Location: Renewable Product Technology Research2017 Annual Report
This project creates new chemical and biochemical processes to produce value-added products from biomass, particularly from plant lipids and lignocellulose. The new, bio-based value-added products will create new markets and expand existing markets for vegetable oils and agrimaterials, enhancing the profitability of small- and medium-sized agribusinesses, which in turn benefits the local rural economy. New products will be developed that improve the health and safety of the American public, extend the shelf life of consumer products, and provide biobased alternatives and substitutes for petroleum-based chemicals. We will collaborate within the project, with other Agricultural Research Service researchers, with academic researchers and industrial partners to reach the following objectives. Objective 1: Enable, from a technological perspective, commercially-viable microbial, enzymatic, and chemical processes to produce commercial products from vegetable oils. Subobjective 1.A: Evaluate marketable oil derivatives under conditions of use. Subobjective 1.B: Produce polyol oils and oxygenated fatty acids from soybean oil through novel microbial biocatalysis. Objective 2: Enable new commercial encapsulation systems for controlled-release of bioactive molecules. Objective 3: Enable new commercial processes for the production of industrial chemicals from vegetable oils or lignocellulosics.
The objectives of this research are accomplished using strategies that include isolated enzymes in unconventional media, microbial strain development and fermentation, encapsulation and controlled release of bioactive molecules, high temperature, inorganic catalytic conversions, chemical/biochemical syntheses, and analytical analyses using state of the art equipment and facilities. Approaches for this project currently include the following areas of research: Vegetable oil-based biochemicals. We develop chemical and biochemical systems for the conversion of seed oils to value-added specialty/commodity chemicals. Our approach is to use isolated enzymes, whole microorganisms, and inorganic catalysts to modify domestically produced vegetable oils to introduce functional features valuable to consumer marketplaces. While the industry accepts such new molecules upon adequate safety testing, stronger product claims based on efficacy still need to be substantiated. Biochemical, cellular, and tribological analyses are undertaken to establish the metabolic fate and influence of the novel vegetable oil derivatives. No human or live animal testing is needed. Encapsulation and timed release of bioactive molecules. We develop phospholipid-based encapsulation systems (i.e. liposomes) that limit the release of bioactive molecules and protect the bioactives from degradation. Liposomes are used to encapsulate the bioactives of interest and the bioactives-loaded liposomes are further compartmentalized within a secondary liposome for increased protection. The multicompartmentalized liposome system provides increased protection and controlled release of the bioactive molecule. The liposome encapsulated bioactive systems are analyzed for stability and release rate of the bioactive molecules. Highly stable encapsulation and controlled release systems are highly desirable in the functional foods and beverage industries. Integrated biorefinery systems for biochemicals. We couple biomass pretreatment with catalytic conversions to form integrated processes to convert lignocellulosics and lipids into bio-based chemicals that replace petroleum-based products. Whole biomass, crop residue or dedicated crops (e.g. switchgrass), is milled and extracted with hot water to produce a mixture of lignin and sugars. Lipids are treated to introduce oxygen atoms into the fatty acids. These pretreated materials are subjected to catalytic conversion to produce bio-based chemicals. The catalysts are designed and synthesized with specific capabilities to produce targeted agri-based chemicals. The pretreatment and catalytic conversion steps are developed to demonstrate the technical feasibility of a continuous pretreatment/catalytic conversion technology platform for use in biorefineries.
Progress was made on all three objectives of this project with the goal to discover and develop commercially viable, value-added, biobased materials and conversion processes. The progress from this research supports ARS Strategic Plan (2012-2017) Goal 1.3.C, Develop non-food, non-fuel biobased products and sustainable technologies/processes and addresses National Program 306 (Quality and Utilization of Agricultural Products) Action Plan (2015-2019) Problem Statement 1.B) New bioactive ingredients and functional foods, Problem Statement 2.A.i) Increase or protect the market demand for [or increase the value of] existing U.S.-produced non-food biobased products derived from agricultural products and byproducts, and Problem Statement 2.B. Enable technologies (1) expanding market applications of existing biobased products, and (2) producing new marketable non-food biobased products derived from agricultural products and byproducts, and estimate the potential economic value of new products. Objective 1 • The synthesis of a novel series of medium chain length, medium to highly branched sulfur-containing fatty acid esters was scaled-up to produce quantities sufficient for application testing by collaborators as performance improving additives in vegetable oil-based and synthetic engine lubricants. • The improved photostability and efficacy of commercial ultraviolet-absorbing active ingredients used in retail cosmetic and personal care products was quantified when co-formulated with ARS’ patented and licensed vegetable oil-based biomaterial. • Identified more than 40 odd numbered fatty acids and more than 70 hydroxylated fatty acid acylglycerol molecular species from an edible mushroom from the Philippines. Collaborators are evaluating these acylglycerol molecule species for biological activities (e.g. antimicrobial, antifungal, and antitumor). Objective 2 • A novel encapsulating system using large liposomes inside giant liposomes has been developed and demonstrated to have controlled release of a biobased antioxidant. • A novel antioxidant lipid was synthesized and demonstrated to form spherical nanostructures with properties dependent on the ionic character. Objective 3 • An inexpensive catalyst was developed that effectively converts furfural to furfuryl alcohol. This catalyst differs from the commercially available catalysts in that it does not contain toxic chromium and has lower selectivity to the side product methylfuran. • More catalysts were screened for the conversion of xylose to the novel biobased compound 1,5-dihydroxypentanone. As the focus of biobased chemicals is shifting from drop-in replacements toward novel chemicals, this diol could become an attractive target for biorefineries looking to utilize xylose. • Corn cobs were treated with hot flowing water to produce a biomass-rich stream of chemical intermediates. This hydrolysate was treated with catalysts to produce 1,5-dihydroxypentanone and other important chemicals.
