Progress 10/01/23 to 09/30/24
Outputs PROGRESS REPORT Objectives (from AD-416): Objective 1. Stabilize sensitive and bioactive food ingredients, improve shelf-life, and reduce food waste with optimized natural antioxidants and plant extracts. Sub-Objective 1.A. Evaluate antioxidant activity of combinations of antioxidants in frying oils and fried foods. Sub-objective 1.B. Evaluate antioxidants or natural antioxidant extracts for protection of polyunsaturated and omega-3 oils and bioactive lipids and to extend shelf-life of whole foods and food ingredients. Objective 2. Enable oleogel applications to reduce saturated fats in foods. Sub-Objective 2.A. Investigate and optimize the physical and sensory properties as well as the oxidative stability of edible oleogels. Sub-objective 2.B. Evaluate interesterified natural waxes, waxes with vegetable oils, fatty alcohols or fatty acids, as potential new oleogelators. Objective 3. Improve commercial value and sustainable food production through recovery of healthful bioactive ingredients from food processing by-products or waste. Approach (from AD-416): Approximately 30% of the food supply in the United States is wasted and the worldwide problem is even larger. This waste represents a large strain on the environment and on the entire food production enterprise. According to the Food and Drug Administration (FDA), about 20% of the food waste in the United States is due to confusion about the meaning and safety of foods labeled with best before and use by dates. This means that extending shelf-stability of foods can have an impact in reducing food waste. There is also concern about the healthfulness of processed foods, including the high content of saturated fats, which consumers are advised to limit in the diet. However, reducing the saturated fat content of foods by substituting with healthier fats can influence product texture and mouthfeel, as well as the oxidative stability and shelf-life. The research of the next five years will enable the commercial development of natural antioxidants needed to improve the oxidative stability and shelf-life of foods formulated with a lower saturated fat content. Antioxidants will improve the stability of frying oils, fried foods, and high-value foods such as nuts and protein replacement bars. Oleogels will be developed with improved physical and melting properties for margarines and shortenings and other food applications that require hard fats and will have lower amounts of saturated fats and zero trans fats. New value-added ingredients such as antioxidants and bioactive lipids will be mined and characterized from low-value agricultural inputs. This research, together with complimentary technology and policy development strategies, will contribute to efforts to reduce food waste and improve the healthfulness of the food supply. Sub-objective 1.A is to evaluate the antioxidant activity of combinations of antioxidants in frying oil and fried foods. The overall goal is to develop synergistic antioxidant combinations that can be used to improve frying oil life and the shelf-life of fried foods. In support of Sub- objective 1.A, ARS researchers in Peoria, Illinois, conducted frying studies of sweet potatoes in canola oil with a variety of added antioxidants either alone or in combinations. Then they studied the effect of the antioxidants and combinations on the shelf-life of the sweet potato chips under accelerated storage conditions at a temperature of 55°C, analyzing headspace volatiles, tocopherol and beta- carotene loss from chips, and oxidative stability index (OSI). The secondary goal of their studies was to determine if oxidative stability index (OSI) and tocopherol analysis could be used as faster indicators or predictors for shelf-life. Using canola oil as the negative control, and tert- butylhydroquinone (TBHQ) as the positive control, ARS researchers in Peoria, Illinois, were able to demonstrate increased shelf-life with combinations of antioxidants including ascorbyl palmitate (an oil soluble vitamin C), methionine, and phytosteryl ferulates. Sub-objective 1.B is to evaluate antioxidants or natural antioxidants for protection of polyunsaturated and omega-3 oils and bioactive lipids and to extend shelf-life of whole foods and food ingredients. The milestone for the project was to complete shelf-life testing of margarines or other foods developed with oleogels under Objective 2, and so the progress under Sub-objective 1.B and Sub-objective 2.A are interrelated. In their previous studies, ARS researchers in Peoria, Illinois, found that the mixture of beeswax (BW) and candelilla wax (CDW) provided oleogels with higher gel strength and lower melting point than those with either wax alone. In addition, the improvement by mixing two waxes was also observed with margarine formulations. For the practical application of oleogels with this binary wax system, it was important to examine the physical stability of these margarine systems. Margarines were prepared using a typical formulation containing skim milk, salt, emulsifiers, and other ingredients where conventional fats were replaced with a 5% mixture of BW and CDW (1:1). Margarine samples were evaluated for their firmness, cohesiveness, and adhesiveness during storage at room temperature (21-22°C) after 15, 30, and 60 days. While physical properties of the margarine did not significantly change up to 15 days, firmness and cohesiveness decreased to 89% and 87% from the initial margarine, respectively, after 60 days. In contrast, adhesiveness of the margarine increased by 15% after 60 days. A similar trend was observed with oleogels alone during storage indicating that the decrease in the firmness of margarine may be attributed to the decrease in oleogel firmness. Further studies will be conducted to confirm the current conclusions in this study. In addition, oxidative stability studies with and without added antioxidants will commence, based on the results from Sub-objective 2. Sub-objective 2.A is to investigate and optimize the physical and sensory properties as well as the oxidative stability of edible oleogels. As progress towards this sub-objective, oleogels with a 1:1 mixture of BW and CDW were prepared since ARS researchers in Peoria, Illinois, found these to be one of the most promising wax combinations for use as fat substitutes due to their high gel strength and relatively low melting temperature. They were prepared with three different vegetable oils, olive, soybean, and flaxseed oils that are rich in oleic, linoleic, and linolenic acids, respectively. Two wax concentrations, 3 and 7% and two storage temperatures, 4 and 25°C, were used. Oxidation of oleogels was determined by peroxide value (PV) and conjugated diene value (CDV). PV and CDV of oleogels increased slower than the corresponding bulk oils at 4°C, but they increased faster than those of bulk oils at 25°C indicating that oleogelation decreased oil oxidation during storage at refrigeration temperature but not a room temperature. Most oleogels showed slightly faster oxidation than the fat from a commercial margarine indicating that additional protection is needed for practical product development with these oleogels. Olive oil contained 69.4% oleic acid while soybean oil contained 57.2% linoleic acid as their major fatty acid. Since oleic acid is much more stable than linoleic acid to oxidation, higher oxidative stability was expected with olive oil oleogels. However, olive oil oleogels oxidized faster than soybean oil oleogels indicating that inherent antioxidants in soybean oil effectively prevented oil oxidation. Soybean oil contained higher phenolics (38.5 mg gallic acid equivalent (GAE)/100 g vs. 17.5 mg GAE/ 100g) as well as higher total tocopherols (1643.7 µg/g vs. 316.0 µg/g) than olive oil. Sub-objective 2.B is to evaluate interesterified natural waxes, waxes with vegetable oils, fatty alcohols, or fatty acids, as potential new oleogelators. In progress towards this sub-objective, ARS researchers in Peoria, Illinois, evaluated sophorolipid based hydroxy fatty acids as well as hydrogenated Lesquerella oil as potential oleogelators. ARS researchers in Peoria, Illinois, collaborated with ARS researchers at Wyndmoor, Pennsylvania, who provided some of the hydroxy fatty acids from fermentation of special yeast cultures. ARS researchers also collaborated with ARS researchers in the