Location: Sustainable Biofuels and Co-products Research
2022 Annual Report
Objectives
1. Develop new functional (phenolics derived from fractionated bio-oils, monomeric sugars from carbohydrate, and amino acids) biobased fatty acid products from chemical technologies.
Subobjective 1a: Development of monomeric fatty acid-based products with antimicrobial properties.
Subobjective 1b: Development of polymeric fatty acid products from the monomeric sugar based-fatty acid products.
2. Develop chemical and enzymatic approaches to convert triglycerides derived from low (or no) value waste or bio-residue into valuable commercial products.
3. Develop innovative technologies to modify nonfermentable hemicellulosic and cellulosic carbohydrate polymers isolated from lignocellulosic biomass including agricultural residues, agricultural processing by-products and energy crops into commercially viable novel co-products.
Approach
To address these objectives, research tasks will be performed with industrial partners and other collaborators. The approach will involve catalyst selection, process design, product isolation, purification and characterization methodologies to develop new functional biobased products. First, recyclable solid catalysts will be explored to introduce branching between the functional hydroxyl group and unsaturation on the fatty acid alkyl chain to generate functional fatty acid monomers with improved antimicrobial properties. Second, the functional monomers will be engineered into hydroxylic-oil based polyurethane biopolymers with active hydroxy sites on the surfaces to prevent buildup of bacteria colonies. Third, functional groups will be introduced on unsaturated carbons of the fatty acid chain of triglycerides through chemical and enzymatical methods. The resulting triglyceride-based products will have improved lubricant solubility and low temperature properties. Finally, chemical modification will be developed to utilize the isolated carbohydrate polymer fractions and generate new carbohydrate products. Isolation of carbohydrate polymers will be performed on agriculture processing byproducts and agricultural residues using an improved isolation method. All functional products will be subjected to analytical characterizations for structural identification and will be evaluated for their applications and commercial uses. Attaining these objectives will create superior new antimicrobial, antioxidant, emulsifier, biolubricant, and biopolymer functional materials.
Progress Report
In Subobjective 1a, improvement in the ARS patented fatty acid branching technology, sustainability and cost was explored. In collaboration with an ARS researcher at Wyndmoor, Pennsylvania, who has developed efficient isolation methods to fractionate phenolics from pyrolysis of woody biomass, a unique set of renewable and cost-effective bio-oil (predominantly phenolics) branched fatty acids was made. Through optimization of the branching technology and thorough characterization, preliminary results showed that the hydroxyl group on the phenolics has remained intact. This is important as the hydroxyl functional group plays a crucial role against bacteria. Currently, purification of these bio-oil fatty acid products was initiated using a wiped-film molecular distillation device where various temperatures and pressures were examined to obtain the desired products with high purities. Utilization of phenolics from bio-oil, rather than fossil derived phenolics, to synthesize the branched fatty acids allows this to be a fully bio-based product, which can be potentially used as antimicrobial agents.
In Subobjective 1b, the arabinoxylan from agricultural processing byproduct was isolated and used as a representative sugar to demonstrate its modification via its reaction with a fatty acid derivative to make it more hydrophobic. Multiple experiments were conducted to synthesize and characterize the derivatized sugar. Structural characterization of the products using methods including nuclear magnetic resonance spectroscopy, fourier transform infrared spectroscopy, and degree of substitution measurement. Modification of arabinoxylan, an agricultural processing byproduct, provide an opportunity to regulate its amphiphilic character so as to exploit for various potential applications.
In continuation from last year in Subobjective 1b, the synthesis approach of the sugar-fatty acid conjugate was finalized for further optimization. Parameters for optimizing reaction conditions are being studied. Various isolation procedures were evaluated to recover the final product in good yields and quality. Performance characterization methods are being established for thermal stability and emulsifying properties. The impact of this work will be the utilization of agricultural processing byproducts for making value-added products, such as improved emulsifiers and renewable biopolymeric films for food and non-food applications.
In Objective 2, non-edible beef-tallow collected from a local rendering house was structurally modified through the establishment of a synthetic route to chemically modify animal fats. Reaction parameters have been optimized to obtain high yield of the products with good quality. The modified beef-tallow has been evaluated for improved physio-chemical properties to be potentially used as a base oil for bio-lubricant formulation.
In Objective 3, water-insoluble cellulose was fractionated from an agricultural processing by-product. It was then isolated and solubilized by crosslinking its chains using a calcium chloride chelating agent. This crosslinked method was successful and created a solubilized cellulose solution. The solution was further used to cast films and its physical and mechanical properties were studied. The results showed that with an increase in calcium ion concentration, the tensile strength and elongation at break of the prepared films improved significantly compared to commercial plastic films.
Accomplishments
1. Creating functional arginine-based biocides. The misuse and overuse of antibiotics and biocides have increased microorganism resistance, leading to many global health issues. ARS scientists in Wyndmoor, Pennsylvania, have invented functional arginine-based lipid biocides that are non-volatile with strong antimicrobial activity. These products also exhibit excellent surfactant properties, which can be ideal for antibacterial detergent or soap application. The unique feature of these functional arginine-based derivatives could lead to inhibiting a wide range of microorganisms.
2. Chemical stimulants in synthesis of Omege-3-fatty acid. Omega-3-fatty acid obtained from marine fish contains unpleasant taste and odor and is less stable in nature. ARS scientists in Wyndmoor, Pennsylvania, have successfully identified several chemical stimulants to be used in biosynthesis of Omega-3 fatty acids by an Aurantiochytrium SP microorganism. Usage of identified stimulants in biosynthesis increased the Omega-3 fatty acid production substantially which has a higher level of oxidative stability than that of fish oil.
