Research Project: Chemical Conversion of Biomass into High Value Products

Location: Sustainable Biofuels and Co-products Research

2023 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
Under National Program 306, Product Quality and New Uses, significant progress was made on all three objectives and their subobjectives. Under Subobjective 1a, an effort to develop bio-based compounds with antimicrobial activity, significant progress was made using the patented ARS technology to produce the phenolic- branched fatty acid compounds from non-edible fatty acids such as waste trap greases. Although many challenges were encountered at the purification stage to refine the waste feedstock to an acceptable level, it was obtained with approximately 99% purity which was ideal for a subsequent arylation reaction where several functional phenolic-branched fatty acid products were produced. Scale up to a two-liter reactor is currently being investigated. The antimicrobial efficacy of the functional phenolic-branched fatty acid compounds’ emulsion was then tested against Listeria on apple fruit. Exciting results indicated that the synthesized compounds at levels of 500 part per million had similar antimicrobial activity against Listeria on apple fruit as a 20 µg/mL chlorine solution, a commonly used sanitizer. With the partially supported funds from NIFA-AFRI, the phenolic-branched fatty acid products were polymerized into bio-based antimicrobial bio-epoxy polymers. Excitingly, the bio-epoxy polymers were found to inhibit both Listeria and Escherichia coli (E. coli) bacteria. They are also reusable for at least five consecutive exposures even after thorough washing. Along the line of this branching technology and in collaboration with an ARS researcher at Peoria, Illinois, significant progress was made with the methyl-branched chain fatty acid estolide products. The physical and lubricant property results of these estolide products show that the products have better properties than the traditional linear-chain fatty estolide products and the commonly used petroleum-based products. In Subobjective 1b, a faster microwave assisted (MWA) process was successfully developed to modify the hydrophobicity of sugar polymers like arabinoxylans using short-chain fatty acids. Reaction conditions, like reactants ratio, temperature, and time, were used to synthesize a variety of biopolymers with different degrees of substitution. An isolation process was optimized to remove unreacted reactants and solvent to obtain modified biopolymers in high yields. The modification of biopolymer arabinoxylan was further confirmed using structural characterization by fourier transform infrared (FTIR), thermogravimetric analyzer (TGA), and nuclear magnetic resonance (NMR). These modified biopolymers were evaluated for their emulsification properties in food/non-food applications. Another application of these modified biopolymers was explored to prepare films. After trying several methods, a methodology was optimized for casting biobased/biodegradable films with improved film strength and oxygen barrier properties. Work is in progress to study the mechanical and antimicrobial properties of these films for their potential application as biobased food packaging film/coating. These new value-added products will help in increasing the utilization of agricultural processing byproducts. In Objective 2, non-edible lard was subjected to chemical modification using the previously established procedure to make it a functional triglyceride. Structural identification and purification technique of the synthesized product have been determined. The structurally modified lard has shown advanced properties to be used as bio-lubricant. In another study, two triesters called trimethylolpropane-triisostearate (TMP-ISA) and trimethylolpropane-triisooleate (TMP-IOA) have been synthesized in a green process from naturally derived free fatty acid, i.e., oleic acid. This synthesis process uses reusable catalyst which generates very little/no waste, thus becoming very cost-effective and eco-friendly. These triesters have been characterized with different analytical methods such as NMR, FTIR, gas chromatography mass spectrometry, and liquid chromatography mass spectrometry. Physicochemical and tribological properties, such as density, viscosity, oxidative stability, and cold temperature properties of the triesters, reveal that these compounds can be potentially used as bioingredients for bioproducts. In Objective 3, antimicrobial food packaging films and coatings were developed by using hemicellulose and whey protein isolate conjugate. In vitro and in vivo tests were applied to assess the antimicrobial efficacies of the films against E. coli, Salmonella, Listeria, spoilage fungi, and background bacteria. The physicochemical properties of the films were examined to evaluate their potential for food packaging applications. They have good mechanical properties, low water vapor permeability, and a good oxygen and carbon dioxide barrier. The populations of E. coli, Listeria, and native microorganisms on tomatoes and fresh-cut apples stored at 4 C for up 21 days were drastically reduced by these films. They also significantly inhibited Salmonella and bread fungi growth in media. The hemicellulose B (AX) was crosslinked by laccase (enzyme) treatment. The encapsulating matrices, using crosslinked AX, sodium alginate, and a mixture of crosslinked AX and sodium alginate, were used to investigate the viability of bacteria (Lactobacillus rhamnosus GG, Streptococcus thermophilus, and Bifidobacterium longum) under storage conditions. The crosslinked AX and its mixture with sodium alginate showed the highest encapsulation efficiencies (55-77%) for all three strains. A higher level (approximately 7 logs) of Lactobacillus rhamnosus GG were recovered from the mixture of crosslinked AX and sodium alginate matrices after 28 days of storage under aerobic conditions at 4 C in comparison to sodium alginate matrices (approximately 4 logs). This could be due to the stability of the covalent crosslinked network formed during AX gelation by laccase treatment, which protected bacterial viability. Thus, the crosslinked AX can be a useful ingredient for constructing matrices to encapsulate and protect probiotic bacteria for their targeted delivery to the colon. In collaboration with the South Dakoda University on a NIFA project, the cellulosic fraction from wheat straw was solubilized using zinc ions, and calcium ions with different concentrations by crosslinking this polymer chains. Then its film was prepared and characterized. The result reveals that the increase of calcium ions significantly decrease moisture content, water solubility, water vapor permeability, transparency, and elongation of the films. Films containing high concentration of calcium chloride have tensile strength approximately 2.5 times higher than commercial polyethylene. Moreover, approximately 90% of all the films are biodegradable within a month in soil containing 20% moisture content. Thus, cellulosic fraction extracted from wheat straw biomass has a great potential to replace synthetic non-biodegradable plastic.