BioOils Research Unit, Peoria, Illinois, that provided fully hydrogenated Lesquerella oil, which has 62% hydroxy fatty acids. Using these unique and renewable sources of hydroxy fatty acids, the ARS researchers in Peoria, Illinois, determined the minimum concentration of these substances needed to form an oleogel with soybean oil, and also evaluated the physical and rheological properties of the resulting oleogels in comparison to the industry standard, 12-hydroxy stearic acid, which is extracted from the toxic source, castor seed oil. Objective 3 is to improve commercial value and sustainable food production through recovery of healthful bioactive ingredients from food processing by-products or waste. As progress towards this objective, ARS researchers in Peoria, Illinois, collaborated with ARS scientists in Fort Pierce, Florida, to analyze tocopherols, peroxide value, p-anisidine value, and phytosterols in oil extracted from sour orange oil seeds. Under Objective 3, ARS researchers in Peoria, Illinois, also evaluated silflower seed oil composition, as a potential new drought-resistant perennial oilseed, and potential source of squalene. The effect of bleaching clays on chlorophyll content and oxidative stability of the silflower seed oil was also evaluated. In an agreement with a small business, ARS researchers in Peoria, Illinois, also completed evaluations of the frying stability of a new long-chain monounsaturated frying oil that may soon be commercialized. ARS researchers in Peoria, Illinois, also evaluated major antioxidant components in different coffee retentate extracts and their antioxidant activity revealed that caffeic acid, 3,4-dihydroxybenzoic acid, gallic acid, and chlorogenic acid had strong correlations with the antioxidant activity. For further understanding on their antioxidant activity, each component at the concentration of 0.01% (w/w) in stripped soybean oil, where all the polar compounds were removed, was examined during storage at 35°C for 20 days. It was found that gallic acid was the strongest antioxidant, with activity similar to mixed tocopherols. Caffeic acid also showed strong antioxidant activity after gallic acid. The same study was conducted with stripped flaxseed oil, and caffeic acid and gallic acid were found to be the strongest antioxidants while their activity was not as strong as mixed tocopherols in this oil. Based on these results, ARS researchers in Peoria, Illinois, have decided to change the process to increase the contents of gallic acid and caffeic acid. The first step is to conduct hydrolysis of the coffee retentate under several conditions using different bases, different concentrations of bases, and different temperatures. The hydrolyzed coffee retentate will be extracted with acetone and other solvents, and the concentrations of gallic acid and caffeic acid will be analyzed. ACCOMPLISHMENTS 01 Improving fat substitute properties to reduce saturated fats and prevent heart disease. Current dietary recommendations to help prevent heart disease are to reduce saturated fats in the diet and replace them with vegetable oils that are higher in healthy monounsaturated and polyunsaturated fatty acids. However, replacing fats with oil is difficult to achieve in some food products because oil is not solid at room or refrigerated temperatures. ARS researchers in Peoria, Illinois, were able to demonstrate important interactions between sunflower wax and different types of oil compositions so that achieving fat replacements with specified texture and melting points will be easier to achieve. The information obtained from this study is valuable to fats and oil companies, not only for fundamental understanding on the factors affecting the properties of oleogel-based fat substitutes, but also for the development of healthy food products from these oleogels. 02 Silflower: A potential new perennial oilseed and squalene source for protection of sharks. Silflower is a drought-tolerant perennial plant in the sunflower family native to the central United States. Replacing annual food crops with perennial food crops can protect soil from erosion, reduce pesticide and herbicide use, and increase nutrient and water retention and carbon sequestration. However, to compete economically with annual oilseeds, silflower agronomic trait improvements are needed such as seed size, oil yield, and oil stability. ARS researchers in Peoria, Illinois, analyzed the yield, composition, and oxidative stability of silflower oil. In doing so, they discovered that silflower oil contained unusually high (up to 4.8%) concentrations of squalene, which is in demand in nutraceutical, cosmetic, and pharmaceutical industries. Currently squalene is obtained from shark liver oil, which is controversial due to international concerns with shark overfishing. Silflower oil has similar fatty acid and tocopherol composition to confectionary sunflower oil, the type that is consumed as a snack. In addition, silflower oil stability was compromised by high chlorophyll content, which could be counteracted by refining or by breeding efforts to reduce chlorophyll upon harvest. This information provided breeding strategies to improve the oxidative stability and optimize squalene in silflower oil, so that it can successfully progress from a perennial flower to a perennial climate resilient oilseed crop and renewable squalene source. 03 Industrially important fatty acids from renewable sources and demonstration of their oil-gelling properties. Hydroxy fatty acids have many important uses in industrial chemistry. Unfortunately, castor seed oil, which produces the toxin, ricin, is the only major commercial source of hydroxy fatty acids, so there is great interest in new and renewable sources for hydroxy fatty acids. Sophorolipids from yeast are one potential new source of hydroxy fatty acids. ARS researchers in Peoria, Illinois, and in Wyndmoor, Pennsylvania, evaluated the oleogel properties of sophorolipid derived hydroxy fatty acids and hydroxy fatty acid methyl esters. Oleogels are semi-solid fat-like materials that can be used as fat replacements in foods or as creams for drugs or cosmetics. Materials such as fatty acids, waxes, or monoglycerides, are melted in oils and when they cool, they form a network of fibers or crystals that bind the liquid oil and form a semi-solid similar to a natural fat, and hydroxy fatty acids were one of the first materials that were used to form oleogels. Sophorolipid-derived hydroxy fatty acids were able to form oleogels at 5% -10% in soybean oil, thus may serve as a renewable and non-toxic source of biobased hydroxy fatty acids that could be useful for replacing saturated fats in food and may also be useful in cosmetics and pharmaceuticals.
Impacts (N/A)
Publications
- Winfield, D.D., Dunn, R.O., Moser, J.K., Cermak, S.C., Marks, M.D. 2024. Characterization, physical properties, and potential industrial applications of high oleic pennycress oil. Industrial Crops and Products. https://doi.org/10.1016/j.indcrop.2024.118095.
- Moser, J.K., Ashby, R.D., Yosief, H.O., Msanne, J.N., Peterson, S.C., Bantchev, G.B., Cermak, S.C., Felker, F.C. 2024. Properties of soybean oil oleogels produced from sophorolipid-derived hydroxy fatty acids, methyl esters and hydrogenated Lesquerella seed oil. Journal of the American Oil Chemists' Society. https://doi.org/10.1002/aocs.12843.
- Hwang, H., Liu, S.X., Moser, J.K., Singh, M., Van Tassel, D.L. 2024. Composition and oxidative stability of silflower (Silphium integrifolium) seed oil and its potential as a new source of squalene. Journal of the American Oil Chemists' Society. https://doi.org/10.1002/aocs.12814.
- Hwang, H., Kim, S., Moser, J.K. 2024. Unsaturation and polar compounds of vegetable oils affect the properties of sunflower wax oleogels. European Journal of Lipid Science and Technology. https://doi.org/10.1002/ejlt. 202300205.
- Hwang, H., Moser, J.K. 2024. Wax-based oleogels. In: Palla, C., Valoppi, F. , editors. Advances in Oleogel Development, Characterization, and Nutritional Aspects. Switzerland: Springer Nature. p. 133-155. https://doi. org/10.1007/978-3-031-46831-5.
- Hwang, H.-S., Winkler-Moser, J.K. 2024. Physical and oxidative stability of oleogels during storage. In: Palla, C., Valoppi, F., editors. Advances in Oleogel Development, Characterization, and Nutritional Aspects. Switzerland: Springer Nature. p. 365-395.
