Research Project: Technologies for Producing Marketable Bioproducts

Location: Renewable Product Technology Research

2021 Annual Report

Objectives
The goal of this project is to create new chemical, biochemical, and chemocatalytic processes for economically producing value-added products from biomass, particularly from plant lipids and lignocellulose. Project team members will collaborate within the project, with other ARS researchers, and external partners to reach the following objectives: Objective 1. Enable biochemical/chemical processes to convert commodity crops, crop oils, and byproducts into value-added commercial bioproducts. Objective 2. Develop innovative lipid and biopolymer-based encapsulation systems for delivering, preserving, or promoting the activity of bioactive ingredients. Objective 3. Resolve difficult catalytic processes to produce consumer products and industrial chemicals from crop residue, lignocellulosics, and biorefinery byproducts.

Approach
This research will enhance the economic viability and competitiveness of U.S. agriculture commodities by expanding domestic and global market opportunities associated with the growing bioeconomy through the development of environmentally friendly, value-added food and non-food biobased technologies and products. Plant lipids such as vegetable oil and lecithin are already available in high purity, while lignocellulose is abundant yet chemically complex. To properly exploit these valuable resources, new chemical, biochemical, and chemocatalytic processes must be developed that selectively generate higher value products. The challenge, therefore, centers on finding the most effective chemical, biochemical, and/or chemocatalytic conversion methods, optimizing process reaction conditions for effecting the desired biomass transformations, isolation and purification of the targeted bioproducts, and demonstrating that the bioproducts have equivalent or superior properties to commercially available products. We have developed several distinctive and innovative approaches to reaching our goal. Our approach involves finding and modifying (in some cases) those catalysts and processes that perform the desired biomass transformation. Biochemical/biocatalytic and chemocatalytic methods will be developed to produce select chemicals from vegetable oils and lignocellulosics. Isolated enzymes will be used to convert lipids and lipid byproducts to consumer-targeted products. Designed multi-layered phospholipids and polysaccharide-based nanoparticles will be used to enhance and deliver bioactive ingredients in food and cosmetics. The sourcing of starting materials from agricultural feedstocks and byproducts in each of these endeavors to find solutions to the barriers that exist in the creation of a biobased economy.

Progress Report
Under Objective 1, progress was made on developing new biobased compounds containing phytochemicals. Ferulic acid is a nearly ubiquitous constituent of plants, where it provides strong ultraviolet absorbing and antioxidant properties. These functional traits have long been recognized as being valuable attributes to be exploited for health and personal care applications. We have previously developed technology to transfer ferulic acid to vegetable oils through a process called transesterification. This method also produced glycerol bound to ferulic acid as a byproduct. We purified these natural byproducts in large quantities to determine if they also had functional attributes. The unique production, isolation and purification processes developed under the objective increased the yield of the natural compounds approximately 100-fold compared to previous literature reports, which isolated the compounds by extraction of plants. These natural compounds have demonstrated ultraviolet and antioxidant properties and are being evaluated for antifungal, insecticidal, and antimicrobial activities. Under Objective 2, progress was made on developing biodegradable encapsulation systems using renewable polysaccharides for delivery and preservation of bioactive compounds. A natural, water-insoluble polysaccharide made enzymatically from cane and beet sugar could be converted to nanoparticles using ARS technology and then utilized for encapsulation. The encapsulation system was stable for at least seven months and did not degrade even at temperatures as high as 60 °C. It was determined that this encapsulation system was best suited for trapping and carrying oil-like or water-insoluble bioactives with applications in consumer products. We also investigated the ability of using other polysaccharides to develop similar encapsulation systems using this technology. Under Objective 3, progress was made in increasing the scale of the synthesis of biobased surfactants. We previously developed technology so that several different agriculturally derived sugars and waste sugars (e.g., from the dairy industry) could be linked to a modified oil isolated from Cuphea seed to form surfactants with potential cosmetic, household, and industrial applications. These new surfactants have also been shown to have antimicrobial activity. This invention is not only expected to expand the availability of specialty detergents, but they will contribute to the development of Cuphea as a new crop for marginal Midwestern lands. To be economically practical, these surfactants need to be produced at large scale. Synthesis of surface-active agents prepared from inexpensive sugars and Cuphea lipids has been scaled from tens of milliliters to two liters, resulting in single run preparations that yield up to two hundred grams of product. These products have now been shared with an industrial partner for testing as antiviral cleansers.