Accomplishments
1. A new generation of triesters for bioproducts. Fossil-based products raise concerns regarding biodegradability and toxicity being harmful to the environment. ARS scientists in Wyndmoor, Pennsylvania, have synthesized and characterized a new class of triester from naturally derived fatty acid via a green process where a reusable catalyst is used. The inventive technique generates little to no waste. This novel class of triesters contains both branched fatty acid chains and polyol backbone in the same molecule and thus offers higher thermal/oxidative stability and better fluidity when compared to linear (natural) triglyceride or commercially available petroleum-based product such as poly alpha olefin. In this invention, a renewable resource has been used as feedstock to produce potential bioingredients for bioproducts (for example, cosmetic biolubricant) to replace fossil-based products.

2. Oil-based hydrophobic coatings to prevent leaching of heavy metals. The successful utilization of coal fly ash will help prevent the release of several heavy metal contaminants such as Arsenic, Selenium, Lead, etc., into agricultural and drinking water sources. In collaboration with the University of Illinois on a Department of Energy project, ARS scientists in Wyndmoor, Pennsylvania, have successfully developed a hydrophobic coating using vegetable oil and sulfur for coal fly ash particles. These vegetable oil-based coatings have been shown to prevent the leaching of heavy metals present in coal fly ash particles. These coated fly ash particles exhibit superior performance as filler particles in plastic and elastomeric materials. This could lead to the production of low-cost filler material alternatives to calcium carbonate and carbon black. The results can contribute to lessening the impact of coal-fired power plants, thereby lowering the environmental footprint and bringing relief to communities being hit hard by the loss of jobs in the coal-based power generation supply chain.