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Progress 10/01/22 to 09/30/23
Outputs PROGRESS REPORT Objectives (from AD-416): Objective 1. Stabilize sensitive and bioactive food ingredients, improve shelf-life, and reduce food waste with optimized natural antioxidants and plant extracts. Sub-Objective 1.A. Evaluate antioxidant activity of combinations of antioxidants in frying oils and fried foods. Sub-objective 1.B. Evaluate antioxidants or natural antioxidant extracts for protection of polyunsaturated and omega-3 oils and bioactive lipids and to extend shelf-life of whole foods and food ingredients. Objective 2. Enable oleogel applications to reduce saturated fats in foods. Sub-Objective 2.A. Investigate and optimize the physical and sensory properties as well as the oxidative stability of edible oleogels. Sub-objective 2.B. Evaluate interesterified natural waxes, waxes with vegetable oils, fatty alcohols or fatty acids, as potential new oleogelators. Objective 3. Improve commercial value and sustainable food production through recovery of healthful bioactive ingredients from food processing by-products or waste. Approach (from AD-416): Approximately 30% of the food supply in the United States is wasted and the worldwide problem is even larger. This waste represents a large strain on the environment and on the entire food production enterprise. According to the Food and Drug Administration (FDA), about 20% of the food waste in the United States is due to confusion about the meaning and safety of foods labeled with best before and use by dates. This means that extending shelf-stability of foods can have an impact in reducing food waste. There is also concern about the healthfulness of processed foods, including the high content of saturated fats, which consumers are advised to limit in the diet. However, reducing the saturated fat content of foods by substituting with healthier fats can influence product texture and mouthfeel, as well as the oxidative stability and shelf-life. The research of the next five years will enable the commercial development of natural antioxidants needed to improve the oxidative stability and shelf-life of foods formulated with a lower saturated fat content. Antioxidants will improve the stability of frying oils, fried foods, and high-value foods such as nuts and protein replacement bars. Oleogels will be developed with improved physical and melting properties for margarines and shortenings and other food applications that require hard fats and will have lower amounts of saturated fats and zero trans fats. New value-added ingredients such as antioxidants and bioactive lipids will be mined and characterized from low-value agricultural inputs. This research, together with complimentary technology and policy development strategies, will contribute to efforts to reduce food waste and improve the healthfulness of the food supply. Sub-objective 1.A is to evaluate the antioxidant activity of combinations of antioxidants in frying oil and fried foods. The overall goal is to develop synergistic antioxidant combinations that can be used to improve frying oil life. In support of Sub-objective 1.A. (Publication 1, Accomplishment 1), sodium and potassium carbonates and bicarbonates, which are common food ingredients, were shown to have strong antioxidant activity in soybean oil and several other oils at frying temperature, which was verified in frying studies. The bicarbonates were then proven to enhance and preserve tocopherols (naturally present antioxidant and vitamin E components) in vegetable oils. In addition, the carbonates and bicarbonates were further shown to have either additive or synergistic interactions with other commercial natural antioxidants such as rosemary extract, epigallocatechin gallate (from green tea extracts), ascorbic acid (vitamin C), and ascorbyl palmitate (a vitamin C analog). In addition to the publication, this research was presented at the 2023 American Oil Chemists Society (AOCS) Annual Meeting. Additional progress towards Sub-objective 1.A. was to evaluate the effect of corn fiber extracts (also related to Objective 3) on stability of soybean oil during frying of tortilla chips. While the corn fiber extracts were shown to be excellent antioxidants in the frying oils and to slow degradation of soybean oil tocopherols during frying, they did not improve the activity of rosemary extracts during testing. This work is complete and has been presented at the American Oil Chemists Society Annual Meeting and a manuscript is in progress. Sub-objective 1.B is to evaluate antioxidants or natural antioxidants for protection of polyunsaturated and omega-3 oils and bioactive lipids and to extend shelf-life of whole foods and food ingredients. Due to some setbacks in personnel, equipment, and administrative issues for sensory analysis, we chose to focus on other goals for this objective, while sensory testing will be delayed until these issues are resolved. This fiscal year, we focused on methods to screen antioxidants for shelf-life improvement, and developing a new method based on nuclear magnetic resonance (NMR) for quantitative analysis of lipid aldehydes, peroxides, and epoxides that form during lipid oxidation. Shelf-life studies are time-consuming, because even accelerated studies at 55 degrees C may take a minimum of two weeks, depending on the inherent stability of the control food product. In the past fiscal year, we developed sweet potato chips (containing the bioactive lipid beta-carotene, which is pro-vitamin A) fried in canola oil as a model food product for studying shelf-life improvement by antioxidants. The results from this research were presented at the 2023 AOCS Annual Meeting and a manuscript is in progress. Recently, we focused on continuing to screen antioxidants for improving shelf-life of sweet potato chips, but also on testing whether using a rapid screening method could correlate with the shelf-life studies. Initial results indicate that the rapid screening method correlated well with accelerated shelf-life studies to at least give a positive indication that an antioxidant(s) added to frying oil during initial stages of frying could improve shelf-life. We plan to replicate these studies and test additional antioxidants and combinations during the next year. Methods for evaluating lipid oxidation during shelf-life studies in bulk oils and in food products call for analysis of both primary lipid oxidation products, such as lipid hydroperoxides, and secondary oxidation products, such as aldehydes, which are measured by a few methods, including headspace analysis of volatile aldehydes, and p-anisidine value, which is a non-specific measure of non-volatile aldehydes. These methods are old, require a lot of hazardous solvents as well as toxic compounds (p-anisidine), and are also very non-specific as well as not being very quantitative. Thus, we searched the literature and found a new method using band-selective NMR, and collaborated with the NMR research specialist at ARS in Peoria, Illinois, to adapt this technique for quantitation of 10 classes of hydroperoxides and aldehydes in frying oils as well as bulk oils and oils extracted from foods during shelf-life experiments, thereby reducing solvent and chemical use and waste and improving the quantitative and analytical results. Sub-objective 2.A is to investigate and optimize the physical and sensory properties as well as the oxidative stability of edible oleogels. As progress towards this sub-objective (Publication 3, Accomplishment 2), the firmness of wax-based oleogels containing binary mixtures of beeswax and candelilla wax were shown to be significantly increased by substituting a small proportion of the mixtures with a third wax, sunflower wax. Although sunflower wax has a higher melting point than the other two waxes, this substitution did not alter the melting properties of the mixtures, therefore allowing for firmer oleogels that will not leave a waxy mouthfeel. In further progress towards Sub-objective 2.A, a study was conducted to evaluate the effect of the amount of oil unsaturation on oleogel physical properties. Nine oils with different levels of unsaturation are being tested with two waxes and a binary wax mixture. In addition, these oils are also being stripped of everything except for the triacylglycerols, in order to also evaluate the effect of