternative to porcine and bovine gelatin. This problem can be solved by modifying the functional characteristics of fish gelatin by adding natural ionic polysaccharides, which, under certain conditions, are capable of forming polyelectrolyte complexes with gelatin, creating additional nodes in the spatial network of the gel.

Polyelectrolyte Polysaccharide-Gelatin Complexes: Rheology and Structure.

General features of rheological properties and structural peculiarities of polyelectrolyte polysaccharide-gelatin complexes were discussed in this paper. Experimental results were obtained for typical complexes, such as -carrageenan-gelatin, chitosan-gelatin and sodium alginate-gelatin complexes. A rheological method allows us to examine the physical state of a complex in aqueous phase and the kinetics of the sol-gel transition and temperature dependences of properties as a result of structural changes. The storage modulus below the gelation temperature is constant, which is a reflection of the solid-like state of a material. The gels of these complexes are usually viscoplastic media. The quantitative values of the rheological parameters depend on the ratio of the components in the complexes. The formation of the structure as a result of strong interactions of the components in the complexes was confirmed by UV and FTIR data and SEM analysis. Interaction with polysaccharides causes a change in the secondary structure of gelatin, i.e., the content of triple helices in an -chain increases. The joint analysis of the structural and rheological characteristics suggests that the formation of additional junctions in the complex gel network results in increases in elasticity and hardening compared with those of the native gelatin.

Tailoring Cod Gelatin Structure and Physical Properties with Acid and Alkaline Extraction.

Gelatin (G) was extracted from the skin of Atlantic cod at different pH of the aqueous phase (pH 3, 4, 5, 8 and 9) and at a temperature of 50 ± 1 °C. The yield of gelatin (G3, G4, G5, G8, and G9, respectively) was 49-55% of the dry raw material. The influence of extraction pH on the physicochemical and functional properties of gelatin was studied. Sample G5 was characterized by higher protein content (92.8%) while lower protein content was obtained for sample G3 (86.5%) extracted under more aggressive conditions. Analysis of the molecular weight distribution showed the presence of α- and ß-chains as major components; the molecular weight of the samples ranged between 130 and 150 kDa, with sample G5 having the highest molecular weight. IR spectra of all samples had absorption bands characteristic of fish gelatin. The study of the secondary structure demonstrated higher amounts of ordered triple collagen-like helices for G5 extracted under mild conditions. Accordingly, sample G5 formed gels with high values for the storage modulus and gelling and melting temperatures, which decrease as pH changes into acidic or alkaline regions. In addition, the differential scanning calorimetry data showed that G5 had a higher glass transition temperature and melting enthalpy. Thus, cod skin is an excellent source of gelatin with the necessary physicochemical and functional properties, depending on the appropriate choice of aqueous phase pH for the extraction.