Mathematical Modeling of Alpha-Tocopherol Early Degradation Kinetics to Predict the Shelf-Life of Bulk Oils.

The kinetics of lipid oxidation includes a lag phase followed by an exponential increase in oxidation products, which cause rancidity. Current models focus on the slope of this exponential curve for shelf-life estimation, which still requires the measurement of full oxidation kinetics. In this paper, we analyzed the formation of lipid oxidation products in stripped soybean oil containing different levels of α-tocopherol. The lag phases of lipid hydroperoxides and headspace hexanal formation were found to have a strong positive correlation with the α-tocopherol depletion time. We propose that the kinetics of antioxidant (α-tocopherol) depletion occur during the lag phase and could serve as an early shelf-life indicator. Our results showed that α-tocopherol degradation can be described by Weibull kinetics over a wide range of initial concentrations. Furthermore, we conducted in silico investigations using Monte Carlo simulations to critically evaluate the feasibility and sensitivity of the shelf-life prediction using early antioxidant degradation kinetics. Our results revealed that the shelf life of soybean oil may be accurately predicted as early as 20% of the overall shelf life. This innovative approach provides a more efficient and faster assessment of shelf life, ultimately reducing waste and enhancing product quality.

Synergistic Mechanisms of Interactions between Myricetin or Taxifolin with α-Tocopherol in Oil-in-Water Emulsions.

The antioxidant interactions between α-tocopherol and myricetin in stripped soybean oil-in-water emulsions at pH 4.0 and pH 7.0 were analyzed. At pH 7.0, α-tocopherol (α-TOC):myricetin (MYR) ratios of 2:1 and 1:1 yielded interaction indices of 3.00 and 3.63 for lipid hydroperoxides and 2.44 and 3.00 for hexanal formation, indicating synergism. Myricetin's ability to regenerate oxidized α-tocopherol and slow its degradation was identified as the synergism mechanism. Antagonism was observed at pH 4.0 due to high ferric-reducing activity of myricetin in acidic environment. The interaction between α-tocopherol and taxifolin (TAX) was also investigated due to structural similarities of myricetin and taxifolin. α-Tocopherol and taxifolin combinations exhibited antagonism at both pH 4.0 and pH 7.0. This was associated with taxifolin's inability to recycle α-tocopherol while still increasing the prooxidant activity of iron. The combination of α-tocopherol and myricetin was found to be an excellent antioxidant strategy for oil-in-water emulsions at pH values near neutrality.

Enzymatic Modification of Lecithin for Improved Antioxidant Activity in Combination with Tocopherol in Emulsions and Bulk Oil.

Oxidized α-tocopherol can be regenerated by phosphatidylethanolamine (PE), but current commercial sources of PE are too expensive for use as a food additive. The present study aims to determine the optimal reaction conditions for generating high PE lecithin (MHPEL) enzymatically and to validate the MHPEL's synergism with tocopherol in delaying lipid oxidation in an oil-in-water emulsion system at pH 7 and 4 and in bulk oil. Under optimal conditions of pH 9.0, 37 °C and 4 h, a MHPEL with ∼71.6% PE was obtained from 96% phosphatidylcholine lecithin using phospholipase D from Streptomyces chromofuscus. Mixed tocopherols (300 µmol/kg oil) and MHPEL (1500 µmol/kg oil) synergistically increased both the hydroperoxide and hexanal lag phase of lipid oxidation in stripped soybean oil-in-water emulsions at pH 7 by 3 days. At pH 4, this combination increased the hydroperoxide and hexanal lag phases by 3 and 2 days, respectively. The combination of 50 µmol/kg oil α-tocopherol and 1000 µmol/kg oil MHPEL also synergistically increased the hydroperoxide (5 days) and hexanal (4 days) lag phases in stripped bulk soybean oil. This approach represents a potential clean-label antioxidant system that could have commercial applications to decrease food waste.

Improvement of stability and bioaccessibility of ß-carotene by curcumin in pea protein isolate-based complexes-stabilized emulsions: Effect of protein complexation by pectin and small molecular surfactants.

The impact of different complexes on the properties of ß-carotene-loaded emulsions was investigated by measuring the droplet size, encapsulation efficiency, droplet morphology, and physical stability. The photo and thermal stability of ß-carotene and its bioaccessibility during digestion were also analyzed. Comparing to the emulsions stabilized by other complexes, the emulsion stabilized by the high methoxyl pectin-rhamnolipid-pea protein isolate-curcumin (HMP-Rha-PPI-Cur) complex had the smallest droplet size (17.53 ± 0.15 µm) and the maximum encapsulation efficiency for curcumin (90.33 ± 0.03 %) and ß-carotene (92.16 ± 0.01 %). The emulsion stabilized by the HMP-Rha-PPI-Cur complex exhibited better physical stability against creaming. The retention rate of ß-carotene in the HMP-Rha-PPI-Cur complex-stabilized emulsion was 17.75 ± 0.02 and 33.64 ± 0.02 % after UV irradiation and thermal treatment. The HMP-Rha-PPI-Cur complex-stabilized emulsion also had a higher level of free fatty acid released (43.67 %) and higher bioaccessibility of ß-carotene (32.35 ± 0.02 %).

Ability of Sodium Dodecyl Sulfate (SDS) Micelles to Increase the Antioxidant Activity of α-Tocopherol.

As emulsifiers become saturated on the surface of an emulsion droplet, any additional emulsifier migrates to the aqueous phase. Continuous phase surfactants have been shown to increase α-tocopherol efficacy, but it is unclear if this is the result of chemical or physical effects. The addition of α-tocopherol to an oil-in-water emulsion after homogenization resulted in a 70% increase of α-tocopherol in the continuous phase when sodium dodecyl sulfate (SDS) was at levels that were greater than the SDS critical micelle concentration. Conversely, when α-tocopherol was dissolved in the lipid before emulsification, continuous phase SDS concentrations did not increase. When SDS concentration led to an increase in the aqueous phase α-tocopherol, the oxidative stability of oil-in-water emulsions increased. Data indicated that the increased antioxidant activity was the result of surfactant micelles being able to decrease the prooxidant activity of α-tocopherol. Considering these results, surfactant micelles could be an important tool to increase the effectiveness of α-tocopherol.