additional polar compounds in oil on oleogel physical properties. Sub- objective 2.B was to evaluate interesterified natural waxes, waxes with vegetable oils, fatty alcohols, or fatty acids, as potential new oleogelators. In progress towards this sub-objective, we have substantially completed a study on the physical properties of oleogels made with hydroxy fatty acids and hydroxy fatty acid methyl esters. With some additional testing, this study should be completed and submitted for publication in fiscal year 2023. Additional chemical interesterification of two waxes were attempted, but no promising oleogels were obtained from these results. Therefore, for the next steps, enzymatic interesterification (IE) between wax and palm oil or medium chain triglycerides (MCT) and chemical IE between wax and fatty alcohols or fatty acids are planned for the next fiscal year. Objective 3 is to improve commercial value and sustainable food production through recovery of healthful bioactive ingredients from food processing by-products or waste. As progress towards this objective, we collaborated with ARS scientists in Peoria, Illinois, and Fort Pierce, Florida, to analyze tocopherols, peroxide value, p-anisidine value, and free fatty acids in oil extracted from waste seeds from the commercial sweet orange juicing process and used as a feedstock for biodiesel (Publication 7). We collaborated with pulse and flour researchers at ARS in Peoria, Illinois, to evaluate antioxidant activity of buckwheat flours subjected to different conditions of subcritical water flash release processing (Publication 4), and to evaluate the effect of processing on the headspace beany odor compounds in pinto bean flours subjected to jet-cooking processing (Publication 6). We collaborated with scientists to develop a patented, low-odor and dust-reducing cat litter utilizing soybean hulls and soybean hull biochar (Publication 5). We also conducted extraction and analysis of silflower seed oils, a potential new drought- resistant perennial oilseed, and compared fatty acid composition, oil stability, tocopherols, and other oil quality factors, with native sunflower seed oil, to be presented at the 2023 Institute of Food Technologists (IFT) Annual Meeting, Chicago, Illinois. ACCOMPLISHMENTS 01 Baking soda may allow the use of healthier oils for fried foods. Ideally, restaurants would fry foods in healthy oils that are high in monounsaturated and polyunsaturated fats and low in saturated fats. Unfortunately, polyunsaturated fats quickly break down at the hot temperatures that are used in fryers. ARS researchers in Peoria, Illinois, demonstrated that sodium and potassium carbonates and bicarbonates, which are found in baking soda, baking powder, and are common ingredients in foods, acted as antioxidants when added (at 0.03% to 0.06%) to soybean oil, by protecting the polyunsaturated fatty acids from breaking down when heated at frying oil temperature (180 degrees C) . Potassium carbonate and bicarbonate were found to perform the best, so they were further tested in five additional oils, including avocado oil, canola oil, corn oil, high-oleic soybean oil and olive oil. Breakdown of the polyunsaturated fats was reduced by 17% to 72% compared to the controls. In addition, potassium bicarbonate was evaluated in frying studies of potatoes at 0.06% in soybean oil and canola oil. It outperformed Tert-butylhydroquinone, the most commonly used synthetic antioxidant used in frying oils, which the food industry would like to replace with more natural ingredients. Thus, a common and well-known ingredient used in kitchens and by the food industry may extend the use of healthier oils for restaurant fried foods. 02 Optimizing the texture and melting properties for healthier fat substitutes. Current dietary recommendations to help prevent heart disease are to reduce saturated fats in the diet and replace them with vegetable oils that are higher in healthy monounsaturated and polyunsaturated fatty acids. However, replacing fats with oil is difficult to achieve in some food products because oil is not solid at room or refrigerated temperatures. Melting small amounts of natural waxes with vegetable oils form a solid called an oleogel. Oleogel properties can be changed by using different types and amounts of waxes, but if too much wax is used, it will leave a waxy taste and texture in the mouth. ARS researchers in Peoria, Illinois, discovered that by using certain mixtures of natural waxes that each have different properties, they could maximize the firmness of these oleogels at both room and refrigeration temperature without increasing the melting point. This means oleogels can be made without a waxy mouth feel and with texture and melting properties similar to traditional fats, so that they can be used to replace fats in food products to produce healthier foods. This information will be helpful for food companies as they strive to lower the saturated fat content in a variety of food products. 03 Bioactive lipids in distillers corn oil from U.S. ethanol plants. The United States produces 15 billion gallons of bioethanol per year from corn as the world's largest producer. Most bioethanol plants produce distillers corn oil (DCO) as a valuable co-product, which is used in animal feed and in biodiesel production, but also contains valuable bioactive lipids such as tocopherols, carotenoids, and phytosterols that could potentially be an additional high-value co-product. ARS researchers in Peoria, Illinois, and researchers with Trucent, in Dexter, Michigan, determined the range and variability in fatty acids, bioactive lipids, antioxidant activity, and oxidative stability of DCO collected from 30 bioethanol plants across the United States. DCO samples had higher oxidative stability than commercial corn oil and had extremely low variability in fatty acid composition. Phytosterols and phytosterol conjugates made up almost 2% of the DCO, and there was lower variability in content and composition between plants. The highest variability was in tocopherol, tocotrienol, and carotenoid content and composition, likely because these bioactive lipids are the most susceptible to heat and oxidation. This information will enable bioethanol plants to optimize their processing and extraction conditions to preserve these valuable bioactive lipids for potential valorization.
Impacts (N/A)
Publications
- Moser, J.K., Hwang, H., Felker, F.C., Byars, J.A., Peterson, S.C. 2023. Increasing the firmness of wax-based oleogels using ternary mixtures of sunflower wax with beeswax:candelilla wax combinations. Journal of the American Oil Chemists' Society. 100(5):387-402. https://doi.org/10.1002/ aocs.12679.
- Hwang, H., Moser, J.K. 2022. Bicarbonates and carbonates as antioxidants in vegetable oils at frying temperatures. Journal of Food Science. 88(2) :717-731. https://doi.org/10.1111/1750-3841.16442.
- Moser, J.K., Hwang, H., Byars, J.A., Vaughn, S.F., Aurandt-Pilgrim, J., Kern, O. 2022. Variations in phytochemical content and composition in distillers corn oil from 30 U.S. ethanol plants. Industrial Crops and Products. 193. Article 116108. https://doi.org/10.1016/j.indcrop.2022. 116108.
- Plumier, B.M., Kenar, J.A., Felker, F.C., Moser, J.K., Singh, M., Byars, J. A., Liu, S.X. 2023. Effect of subcritical water flash release processing on buckwheat flour properties. Journal of the Science of Food and Agriculture. 103(4):2088-2097. https://doi.org/10.1002/jsfa.12399.
- Vaughn, S.F., Liu, S.X., Berhow, M.A., Moser, J.K., Peterson, S.C., Selling, G.W., Hay, W.T., Jackson, M.A., Skory, C.D. 2023. Production of an odor-reducing, low-dust, clumping cat litter from soybean hulls and soybean hull biochar. Bioresource Technology Reports. 21. Article 101317. https://doi.org/10.1016/j.biteb.2022.101317.
- Moser, B.R., Dorado, C., Bantchev, G.B., Winkler-Moser, J.K., Doll, K.M. 2023. Production and evaluation of biodiesel from sweet orange (Citrus sinensis) lipids extracted from waste seeds from the commercial orange juicing process. Fuel. 342. Article 127727. https://doi.org/10.1016/j.fuel. 2023.127727.
- Felker, F.C., Kenar, J.A., Singh, M., Moser, J.K., Byars, J.A. 2023. Comparison of raw and excess steam jet-cooked/drum-dried pinto bean flours and their effects on ground beef patties. Journal of Food Processing and Preservation. Article 5915625. https://doi.org/10.1155/2023/5915625.
