Effect of non-covalent binding of tannins to sodium caseinate on the stability of high-internal-phase fish oil emulsions.

ABSTRACT

In this study, we designed the noncovalent binding of sodium caseinate (SC) to tannic acid (TA) to stabilize high internal phase emulsions (HIPEs) used as fish oil delivery systems. Hydrogen bonding was the dominant binding force, followed by weak hydrophobic interaction and weak van der Waals forces, as demonstrated by FTIR, fluorescence spectroscopy, and molecular docking experiments, with a binding constant of 3.25 × 106, a binding site of 1.2, and a static quenching of the binding. Increasing SCTA from SC to 21 decreased the particle size from 107.37 ± 10.66 to 76.07 ± 2.77 nm and the zeta potential from -6.99 ± 2.71 to -22 ± 2.42 mV. TA increased the interfacial tension of SC, decreased the surface hydrophobicity from 1.3 × 104 to 1.6 × 103 and improved the oxidation resistance of SC. The particle size of high internal phase emulsions stabilized by complexes with different mass ratios (SCTA from 10 to 21) increased from 4.9 ± 0.02 to 12.9 µm, the potential increased from -32.37 ± 2.7 to -35.07 ± 2.58 mV, and the instability index decreased from 0.75 to 0.02. Thicker interfacial layers could be observed by laser confocal microscopy, and an increase in the storage modulus indicated a formation of a stronger gel network. SCTA of 10 showed emulsion breakage after 14 d of storage at room temperature. SCTA of 21 showed the lowest degree of oil-water separation after freeze-thaw treatment. Especially, the most stable high endo-phase emulsion (at SCTA of 21) prepared at each mass ratio was selected for further stability exploration. The emulsion particle size increased only from 15.63 ± 0.06 to 22.27 ± 0.35 µm at salt ion concentrations of 50-200 mM and to 249.33 ± 31.79 µm at 300 mM. The instability index and storage modulus of the high endo-phase emulsions increased gradually with increasing salt ion concentrations. At different heating temperatures (55-85 °C), the instability index of the high internal phase emulsion gradually decreased and the storage modulus gradually increased. Meanwhile, at 50 °C for 15 d of accelerated oxidation, the content of hydroperoxide decreased from 53.32 ± 0.18 to 37.48 ± 0.77 nmol/g, about 29.7 %, and the thiobarbituric acid value decreased from 1.06 × 103 to 0.8 × 103, about 24.5 %, in the high endo-phase emulsions prepared by 21 SCTA compared to the fish oils, and the SC-stabilized high endo-phase only emulsion broke at the sixth day of oxidation. From the above findings, it was concluded that the high internal phase emulsion prepared with SCTA of 21 can be used as a good delivery system for fish oil.