Phenolic compounds as antioxidants to improve oxidative stability of menhaden oil-based structured lipid as butterfat analog
Introduction
Oxidation is one of the leading causes of economic loss in the food industry. The lipid components, especially polyunsaturated fatty acids (PUFA), are the most important contributors to oxidative deterioration in foods. Lipid oxidation not only produces off-flavor but can also decrease nutritional value and cause safety concerns in foods. As a major component of foods and tissues, lipids not only affect traits in foods, such as texture, structure, mouthfeel, flavor, and color, but are also important contributors to many biological functions. Some PUFA are essential nutrients. Aside from functioning as energy storage material, a diverse range of biological functions also require PUFA, such as regulation of inflammatory response and hormone production, and aiding neural development and function (Akoh, 2017).
Recently, a structured lipid (SL) rich in eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) was synthesized through the acidolysis of menhaden oil with caprylic and stearic acid using Lipozyme® 435, a commercially available food grade lipase, as catalyst (Willett, Martini, & Akoh, 2019). EPA and DHA are beneficial to human health, lowering the risk of cardiovascular and neurodegenerative diseases (Cicero, Reggi, Parini, & Borghi, 2012). Medium-long-medium chain fatty acid (MLM)-type triacylglycerols (TAG) have enhanced nutritional and functional properties compared to the natural oils and fats (Mota et al., 2020). Due to the lipase preference of the sn-1/3 positions and the high levels of EPA and DHA at the sn-2 position of the menhaden oil TAG, a high proportion (31.9 ± 0.47%) of MLM-type TAG was produced as SL (Willett et al., 2019). The thermal behavior of the SL was also improved because of the incorporation of stearic acid. This SL has the potential for use as a healthier alternative to highly saturated fats, such as butterfat, which have been associated with increased levels of low-density lipoprotein cholesterol and increased risks of cardiovascular diseases and stroke (Micha & Mozaffarian, 2010). Moreover, PUFA in SL could help maintain its semisolid property while refrigerated or frozen, whereas the texture of butterfat would be hardened significantly, causing long waiting time before consumption or processing. However, as mentioned earlier, high levels of PUFA would lead to low oxidative stability, a short shelf-life, and safety concerns. The addition of antioxidant(s) could be a solution to the quality deterioration caused by lipid oxidation.
Many antioxidants, including synthetic and some natural antioxidants, are phenolic compounds, such as tocopherols (TOC) and tocotrienols, gallic acid (GA) and its derivatives, ferulic acid (FA), caffeic acid (CA), butylated hydroxytoluene (BHT), butylated hydroxy anisole (BHA), and tertiary butyl hydroquinone (TBHQ). Plant-derived phenolics are natural antioxidants and have attracted substantial interest due to their beneficial, functional, and nutritional properties, which include antioxidant and antimicrobial activities (Lee et al., 2009). Phenolic acids, such as GA, FA, and CA, are potent antioxidants that universally exist abundantly in plants functioning as antioxidants in plants, performing the roles of reducing agents, free radical scavengers, and quenchers of singlet oxygen formation (Ghasemzadeh & Ghasemzadeh, 2011). 1-o-Galloylglycerol (GG) is a secondary phenolic metabolite of many plants and can be synthesized chemically or enzymatically (Zhang & Akoh, 2019). It is a GA glycerol ester with ester functionality located at the sn-1 position of the glycerol moiety while the other two hydroxyl groups remain unesterified. Recently, GG synthesis was simplified and achieved in high yield on a large-scale via the glycerolysis of propyl gallate (PG) using Lipozyme® 435 (Zhang & Akoh, 2020), making its application in foods plausible. Rosemary extract (RE) is one of the major sources of natural antioxidants used commercially in food at present (Wang et al., 2017). The active components of RE consists of carnosol, carnosic acid (CRA), and rosmarinic acid (RA), all of which are phenolics (Frankel, Huang, Aeschbach, & Prior, 1996a). Considering the concentrations and efficacies of the active compounds in RE, CRA is the major source of its antioxidant activity in bulk oil (Frankel et al., 1996a, Frankel et al., 1996b, Wellwood and Cole, 2004).
Herein, we report the antioxidant activities of GA, PG, GG, FA, CA, CRA, RA, TOC, and BHT in a menhaden oil-based SL that may have the potential for use as butterfat analog. Synthetic antioxidant, BHT was used as reference substance for comparative purposes. The food industry has shown interest in replacing synthetic antioxidants, such as BHT that are harmful to health with natural and less harmful antioxidants. The differences on the effects of selected antioxidants in SL were investigated using an accelerated oxidation test. The effectiveness of the tested compounds in SL was evaluated at different stages of oxidation by measuring peroxide value (PV), p-anisidine value (pAV), and total oxidation (TOTOX) value. Hydrolysis of TAG was monitored using high-performance liquid chromatography (HPLC). The degradation of PUFA in SL during the accelerated oxidation test was monitored using gas chromatography (GC) and 1H nuclear magnetic resonance (NMR) spectroscopy. The oxidation induction time (OIT) of SL with different antioxidants/antioxidant combinations was evaluated by differential scanning calorimetry (DSC). The slip melting point, thermal behavior, solid fat content (SFC), rheological property, crystalline microstructure, and polymorphism of SL were also determined and compared with butterfat.
Section snippets
Chemicals and reagents
GA, PG, TOC, FA, CA, RA, and BHT were purchased from Sigma-Aldrich (St. Louis, MO, USA). RE was purchased from United States Pharmacopeia (Rockville, MD, USA). CRA was generously provided by Hunan Shineway Enterprise (Changsha, China). All solvents used in this study were HPLC grade and purchased from local chemical suppliers. All chemicals were used without further purification.
Preparation of 1-o-galloylglycerol and lipids
GG was synthesized using the alcoholysis of PG with glycerol as described previously (Zhang & Akoh, 2020). Briefly,
Physicochemical comparison of menhaden oil-based structured lipid and butterfat
As shown in Table 1, SL showed similar melting point and melting completion temperatures to butterfat. The crystallization onset temperature of SL was significantly higher than that of butterfat, indicating SL could crystallize at higher temperatures than butterfat. The results from the heating–cooling sweeps (Fig. 1.a and 1.b) were in agreement with the DSC results. Fig. 1.a and 1.b show the plots of storage (G′) and loss (G″) moduli of SL and butterfat as function of temperature. At the
Conclusions
A SL butterfat analog with similar melting point, solid fat content, thermal behavior, rheological property, and polymorphism was produced using the enzymatic acidolysis of menhaden oil with caprylic and stearic acids. Nine phenolic compounds and their mixtures were investigated as antioxidants to increase the oxidative stability of this butterfat analog. Using a single compound at 100 ppm, GG, RA, and BHT showed the greatest ability to delay the oxidation. For antioxidant combinations, a
CRediT authorship contribution statement
Siyu Zhang: Conceptualization, Methodology, Formal analysis, Investigation, Data curation, Writing - original draft. Sarah A. Willett: Investigation, Writing - review & editing. Joseph R. Hyatt: Investigation, Writing - review & editing. Silvana Martini: Writing - review & editing, Funding acquisition. Casimir C. Akoh: Conceptualization, Methodology, Supervision, Writing - review & editing, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgement
This project was supported by Agricultural and Food Research Initiative Grant No. 2017-67017-26476 from the USDA National Institute of Food and Agriculture, Improving Food Quality-A1361. The authors also would like to thank Food Science Research, University of Georgia for partial support of this work. Special thanks go to Dr. John Glushka from the Complex Carbohydrate Research Center NMR spectroscopy facility, University of Georgia, for assisting with NMR analysis.
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