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Progress 10/01/21 to 09/30/22
Outputs PROGRESS REPORT Objectives (from AD-416): Objective 1. Stabilize sensitive and bioactive food ingredients, improve shelf-life, and reduce food waste with optimized natural antioxidants and plant extracts. Sub-Objective 1.A. Evaluate antioxidant activity of combinations of antioxidants in frying oils and fried foods. Sub-objective 1.B. Evaluate antioxidants or natural antioxidant extracts for protection of polyunsaturated and omega-3 oils and bioactive lipids and to extend shelf-life of whole foods and food ingredients. Objective 2. Enable oleogel applications to reduce saturated fats in foods. Sub-Objective 2.A. Investigate and optimize the physical and sensory properties as well as the oxidative stability of edible oleogels. Sub-objective 2.B. Evaluate interesterified natural waxes, waxes with vegetable oils, fatty alcohols or fatty acids, as potential new oleogelators. Objective 3. Improve commercial value and sustainable food production through recovery of healthful bioactive ingredients from food processing by-products or waste. Approach (from AD-416): Approximately 30% of the food supply in the United States is wasted and the worldwide problem is even larger. This waste represents a large strain on the environment and on the entire food production enterprise. According to the Food and Drug Administration (FDA), about 20% of the food waste in the United States is due to confusion about the meaning and safety of foods labeled with best before and use by dates. This means that extending shelf-stability of foods can have an impact in reducing food waste. There is also concern about the healthfulness of processed foods, including the high content of saturated fats, which consumers are advised to limit in the diet. However, reducing the saturated fat content of foods by substituting with healthier fats can influence product texture and mouthfeel, as well as the oxidative stability and shelf-life. The research of the next five years will enable the commercial development of natural antioxidants needed to improve the oxidative stability and shelf-life of foods formulated with a lower saturated fat content. Antioxidants will improve the stability of frying oils, fried foods, and high-value foods such as nuts and protein replacement bars. Oleogels will be developed with improved physical and melting properties for margarines and shortenings and other food applications that require hard fats and will have lower amounts of saturated fats and zero trans fats. New value-added ingredients such as antioxidants and bioactive lipids will be mined and characterized from low-value agricultural inputs. This research, together with complimentary technology and policy development strategies, will contribute to efforts to reduce food waste and improve the healthfulness of the food supply. Sub-objective 1.A. is to evaluate the antioxidant activity of combinations of antioxidants in frying oils and fried foods. The overall goal of this sub-objective is to develop synergistic antioxidant combinations that can be used to improve frying oil life as well as the shelf-life of fried foods. The 24-month milestone was to have completed screening mixtures of antioxidants for shelf-life improvement. We started with screening tests using a small-scale protocol that we had previously developed. However, this was producing inconsistent results and could not be adapted to produce enough product for shelf-life analysis, so we altered the research flow to instead develop frying and shelf-life protocols for scaled up studies, originally scheduled as the 36-month milestone. These were found to be adaptable for screening studies as well. Sweet potato chips, which are a good source of beta-carotene, a pro- vitamin A carotenoid, were chosen as a model food product so that the effects of antioxidants on shelf-life can be evaluated wholistically to include texture, nutritional value, and changes due to co-oxidation of the oil, beta-carotene and carotenoids, as well as proteins. We performed shelf-life studies under moderate (35 degrees C) as well as accelerated conditions (45 degrees C), and headspace volatiles were measured to identify the key chemical compounds that either developed (oxidation products) or degraded (sweet potato flavor compounds) during storage. Procedures for testing the crispness of chips over time, color, near- infrared analysis, moisture content, total fat content, surface and penetrated oil content, chip tocopherol and carotenoid contents were all determined. This has driven progress towards large-scale studies forward and was found to be adaptable for the screening studies as well. In addition, to develop improved natural antioxidants to replace synthetic antioxidants for frying oils, amino acids, which were previously found to have strong antioxidant activity, were modified by mixing with inorganic bases to produce amino acid salts. The modified versions of amino acids had stronger antioxidant activity than the corresponding amino acids. They were also effective in other vegetable oils including olive, high oleic soybean, canola, avocado, and corn oils. Thus, antioxidant activity of amino acids can be improved by the reaction with an inorganic base. For example, the modified version of phenylalanine at 0.12% more effectively prevented oil oxidation than tert- butyl hydroquinone (TBHQ), a synthetic antioxidant, at its legal concentration limit (0.02%) indicating potential as a new antioxidant for frying. Sub-objective 1.B. is to evaluate antioxidants or natural antioxidants for protection of polyunsaturated and omega-3 oils and bioactive lipids and to extend shelf-life of whole foods and food ingredients. The goal for this research is to develop antioxidant systems to prevent oxidation and increase shelf-life of bulk oils, emulsions, peanuts and nuts, and/or other foods. Since amino acids had strong antioxidant activity in frying oil, preliminary studies were conducted to evaluate the effect of methionine on soybean oil oxidation and shelf-life under mildly accelerated storage conditions (35 degrees C). Methionine at 0.1, 0.2, and 0.3%, which had the strongest antioxidant activity among other amino acids at frying temperature, did not significantly reduce the oxidation of soybean oil or increase its shelf-life. Thus, it is considered that the mechanism of amino acid antioxidant activity may be related to high- temperature reactions of amino acid that do not occur at a storage temperature. Sub-objective 2.A. is to investigate and optimize the physical and sensory properties as well as the oxidative stability of edible oleogels. The overall goal of this research is to develop prototype oleogel-based structured fats for use in margarines, shortenings, and nut/seed butters. The 24-month milestone was to develop prototype margarine, spread, shortening or other foods using oleogels, and to conduct preliminary evaluation of physical and functional properties. The milestone was met after 12-months when a paper was published in 2021 on the chemical and physical properties of margarines developed with binary wax combinations. In additional progress towards this objective, work was completed and published on the sensory (flavor and texture) properties of peanut butter stabilized with beeswax, candelilla wax, rice bran wax, and sunflower wax. Several wax types and levels were found to produce peanut butter with similar sensory properties to peanut butter made with conventional stabilizers, which use fully hydrogenated oils to bind the excess oil and alter the texture in peanut butter and other nut/seed spreads. A third study was completed under this sub-objective where margarines were developed with hempseed oil oleogels and the properties were evaluated. Also, in collaboration with scientists at Sejong University (Seoul, Korea) , utilization of oleogels with binary oleogelator blends of candelilla wax and glycerol monostearate (GMS), a food-grade monoglyceride, were studied in confectionary fillings. These blends were previously shown to have improved melting and texture properties compared to oleogels with candelilla wax or GMS alone. Of the combinations studied, filling cream made with the 60% candelilla wax and 40% GMS oleogel had similar textural properties to filling cream made with conventional shortening, and the level of saturated fatty acids in the new filling creams was distinctly reduced from 36.2% to 10.3%. Sub-objective 2.B. is to evaluate interesterified natural waxes, waxes with vegetable oils, fatty alcohols or fatty acids, as potential new oleogelators. The overall goal of this research is to develop new oleogelators with a wider profile of solid fat content, melting, and other physical properties. The 24-month milestone for this objective was to complete