Review Publications
Kohli, K., Chandrasekaran, S.R., Prajapati, R., Kunwar, B., Al-Salem, S., Moser, B.R., Sharma, B.K. 2022. Pyrolytic depolymerization mechanisms for post-consumer plastic wastes. Energies. 15(23). Article 8821. https://doi.org/10.3390/en15238821.
Sunder, S., Singh, B., Kaur, A., Yadav, M.P. 2022. Impact of infrared and dry air roasting on antioxidant potential, oxidative stability, chemical characteristics and fatty acid profile of black and white sesame (Sesamum indicum L.) oil. Journal of Food Processing and Preservation. https://doi.org/10.1111/jfpp.17252.
Hashem, M.A., Payel, S., Hasan, M.A., Raihan, A.A., Sarker, M.I. 2023. Effect of age and gender of animal on physicomechanical properties of Bangladeshi goat leather. Small Ruminant Research. https://doi.org/10.1016/j.smallrumres.2023.106933.
Huang, K., Fan, X., Ashby, R.D., Lew, H.N. 2021. Structure-activity relationship of antibacterial bio-based epoxy polymers made from phenolic branched fatty acids. Progress in Organic Coatings. 155:106228. https://doi.org/10.1016/j.porgcoat.2021.106228.
Ryu, V.N., Chuesiang, P., Corradini, M., McLandsborough, L., Jin, Z.T., Lew, H.N., Fan, X. 2022. Synergistic photoinactivation of Escherichia coli and Listeria innocua by curcumin and lauric arginate ethyl ester micelles. LWT - Food Science and Technology. 173:114317. https://doi.org/10.1016/j.lwt.2022.114317.
Ryu, V.N., Chuesiang, P., Lew, H.N., Ashby, R.D., Fan, X. 2022. Sustainable bio-based antimicrobials derived from fatty acids: synthesis, safety, and efficacy. Critical Reviews in Food Science and Nutrition. https://doi.org/10.1080/10408398.2022.2160430.
Biresaw, G., Chen, Y., Chen, L., Ngo, H., Wagner, K., Vermillion, K., Cermak, S.C. 2022. Iso-oleic estolide products with superior cold flow properties. Industrial Crops and Products. 182. Article 114857. https://doi.org/10.1016/j.indcrop.2022.114857.
Suri, K., Singh, B., Kaur, A., Yadav, M.P. 2023. Physicochemical characteristics, oxidative stability, pigments, fatty acid profile and antioxidant properties of co-pressed oil from blends of peanuts, flax seeds and black cumin seeds. Food Chemistry Advances. https://doi.org/10.1016/j.focha.2023.100231.
Moser, B.R., Cermak, S.C., Doll, K.M., Kenar, J.A., Sharma, B.K. 2022. A review of fatty epoxide ring opening reactions: Chemistry, recent advances, and applications. Journal of the American Oil Chemists' Society. 99(10):801-842. https://doi.org/10.1002/aocs.12623.
Biswas, A., Cheng, H.N., Kuzniar, G.M., He, Z., Kim, S., Furtado, R.F., Alves, C.R., Sharma, B.K. 2023. Bilayer films of Poly(lactic acid) and cottonseed protein for packaging applications. Polymers. 15(6). Article 1425. https://doi.org/10.3390/polym15061425.
Hashem, M.A., Payel, S., Mim, S., Hasan, M.A., Nur-A-Tomal, M.S., Rahman, M.A., Sarker, M.I. 2022. Chromium adsorption on surface activated biochar made from tannery liming sludge: A waste-to-wealth approach. Water Science and Engineering Journal. 15(4):328-336. https://doi.org/10.1016/j.wse.2022.09.001.
Yosief, H.O., Sarker, M.I., Hussain, S.A., Muir, Z.E. 2022. Effective removal of manure/mud balls from cattle hides using thioglycolate salt containing formulations. Journal of American Leather Chemists Association. 117:359-366.
Yosief, H.O., Sarker, M.I., Bantchev, G.B., Dunn, R.O., Cermak, S.C. 2022. Chemical modification of beef tallow for lubricant application. Industrial and Engineering Chemistry Research. 61(27):9889-9900. https://doi.org/10.1021/acs.iecr.2c01207.
Sarker, M.I., Lew, H.N., Sharma, B.K., Wagner, K., Jones, K.C., Powell, M.J. 2023. Green synthesis of trimethylolpropane triisostearate and triisooleate for usage as bio-lubricants. Tribology International. https://doi.org/10.1016/j.triboint.2023.108649.
Hotchkiss, A.T., Chau, H.K., Strahan, G.D., Nunez, A., Harron, A.F., Simon, S., White, A.K., Yadav, M.P., Yeom, H. 2022. Carrot rhamnogalacturonan I structure and composition changed during 2017 in California. Food Hydrocolloids. https://doi.org/10.1016/j.foodhyd.2022.108411.
Jin, Z.T., Yadav, M.P., Qi, P.X. 2023. Antimicrobial and physiochemical properties of films and coatings prepared from bio-fiber gum and whey protein isolate conjugates. Food Control. 148:109666. https://doi.org/10.1016/j.foodcont.2023.109666.