Accomplishments
1. Biobased sanitizers from sugars and seed oil. Surfactants are the primary component of detergents and are used in a wide range of products including cosmetics, foods, paints, and agricultural herbicides. ARS researchers at Peoria, Illinois, created a new class of surfactant by combining two different proprietary ARS technologies that allow commonly used sugars to be chemically linked to a compound derived from the seed oil obtained from the new row crop Cuphea. The sugars can include glucose and maltose, which are obtained from corn starch, and lactose, a waste sugar from the dairy industry. These new surfactants are low foaming and kill bacteria on contact making them suitable for use in cleansers and sanitizers and are being commercialized. New uses for Cuphea oil make this alternative crop economically attractive to farmers with marginal lands where Cuphea grows well.

2. Water resistant sugar-based delivery system. Personal care products often rely on encapsulation of ingredients to stabilize product and allow controlled release of active ingredients. Consumers are demanding more natural ingredients in personal care products, making it essential that these delivery systems are made of natural and biodegradable material. Using high-pressure methods, ARS researchers at Peoria, Illinois, showed that biobased polysaccharides were converted into a long-lasting delivery system that was stable at high temperatures. This delivery system successfully carried oil-like bioactive and antimicrobial ingredients. This encapsulation system can be used in skin care products, pharmaceutical products, and agricultural products, expanding the market for sugars produced as byproducts from biorefining of agricultural materials.

Review Publications
Vaughn, S.F., Moser, J.K., Berhow, M.A., Byars, J.A., Liu, S.X., Jackson, M.A., Peterson, S.C., Eller, F.J. 2020. An odor-reducing, low dust-forming, clumping cat litter produced from Eastern red cedar (Juniperus virginiana L.) wood fibers and biochar. Industrial Crops and Products. 147. Article 112224. https://doi.org/10.1016/j.indcrop.2020.112224.
Appell, M.D., Tu, Y., Compton, D.L., Evans, K.O., Wang, L.C. 2020. Quantitative structure-activity relationship study for prediction of antifungal properties of phenolic compounds. Structural Chemistry. 31:1621-1630. https://doi.org/10.1007/s11224-020-01549-1.
Gonzalez, J.M., Boddu, V.M., Jackson, M.A., Moser, B.R., Ray, P. 2020. Pyrolysis of creosote-treated railroad ties to recover creosote and produce biochar. Journal of Analytical and Applied Pyrolysis. 149. Article 104826. https://doi.org/10.1016/j.jaap.2020.104826.
Elsayed, I., Jackson, M.A., Hassan, E. 2020. Catalytic hydrogenation and etherification of 5-Hydroxymethylfurfural into 2-(alkoxymethyl)-5-methylfuran and 2,5-bis(alkoxymethyl)furan as potential biofuel additives. Fuel Processing Technology. 213. Article 106672. https://doi.org/10.1016/j.fuproc.2020.106672.
Evans, K.O., Skory, C.D., Compton, D.L., Cormier, R., Cote, G., Kim, S., Appell, M.D. 2020. Development and physical characterization of alpha-glucan nanoparticles. Molecules. 25(17). Article 3807. https://doi.org/10.3390/molecules25173807.
Vaughn, S.F., Byars, J.A., Jackson, M.A., Peterson, S.C., Eller, F.J. 2021. Tomato seed germination and transplant growth in a commercial potting substrate amended with nutrient-preconditioned Eastern red cedar (Juniperus virginiana L.) wood biochar. Scientia Horticulturae. 280. Article 109947. https://doi.org/10.1016/j.scienta.2021.109947.
Appell, M.D., Compton, D.L., Evans, K.O. 2020. Predictive quantitative structure-activity relationship modeling of the antifungal and antibiotic properties of triazolothiadiazine compounds. Methods and Protocols. 4(1). Article 2. https://doi.org/10.3390/mps4010002.
Price, N.P., Jackson, M.A., Hartman, T.M., Branden, G., Ek, M., Koch, A., Kennedy, P.D. 2021. Branched chain lipid metabolism as a determinant of the N-acyl variation of Streptomyces natural products. ACS Chemical Biology. 16(1):116-124. https://doi.org/10.1021/acschembio.0c00799.
Moser, B.R., Jackson, M.A., Doll, K.M. 2021. Production of industrially useful and renewable p-cymene by catalytic dehydration and isomerization of perillyl alcohol. Journal of the American Oil Chemists' Society. 98(3):305–316. https://doi.org/10.1002/aocs.12468.
Hering, J., Dunevall, E., Snijder, A., Eriksson, P., Jackson, M.A., Hartman, T.M., Ting, R., Chen, H., Price, N.P., Branden, G., Ek, M. 2020. Exploring the active site of the antibacterial target MraY by modified tunicamycins. ACS Chemical Biology. 15(11):2885-2895. https://doi.org/10.1021/acschembio.0c00423.