preliminary reactions and composition analysis of reaction products. A preliminary study was conducted for the chemical interesterification of two waxes to improve the physical properties of wax-based oleogels. Chemical interesterification included six combinations of four waxes (beeswax, sunflower wax, rice bran wax, and candelilla wax). The interesterified product with rice bran wax and sunflower wax resulted in soybean oil oleogels with significantly higher firmness than that those with pure wax and with the mixture of two waxes. However, additional repeated experiments found inconsistent results, perhaps due to non-specificity of the chemical interesterification reactions. Therefore, the chemical reaction conditions are being modified to produce consistent products, and enzymatic interesterification methods are also being considered for future research. Additional research under this sub-objective included a collaboration with ARS researchers in Wyndmoor, Pennsylvania, to evaluate the oleogelation properties of novel fatty alcohols. The preliminary investigations have determined the minimum gelation concentrations for oleogel formation, the thermal properties (melting and crystallization profiles), and microscopic evaluation of the oleogel microstructure. The goal for Objective 3 is to develop new sources of antioxidants, bioactive lipids, or wax from agricultural processing fractions or coproducts. The 24-month milestones were to improve/optimize extraction of corn fiber and/or corn bran for phytosteryl ferulates and other phenolic antioxidants and to evaluate improved coffee retentate and/or fruit pomace extracts in bulk oils (frying and/or storage studies). As progress towards the first milestone, extractions of corn bran and corn fiber were carried out using different solvent types and temperatures using accelerated solvent extraction to determine best conditions for increasing yield, antioxidant activity, and ferulate phytosterol esters. In addition, wax was extracted from soybean hull crude lipid extracts, and characterized for its main chemical components, and upon scale-up the soybean hull wax will be tested for oleogelation properties. Research was also conducted to develop methods to improve the antioxidant activity of spent coffee ground (SCG) extracts, which were previously shown to have stronger antioxidant activity than other commercial natural antioxidants in soybean oil and fish oil. We attempted to improve the activity of the SCG extracts by chemical modification, however, the modification only resulted in minor improvement to the antioxidant activity. Essential oils often contain unique and effective antioxidants, but their strong flavor and odor limits how much that can be used in foods. ARS researchers in Peoria, Illinois collaborated with scientists from University of Putra, in Selangor, Malaysia, and Agricultural University in Faisalabad, Pakistan, to evaluate the antioxidant activity of fractionated and nanoencapsulated essential oils from Indian Blackberry (Syzygium cumini) leaves. By fractionating the essential oils, the chemicals that impart the strong flavor were removed. It was found that less aromatic fractions retained similar antioxidant activity to the volatile fractions. In addition, most of the fractions also maintained antioxidant activity when encapsulated in nanoparticles. We also collaborated with scientists at University of Illinois in Urbana- Champaign, Illinois, to characterize the lipid content and compositional profile from oil recovered after simultaneous saccharification and co- fermentation of biomass for ethanol production. This research helps to develop methods for producing multiple biofuel feedstocks (biodiesel and ethanol) from a single biomass source. ACCOMPLISHMENTS 01 Demonstrated new natural antioxidants to enable the use of healthier frying oil.. During deep fat frying, oil quality is deteriorated by lipid oxidation. Vegetable oils such as soybean oil are high in healthy polyunsaturated fatty acids including omega-3 fatty acids, but these oils quickly deteriorate during frying, reducing their usable fry-life and sometimes producing toxic substances. Therefore, more stable oils such as palm oil and other tropical oils are widely used by the food industry and in restaurants, which can cause many health problems for consumers due to their high content of saturated fats. ARS researchers in Peoria, Illinois, recently reported that certain amino acids can effectively prevent oxidation of vegetable oils such as soybean oil during frying. Their activity was shown to be significantly improved by converting the free amino acids to either sodium or potassium salts. Among the amino acid salts studied, phenylalanine potassium salt had the strongest antioxidant activity, which was demonstrated in oils including soybean, olive, high oleic soybean, canola, avocado, and corn oil. A frying study with potato cubes in soybean oil showed that phenylalanine potassium salt at 0.12% had significantly stronger antioxidant activity than tert-butyl hydroquinone, a widely used synthetic antioxidant for frying oils, at its legal limit (0.02%). This study demonstrated that simple amino acid salts could replace synthetic antioxidants used in frying oils, which would benefit consumers by enabling the use of healthier oils for frying, preventing production of toxic substances, and avoiding the use of potentially toxic synthetic antioxidants. This is of great interest to oil and food companies that seek natural and clean-label alternatives to synthetic antioxidants, and the ability to use U.S. produced vegetable oils rather than imported oils. 02 Utilized hemp seed oil oleogels for healthy margarines. Plant based spreads or so-called plant butters are currently surging in the marketplace, in conjunction with other plant-based food and proteins. Conventional solid fats used in margarines and other related products contain high levels of saturated fatty acids, which are known to have negative health effects. Hemp seed oil is high in healthy polyunsaturated fatty acids including omega-3 fatty acids, as well as other substances that have health benefits such as anti- inflammatory activities, blood lipid profile improvement, and protection from oxidative stress. To utilize hempseed oil as a major ingredient in margarine or spread, ARS researchers in Peoria, Illinois, made hemp seed oil oleogels by adding small amounts of melted natural waxes to the liquid oil, which then crystallized upon cooling to form a semisolid network that entrapped the liquid oil. The oleogels were demonstrated to be able to replace solid fats in spreadable margarines. Margarines with the same hardness of commercial margarine spreads were made by adding less than 3% wax. However, the firmness of a stick margarine could not be achieved with up to 7% wax. Depending on whether the desired product is a spreadable margarine or a stick margarine, hemp seed oil oleogels could be used to replace conventional solid fats fully or partially in formulations, thereby reducing the saturated fat content. This information is important for food companies that are seeking to develop healthier spreads by incorporating oils with low levels of saturated fats and healthful bioactive components.
Impacts (N/A)
Publications
- Jia, Y., Kumar, D., Winkler-Moser, J.K., Dien, B.S., Rausch, K., Tumbleson, M.E., Singh, V. 2022. Coprocessing corn germ meal for oil recovery and ethanol production: a process model for lipid-producing energy crops. Processes. 10(4). Article 661. https://doi.org/10.3390/pr10040661.
- Kim, M., Hwang, H., Jeong, S., Lee, S. 2021. Utilization of oleogels with binary oleogelator blends for filling creams low in saturated fat. LWT - Food Science and Technology. 155. Article e112972. https://doi.org/10.1016/ j.lwt.2021.112972.
- Shaheen, R., Hanif, M.A., Nisar, S., Rashid, U., Sajid, Z., Shehzad, M.R., Winkler-Moser, J.K., Alsalme, A. 2021. Seasonal variation, fractional isolation and nanoencapsulation of antioxidant compounds of indian blackberry (Syzygium cumini). Antioxidants. 2021; 10(12). Article 1900. https://doi.org/10.3390/antiox10121900.
- Winkler-Moser, J.K., Anderson, J.A., Hwang, H. 2022. Texture and flavor evaluation of peanut butter stabilized with natural waxes. Journal of Food Science. 87(4):1851-1864. https://doi.org/10.1111/1750-3841.16118.
- Hwang, H., Winkler-Moser, J.K., Liu, S.X. 2022. Antioxidant activity of amino acid sodium and potassium salts in vegetable oils at frying temperatures. Journal of the American Oil Chemists' Society. 99(5):407-419. https://doi.org/10.1002/aocs.12585.
- Hwang, H., Kim, S., Moser, J.K., Lee, S.L., Liu, S.X. 2022. Feasibility of hemp seed oil oleogels structured with natural wax as solid fat replacement in margarine. Journal of the American Oil Chemists' Society. https://doi.org/10.1002/aocs.12619.
