Research Project: Chemical Conversion of Biomass into High Value Products

Location: Sustainable Biofuels and Co-products Research

2021 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
Production of functional lipid products. A multi-step synthesis route for producing the monomeric fatty acid-based arginate products was improved, and it was discovered that the feedstock containing the functional (hydroxyl) group had a significant effect on both synthesis scenarios and product yields. Thus, the reaction conditions on varying the Lewis acid catalyst selection and its catalytic loading were systematically investigated to ensure that the hydroxyl group was preserved. Thorough characterization using analytical tools such as Fourier transform infrared spectroscopy and nuclear magnetic resonance showed that the products' hydroxyl group has remained intact. This new information provides a better understanding of how to modify the synthetic route to produce the products more efficiently. The results have been filed in the U.S. non-provisional patent application (Serial No. 17/186,958). Structural modification of chicken fats. Non-edible chicken fat collected from local rendering houses was converted into a modified fat via chemical synthesis by adding functional groups to the molecule. This modified chicken fat exhibited improved physical and tribological properties, which can be used as lubricant ingredients. Modification of biobased carbohydrate polymers. Hemicellulose-B, also called bio-fiber gum (BFG), can be modified by conjugating it with whey protein isolate (WPI) to make a high-quality film-forming material. Thus, the BFG and WPI were conjugated with glycerol and carvacrol (an antibacterial agent), resulting in superior antimicrobial food packaging film and coating. The antimicrobial efficacies of the film were evaluated and found to effectively reduce the populations of E. coli, Listeria, and native microorganisms in tomatoes and fresh-cut apples, as well as populations of Salmonella and bread fungi in growth media. The film has high mechanical strength and low permeability to oxygen and carbon dioxide. The film and coating can be used on food by the direct surface coating and headspace releasing methods. This discovery will benefit food industries and U.S. farmers by converting their agricultural processing by-products into highly valuable packaging materials.

Accomplishments
1. Valuable ingredients from low (or no) valued fats/lipid. USDA-ARS scientists in Wyndmoor, Pennsylvania, have chemically converted the lesser valued lipids non-edible chicken fat into high value-added products. Fatty acid amide derivatives synthesized from free fatty acids are biologically active with an excellent inhibitory effect against gram-positive food-borne pathogen bacteria. The non-edible chicken fat is chemically modified by incorporating at the molecular level to improve oxidative stability and thickness, making it a strong lubricant. This invention would reduce the cost of managing waste, offer a cheaper alternative to produce valuable ingredients, and replace petroleum-based lubricants, which are not biodegradable and harmful to the environment and humans.

Review Publications
Yadav, M.P., Kaur, A., Singh, B., Simon, S., Kaur, N., Powell, M.J., Sarker, M.I. 2021. Extraction and characterization of lipids and phenolic compounds from the brans of different wheat varieties. Food Hydrocolloids. https://doi.org/10.1016/j.foodhyd.2021.106734.
Yan, J., Zhang, B., Feng, L., Yan, W., Wu, F., Lv, P., Jia, X., Yadav, M.P., Yin, L. 2020. Diverse mechanical properties and microstructures of sorghum bran arabinoxylans/soy protein isolate mixed gels by duo-induction of peroxidase and calcium ions. Food Hydrocolloids. https://doi.org/10.1016/j.foodhyd.2020.105946.
Kaur, A., Singh, B., Yadav, M.P., Bhinder, S., Singh, N. 2020. Isolation of arabinoxylan and cellulose-rich arabinoxylan from wheat bran of different varieties and their functionalities. Food Hydrocolloids. https://doi.org/10.1016/j.foodhyd.2020.106287.
Stoklosa, R.J., Latona, R.J., Powell, M.J., Yadav, M.P. 2020. Influence of phenolic acid content on the antioxidant capacity of hemicellulose from sorghum plant fractions. BioResources. 15(4):7933-7953.
Singh, B., Singh, J.P., Kaur, A., Yadav, M.P. 2021. Insights into the chemical composition and bioactivities of citrus peel essential oils. Food Research International. https://doi.org/10.1016/j.foodres.2021.110231.
Suri, K., Singh, B., Kaur, A., Yadav, M.P., Singh, N. 2020. Influence of microwave roasting on chemical composition, oxidative stability and fatty acid composition of flaxseed (Linum usitatissimum L.) oil. Food Chemistry. https://doi.org/10.1016/j.foodchem.2020.126974.
Yan, W., Zhang, B., Yadav, M.P., Feng, L., Yan, J., Jia, X., Yin, L. 2020. Corn fiber gum-soybean protein isolate double network hydrogel as oral delivery vehicles for thermosensitive bioactive compounds. Food Hydrocolloids. https://doi.org/10.1016/j.foodhyd.2020.105865.
Kaur, N., Singh, B., Kaur, A., Yadav, M.P., Singh, N., Ahlawart, A.K., Singh, A.M. 2020. Effect of growing conditions on proximate composition, mineral, antioxidant properties, amino acid and phenolic composition of wheatgrass from different wheat varieties. Food Chemistry. https://doi.org/10.1016/j.foodchem.2020.128201.
Sarker, M.I., Long, W., Liu, C. 2020. Efficacy of aqueous solution of n-halamine to reduce microbiological contamination on cattle hides for meat safety with byproduct quality assurance. Journal of American Leather Chemists Association. 115:330-336.
Yosief, H.O., Hussain, S.A., Sarker, M.I., Annous, B.A. 2020. Efficacy of fatty acid amide derivatives against listeria monocytogenes. ChemistrySelect. https://doi.org/10.1002/slct.202003501.
Zhang, J., Nunez, A., Strahan, G.D., Ashby, R.D., Huang, K., Moreau, R.A., Yan, Z., Chen, L., Lew, H.N. 2020. An advanced process for producing structurally selective dimer acids to meet new industrial uses. Industrial Crops and Products. https://doi.org/10.1016/j.indcrop.2020.112132.
Hotchkiss, A.T., Chau, H.K., Strahan, G.D., Nunez, A., Simon, S., White, A.K., Yadav, M.P., Dieng, S., Hirsch, J. 2020. Blueberry fiber pectin, xyloglucan and anthocyanin structure and function. Food Hydrocolloids. https://doi.org/10.1016/j.foodhyd.2020.106572.