1. Lubricant additives from a modified dietary supplement. Establishing and growing a billion ton bioeconomy as a component of the U.S. economy requires the development of processes to convert sustainable agricultural commodities and materials to novel, higher value, non-food products with useful properties. ARS scientists in Peoria, Illinois, have developed a process using a solid acid catalyst to convert lipoic acid, a sulfur-containing, fatty acid dietary supplement, and various alcohols into vegetable oil soluble materials with good lubricant additive properties. Collaborators demonstrated the improved performance (e.g. peak oxidative temperature, four-ball extreme pressure, viscosity index) of both vegetable oil-based and synthetic lubricants when formulated with the lipoate materials. This technology expands the application of the existing dietary supplement, lipoic acid, from the health and personal care markets to new industrial markets.
2. Conversion of furfural to furfuryl alcohol. Non-food, non-fuel biobased products derived from renewable agricultural resources represent a small fraction of the market for petroleum-based industrial products. New and/or improved sustainable technologies and processes which facilitate the development of biobased products are needed to increase market share. ARS scientists in Peoria, Illinois, have demonstrated the conversion of the sugar-based compound from biomass, furfural, to the industrially valuable product furfuryl alcohol. While this conversion has been known for decades, the newly described process uses benign catalyst components that can replace the currently used chromium-based catalysts. This improved, more environmentally benign conversion process demonstrates that the industrial valuable chemical, furfuryl alcohol, can be produced from sustainable, domestically sourced biomass.
3. Bio-based antioxidants from vegetable oils. Food companies continuously look for methods to improve quality and shelf-life by limiting oxidation of fats and oils in food during storage to prevent deterioration. ARS scientists in Peoria, Illinois, demonstrated that bio-based ingredients enzymatically produced from soybean oil and olive oil have antioxidant properties and that these ingredients can be organized into hollow, spherical nanostructures to be used as delivery systems for oxidatively sensitive activities. This work demonstrates further suitability of combining antioxidants from agricultural waste with vegetable oil-based lipids to develop technologies that inhibit product degradation and improve storage to optimize product quality delivered to the consumer.
Compton, D.L., Evans, K.O., Appell, M. 2016. Experimental and theoretical study of the influence of water on hydrolyzed product formation during the feruloylation of vegetable oil. Journal of the Science of Food and Agriculture. 97(9):3022-3029. doi: 10.1002/jsfa.8145.
Evans, K.O., Compton, D.L. 2017. Phosphatidyl-hydroxytyrosol and phosphatidyl-tyrosol bilayer properties. Chemistry and Physics of Lipids. 202:69-76.
Compton, D.L., Goodell, J., Berhow, M.A., Kenar, J.A., Cermak, S.C., Evans, K.O. 2017. Feruloylated products from coconut oil and shea butter. Journal of the American Oil Chemists' Society. 94:397-411.
Dulay, R.M., Miranda, L.A., Malasaga, J.S., Kalaw, S.P., Reyes, R.G., Hou, C.T. 2016. Antioxidant and antibacterial activities of acetonitrile and hexane extracts of Lentinus tigrinus and Pleurotus djamour. Biocatalysis and Agricultural Biotechnology. 9:141-144.
Jackson, M.A., Blackburn, J.A., Price, N.P.J., Vermillion, K.E., Peterson, S.C., Ferrence, G.M. 2016. A one-pot synthesis of 1,6,9,13-tetraoxadispiro(188.8.131.52)tetradecane by hydrodeoxygenation of xylose using a palladium catalyst. Carbohydrate Research. 432:9-16. doi: 10.1016/j.carres.2016.06.003.
Finkenstadt, V.L., Bucur, C., Cote, G.L., Evans, K.O. 2017. Bacterial exopolysaccharides for corrosion resistance on low carbon steel. Journal of Applied Polymer Science. doi: 10.1002/app.45032.
Hou, C.T., Lin, J.T., Dulay, R.R., Ray, K.J. 2017. Identification of molecular species of acylglycerols of Philippine wild edible mushroom, Ganoderma lucidum. Biocatalysis and Agricultural Biotechnology. 9:19-27.
Vaughn, S.F., Kenar, J.A., Tisserat, B., Jackson, M.A., Joshee, N., Vaidya, B.N., Peterson, S.C. 2017. Chemical and physical properties of Paulownia elongata biochar modified with oxidants for horticultural applications. Industrial Crops and Products. 97:260-267.
Hou, C.T., Lin, J.T., Dulay, R.M., Ray, K.J. 2017. Identification of the molecular species of acylglycerols containing hydroxy fatty acids in wild edible mushroom Ganoderma lucidum. Biocatalysis and Agricultural Biotechnology. 10:411-419. doi:10.1016/j.bcab.2017.05.003.