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Progress 10/01/20 to 09/30/21
Outputs PROGRESS REPORT Objectives (from AD-416): Objective 1. Stabilize sensitive and bioactive food ingredients, improve shelf-life, and reduce food waste with optimized natural antioxidants and plant extracts. Sub-Objective 1.A. Evaluate antioxidant activity of combinations of antioxidants in frying oils and fried foods. Sub-objective 1.B. Evaluate antioxidants or natural antioxidant extracts for protection of polyunsaturated and omega-3 oils and bioactive lipids and to extend shelf-life of whole foods and food ingredients. Objective 2. Enable oleogel applications to reduce saturated fats in foods. Sub-Objective 2.A. Investigate and optimize the physical and sensory properties as well as the oxidative stability of edible oleogels. Sub-objective 2.B. Evaluate interesterified natural waxes, waxes with vegetable oils, fatty alcohols or fatty acids, as potential new oleogelators. Objective 3. Improve commercial value and sustainable food production through recovery of healthful bioactive ingredients from food processing by-products or waste. Approach (from AD-416): Approximately 30% of the food supply in the United States is wasted and the worldwide problem is even larger. This waste represents a large strain on the environment and on the entire food production enterprise. According to the Food and Drug Administration (FDA), about 20% of the food waste in the United States is due to confusion about the meaning and safety of foods labeled with best before and use by dates. This means that extending shelf-stability of foods can have an impact in reducing food waste. There is also concern about the healthfulness of processed foods, including the high content of saturated fats, which consumers are advised to limit in the diet. However, reducing the saturated fat content of foods by substituting with healthier fats can influence product texture and mouthfeel, as well as the oxidative stability and shelf-life. The research of the next five years will enable the commercial development of natural antioxidants needed to improve the oxidative stability and shelf-life of foods formulated with a lower saturated fat content. Antioxidants will improve the stability of frying oils, fried foods, and high-value foods such as nuts and protein replacement bars. Oleogels will be developed with improved physical and melting properties for margarines and shortenings and other food applications that require hard fats and will have lower amounts of saturated fats and zero trans fats. New value-added ingredients such as antioxidants and bioactive lipids will be mined and characterized from low-value agricultural inputs. This research, together with complimentary technology and policy development strategies, will contribute to efforts to reduce food waste and improve the healthfulness of the food supply. Significant progress was made under Objective 1 to evaluate antioxidant activity of combinations of antioxidants in frying oils and fried foods. We conducted studies of the antioxidant activity of amino acids in a variety of frying oils and in fried foods and evaluated their antioxidant activity in combination with other natural antioxidants. Amino acids and tocopherols were found to be a highly effective combination of antioxidants for protecting frying oils. In additional experiments, we investigated modifications to amino acids using food-safe ingredients. We also studied combinations of modified amino acids with tocopherols to evaluate their antioxidant activity in frying oil. The modifications were shown to improve antioxidant activity of some of the amino acids, and they were still an effective combination with tocopherols. A new method to further increase the feasibility of commercialization of amino acids as natural antioxidants for frying was proposed and a domestic food ingredient company is interested in this new technology and a collaboration with ARS is being discussed. Progress was also made to evaluate antioxidants or natural antioxidant extracts for protection of polyunsaturated and omega-3 oils and bioactive lipids and to extend shelf-life of whole foods and food ingredients. Tocopherols are powerful antioxidants and the most commonly used natural antioxidant added to foods since they can be easily obtained as a co- product of vegetable oil refining. There is growing interest in tocotrienols, a similar class of natural antioxidants. Vegetable oils contain up to four tocopherols, and four tocotrienols, the composition of which depends on the original source. Each component has slightly different antioxidant activities, so performance of mixtures can be improved by finding the optimum blend of components. As progress towards the first milestone under this objective, we studied the antioxidant activity of individual tocopherols and tocotrienols and three commercial tocopherol mixtures using antioxidant assays. Then we evaluated the performance of the mixtures in fish oil, fish oil ethyl esters, and high oleic sunflower oil using an accelerated testing procedure. While all of the three commercial tocopherol mixtures improved stability of the oils when added at high enough concentrations, we found that one mixture had better performance than the other two, due to the higher concentration of a tocopherol component that had higher antioxidant activity than other tocopherols. This mixture improved oxidative stability of high-oleic sunflower oil by 565% and 869% when added at 0.05% and 0.1%, and improved fish oil stability by 435% and fish oil ethyl ester stability by 530% when added at 0.15%. The results in this study can be used to prepare optimized mixtures of tocopherols to protect polyunsaturated and omega-3 oils and to extend shelf-life of whole foods and food ingredients. Significant progress was made under Objective 2 to investigate and optimize the physical and sensory properties as well as the oxidative stability of edible oleogels. To meet the 12-month milestones, we conducted experiments showing that by adding a small amount of one wax to binary mixtures of two other waxes, we were able to improve the firmness of oleogels without impacting the melting properties. This is an important discovery, as one of the goals of the research is to develop gels with textures similar to conventional solid fats and hydrogenated oils, without the high melting point that can make the product taste or feel waxy when consumed. This work was presented at the annual meeting of the American Oil Chemists Society and a manuscript is being prepared. We also published a paper on the physical properties of margarines made with binary wax mixtures, which also had firmer texture than margarines made from one-wax oleogels. In collaboration with scientists at Sejong University (Seoul, Korea), physical properties and crystal structures of grapeseed oil oleogels prepared with binary systems of two oleogelators, candelilla wax and glyceryl monostearate, were also investigated. We studied the minor ingredients in commercial glyceryl monostearate using nuclear magnetic resonance (NMR) and found that a minor ingredient positively affected the physical properties of oleogels. The binary blends of candelilla wax and glyceryl monostearate at varying ratios were also incorporated in canola oil oleogels, which were used to replace shortening in the preparation of filling creams. The hardening effect by mixing two oleogelators was also observed in the filling creams. The optimum blending ratio was 60:40 (candelilla wax: glyceryl monostearate), which had the highest firmness as well as the lowest melting temperature. The level of saturated fatty acids in the filling creams prepared with oleogels was reduced from 36.2% to 10.3% compared to that with a conventional shortening, bringing the values in alignment with food industry goals and nutritional recommendations for lower saturated fats in the diet. Also under Objective 2, we evaluated interesterified natural waxes, waxes with vegetable oils, fatty alcohols or fatty acids, as potential new oleogelators. One of the major components in natural waxes are wax esters, which are composed of a chemically bonded fatty acid and fatty alcohol. The chain lengths of each these can range from 16 to 22 carbons, and natural waxes contain mixtures of wax esters with different chain lengths for each component. Oleogel properties are significantly affected by the chain lengths of the components of wax esters. Interesterification is a process that rearranges the components within a mixture using either chemicals or enzymes, and it may improve the physical properties of wax- based oleogels. To meet the 12-month milestone for this objective, chemical interesterification was conducted with six combinations of four waxes (beeswax, sunflower wax, rice bran wax, and candelilla wax). The resulting materials were incorporated in 5% wax-soybean oil oleogels, and their firmness was measured. Among six combinations, two interesterified waxes (products from beeswax and candelilla wax, and those from rice bran wax and sunflower wax) had increased firmness from oleogels with pure wax. This study indicates that physical properties of oleogels can be improved by interesterification of natural waxes. This may allow food companies to produce oleogels with an increasing and improved range of physical properties using these waxes as the building blocks. Objective 3 is to improve commercial value and sustainable food production through recovery of healthful bioactive ingredients from food processing by-products or waste. Soybean hulls are by-products from soybean processing that are currently used as an inexpensive animal feed additive. As progress towards the first milestone, oil was extracted from soybean hulls and the composition of the fatty acids, tocopherols, phytosterols, and total phenolics were studied to determine the total content of these bioactive components. For further studies on possible valuable substances in soybean hulls, additional oil was extracted, and we plan to next characterize soybean hull wax for potential use as an oleogelator, and to test different extraction conditions to improve the antioxidant activity of extracts and the hulls for use as bioactive food ingredients. Corn bran is a by-product derived from the production of corn flakes and other food products. It is currently used as a fiber additive in food products, but it may have better marketability if other bioactive components in the bran are identified and quantified or if new ingredients are developed with enhanced content of bioactive components. Therefore, corn bran was extracted with different solvents ranging from low to high polarity. The yield, content of phytosteryl ferulates, lipid composition, and total phenolics were measured as a first step in this research. In addition, the oils were tested as antioxidants in preliminary heating studies in canola oil. These preliminary studies have helped to narrow down the potential extraction solvents and conditions for further research. We also collaborated with other ARS scientists on a project to evaluate the in vitro digestibility of pea protein isolates and determined the impact of particle size on digestibility. The information collected in this study will be used to recover valuable bioactive ingredients and antioxidants from food processing by-products or wastes. Previously, spent coffee ground extracts obtained by Soxhlet extraction with acetone as solvent was found to have stronger antioxidant activity than other commercial natural antioxidants in soybean oil and fish oil. The extract at 0.25% had similar or stronger antioxidant activity than a synthetic antioxidant, butylated hydroxytoluene, at its legal limit (0. 