3. Highly functional bio-based films. An alternative biodegradable material is needed to replace plastics which lack biodegradability. ARS researchers in Wyndmoor, Pennsylvania, have invented a process to join biofiber gum, an ARS proprietary material, with whey protein isolate to create highly bioactive film forming materials. These bioactive films have been evaluated for their antimicrobial efficacies and mechanical properties. The materials can be used to make food packing films and coatings. These types of biodegradable packaging materials offer an environmentally friendly alternative to petroleum-based plastics.
Review Publications
Yosief, H.O., Sarker, M.I., Bantchev, G.B., Dunn, R.O., Cermak, S.C. 2022. Physico-chemical and tribological properties of isopropyl-branched chicken fat. Fuel. 316. Article 123293. https://doi.org/10.1016/j.fuel.2022.123293.
Yosief, H.O., Sarker, M.I. 2021. Naturally derived fatty acid based antibacterial agents. In: Sarker, M.I., Liu, L., Yadav, M.P. Yosief, H.O., Hussain, S.A., editors. Conversion of Renewable Biomass into Bioproducts. Volume 1392. ACS Symposium Series. Washington, DC: American Chemical Society. p.91-117.
Hussain, S.A., Sarker, M.I. 2021. Sustainable production of medium-chain fatty acids (MCFA). In: Sarker, M.I., Liu, L., Yadav, M.P. Yosief, H.O., Hussain, S.A., editors. Conversion of Renewable Biomass into Bioproducts. Volume 1392. ACS Symposium Series. Washington, DC: American Chemical Society. p. 119-138.
Yadav, M.P., Sarker, M.I. 2021. Functional Co-products from Sorghum Biomass. In: Sarker, M.I., Liu, L., Yadav, M.P. Yosief, H.O., Hussain, S.A., editors. Conversion of Renewable Biomass into Bioproducts. Volume 1392. ACS Symposium Series. Washington, DC: American Chemical Society. p. 7-14.
Kaur, N., Singh, B., Kaur, A., Yadav, M.P. 2022. Impact of growing conditions on proximate, mineral, phenolic composition, amino acid profile, and antioxidant properties of black gram, mung bean, and chickpea microgreens. Journal of Food Processing and Preservation. https://doi.org/10.1111/jfpp.16655.
Wang, Z., Zhang, C., Watson, J., Sharma, B.K., Si, B., Zhang, Y. 2022. Adsorption or direct interspecies electron transfer? A comprehensive investigation of the role of biochar in anaerobic digestion of hydrothermal liquefaction aqueous phase. Chemical Engineering Journal. https://doi.org/10.1016/j.cej.2022.135078.
Sarker, M.I., Liu, C. 2022. A novel approach of removing externally attached debris from animal carcass to ensure meat safety and byproduct quality. Journal of American Leather Chemists Association. 117:96-103.
Gundupalli, M.P., Tantayotai, P., Panakkal, E.J., Chuetor, S., Kirdponpattara, S., Thomas, A.S., Sharma, B.K., Sriariyanun, M. 2022. Hydrothermal pretreatment optimization and deep eutectic solvent pretreatment of lignocellulosic biomass: An integrated approach. Bioresource Technology Reports. https://doi.org/10.1016/j.biteb.2022.100957.
Janaswamy, S., Yadav, M.P., Hoque, M., Bhattarai, S., Ahmed, S. 2022. Cellulosic fraction from agricultural biomass as a viable alternative for plastics and plastic products. Industrial Crops and Products. https://doi.org/10.1016/j.indcrop.2022.114692.
Singhvi, P., Garcia Mainieri, J.J., Ozer, H., Sharma, B.K., Al-Qadi, I.L. 2022. Impacts of field and laboratory long-term aging on asphalt binders. Transportation Research Board. https://doi.org/10.1177%2F03611981221083614.
Kaur, A., Singh, B., Kaur, A., Yadav, M.P., Singh, N. 2021. Impact of intermittent frying on chemical properties, fatty acid composition and oxidative stability of 10 different vegetable oil blends. Journal of Food Processing and Preservation. https://doi.org/10.1111/jfpp.16015.
Hotchkiss, A.T., Chau, H.K., Strahan, G.D., Nunez, A., Simon, S., White, A.K., Dieng, S., Heuberger, E., Yadav, M.P., Hirsch, J. 2022. Structural characterization of red beet fiber pectin. Food Hydrocolloids. 129:107549. https://doi.org/10.1016/j.foodhyd.2022.107549.
Yan, W., Zhang, M., Zhang, M., Yadav, M.P., Jia, X., Yin, L. 2022. Effect of arabinoxylans with different molecular characteristics on the gelatinization and long-term retrogradation behavior of wheat starch. Carbohydrate Polymers. https://doi.org/10.1016/j.carbpol.2022.119581.
Hussaini, S.R., Sarker, M.I., Yosief, H.O., Yadav, M.P. 2021. Evaluation of diverse biochemical stimulants to enhance growth, lipid and docosahexaenoic acid (DHA) production of aurantiochytrium Sp. ATCC PRA-276. Biocatalysis and Agricultural Biotechnology. https://doi.org/10.1016/j.bcab.2021.102122.