02%). This fiscal year, a preliminary study was conducted on the modification of the extract from spent coffee ground. The extract was treated with a base, sodium bicarbonate, and examined for its antioxidant activity in soybean oil during storage at 35 °C. The results showed that the treatment of the extract with a base could further improve the activity of the extract. Since natural antioxidants generally have inferior antioxidant activity to their synthetic counterparts, improving the efficacy of natural antioxidants is critical to their practical application. The method developed in this study can be applied to other natural antioxidants to enhance their activity. We also collaborated with scientists at the University of Illinois to improve the recoveries of oil and hydrolyzed sugars from corn germ meal by different hydrothermal and fermentations treatments. This work enables the development and optimization of the yield of co-products of energy crop utilization. Record of Any Impact of Maximized Teleworking Requirement: Maximized telework posture has impacted our project by slowing our ability to conduct laboratory experiments due to the lack of personnel on site. Thus far, we have been able to complete or substantially meet our milestones. However, milestones for the second year of this project may be delayed or we may need to adjust the milestones. We are currently evaluating our situation and will communicate with leadership prior to making any changes or adjustments. Due to the epidemic and maximized telework, we are not able to conduct sensory studies. ACCOMPLISHMENTS 01 Natural antioxidants extracted from Osage orange fruits.. Oxidation of vegetable or fish oils, or the natural oils in foods, causes off- flavors and odors, destroys essential fatty acids and other nutrients, and reduces the shelf-life of the oils and foods. There is a strong desire by the food industry and proponents of clean labels and natural foods to develop natural antioxidants to replace synthetic antioxidants that are currently used in foods. Osage orange tree is common throughout the midwestern and southwestern regions of the United States, and the fruits from this tree are underutilized despite high content of osajin and pomiferin, two potent antioxidants. ARS scientists at Peoria, Illinois, developed a very efficient extraction method to isolate a high-concentration mixture of osajin and pomiferin. These scientists studied the antioxidant activity of this extract in soybean oil and fish oil during storage at 25 and 40 °C. The antioxidant activity of Osage orange fruit extract was stronger than commercial natural antioxidants such as rosemary extract and Vitamin E (mixed tocopherols) and similar to or stronger than the most commonly used synthetic antioxidant, butylated hydroxytoluene (BHT). These results indicated that the Osage orange fruit extract was effective as an antioxidant and prevented the off-flavors and odors that occur when oils are oxidized. Although these extracts should be further tested to determine their safety this study demonstrated that the Osage orange fruit extract has great potential as an antioxidant for edible oils. 02 Making margarines with lower saturated fat.. Margarines are traditionally prepared using mixtures of hard fats, such as palm oil or hydrogenated oils, liquid vegetable oils, water, and other ingredients. They are used as table spreads and for baking and cooking. Current recommendations call for reducing saturated fats in the diet because their consumption increases the risk of high cholesterol, atherosclerosis, and heart disease. Therefore, ARS scientists at Peoria, Illinois, are developing replacements for the high saturated fats that are used in margarines using oleogels made from small amounts of natural waxes mixed with liquid oil. The scientists previously found that mixtures of oil with candelilla wax or beeswax provided oleogels with increased firmness but lower melting points. To improve on these mixtures, margarines made with oil and mixtures of candelilla wax and beeswax, and they had higher firmness and lower melting points than margarines made with each single wax. Reducing the melting point will allow the margarine to melt in the mouth, which is preferred by consumers. This study showed that properties of oleogel-based margarines such as firmness and melting properties could be improved by mixing two waxes, and that these oleogels could be used to replace saturated fats to prepare margarines.
Impacts (N/A)
Publications
- Hwang, H., Moser, J.K. 2020. Properties of margarines prepared from soybean oil oleogels with mixtures of candelilla wax and beeswax. Journal of Food Science. 85(10):3293-3302. https://doi.org/10.1111/1750-3841.15444.
- Jia, Y., Kumar, D., Moser, J.K., Dien, B.S., Singh, V. 2020. Recoveries of oil and hydrolyzed sugars from corn germ meal by hydrothermal pretreatment: a model feedstock for lipid-producing energy crops. Energies. 13(22). Article 6022. https://doi.org/10.3390/en13226022.
- Byars, J.A., Singh, M., Kenar, J.A., Felker, F.C., Moser, J.K. 2021. Effect of particle size and processing method on starch and protein digestibility of navy bean flour. Cereal Chemistry. 98(4):829-839. https:// doi.org/10.1002/cche.10422.
- Hwang, H-S., Winkler-Moser, J.K., Tisserat, B., Harry-O'kuru, R.E., Berhow, M.A., Liu, S.X. 2020. Antioxidant activity of Osage orange extract in soybean oil and fish oil during storage. Journal of the American Oil Chemists' Society. 98(1):73-87. https://doi.org/10.1002/aocs.12458.
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Progress 10/01/19 to 09/30/20
Outputs Progress Report Objectives (from AD-416): Objective 1. Stabilize sensitive and bioactive food ingredients, improve shelf-life, and reduce food waste with optimized natural antioxidants and plant extracts. Sub-Objective 1.A. Evaluate antioxidant activity of combinations of antioxidants in frying oils and fried foods. Sub-objective 1.B. Evaluate antioxidants or natural antioxidant extracts for protection of polyunsaturated and omega-3 oils and bioactive lipids and to extend shelf-life of whole foods and food ingredients. Objective 2. Enable oleogel applications to reduce saturated fats in foods. Sub-Objective 2.A. Investigate and optimize the physical and sensory properties as well as the oxidative stability of edible oleogels. Sub-objective 2.B. Evaluate interesterified natural waxes, waxes with vegetable oils, fatty alcohols or fatty acids, as potential new oleogelators. Objective 3. Improve commercial value and sustainable food production through recovery of healthful bioactive ingredients from food processing by-products or waste. Approach (from AD-416): Approximately 30% of the food supply in the United States is wasted and the worldwide problem is even larger. This waste represents a large strain on the environment and on the entire food production enterprise. According to the Food and Drug Administration (FDA), about 20% of the food waste in the United States is due to confusion about the meaning and safety of foods labeled with �best before� and �use by� dates. This means that extending shelf-stability of foods can have an impact in reducing food waste. There is also concern about the healthfulness of processed foods, including the high content of saturated fats, which consumers are advised to limit in the diet. However, reducing the saturated fat content of foods by substituting with healthier fats can influence product texture and mouthfeel, as well as the oxidative stability and shelf-life. The research of the next five years will enable the commercial development of natural antioxidants needed to improve the oxidative stability and shelf-life of foods formulated with a lower saturated fat content. Antioxidants will improve the stability of frying oils, fried foods, and high-value foods such as nuts and protein replacement bars. Oleogels will be developed with improved physical and melting properties for margarines and shortenings and other food applications that require hard fats and will have lower amounts of saturated fats and zero trans fats. New value-added ingredients such as antioxidants and bioactive lipids will be mined and characterized from low-value agricultural inputs. This research, together with complimentary technology and policy development strategies, will contribute to efforts to reduce food waste and improve the healthfulness of the food supply. This new project plan 5010-44000-054-00D, "Increasing Food Shelf-Life, Reducing Food Waste, and Lowering Saturated Fats with Natural Antioxidants and Oleogels" replaces 5010-44000-052-00D. Project plan has been certified by 306 OSQR cycle.
Impacts (N/A)
Publications
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