Research Project: Technologies for Producing Biobased Chemicals

Location: Renewable Product Technology Research

2016 Annual Report

Objectives
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.

Approach
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 Report
The Objectives of this project, “Technologies for Producing Biobased Chemicals,” are: 1) Enable, from a technological perspective, commercially-viable microbial, enzymatic, and chemical processes to produce commercial products from vegetable oils; 2) Enable new commercial encapsulation systems for controlled-release of bioactive molecules; and 3) Enable new commercial processes for the production of industrial chemicals from vegetable oils or lignocellulosics. During the first 12 months of the project, ARS scientists in Peoria, Illinois, have made the following progress toward these objectives: Objective 1 • A family of 10 short to medium, linear to highly branched chained lipoic acid esters were synthesized and characterized and their physical properties tested in natural vegetable oils and synthetic oils used for engine lubricants. • A novel, coconut oil-based material modified with a lignin component was developed for commercial production. The material possesses excellent ultraviolet absorbing and antioxidant properties for use in the personal care industry. • A microbial strain of Pseudomonas was identified that produces unique fatty acid and acyl glycerol species. • Gram quantities of lipid fractions from native Philippine, medicinal mushrooms were isolated and the lipid and fatty acid species determined by collaborators. Objective 2 • Biobased antioxidants made from commodity vegetable oils modified with lignin components are being tested for their general ability to scavenge free radicals and their abilities to prevent chemical damage caused by different classes of free radicals in liposomal systems. • A novel encapsulating system using large liposomes inside giant liposomes was developed, and is being studied as a controlled release mechanism for biobased antioxidants and active ingredients. Objective 3 • A pretreatment method for the conversion of switchgrass to biobased chemicals has been developed. Hot water extraction allows for 75% of the starting weight of milled switchgrass to be readied for conversion to useful chemicals when treated with hydrogen over select catalysts.

Accomplishments
1. Bio-based, commodity chemicals from biomass. Farm field residues and dedicated crops hold great potential as sources of industrial chemicals. ARS scientists in Peoria, Illinois, have improved a method for using biomass to manufacture bio-based chemicals. A one-pot reaction has been developed that converts the sugar xylose to a novel, oxygen-rich compound in good yields, which can be used for making polymers. The importance in using xylose as a starting material lies in its origin in hemicellulose. Hemicellulose is a large portion of crop residue, so its utilization can add value to both field residue and dedicated crops.

2. Personal care ingredients from vegetable oils. To establish a bio-economy that can displace petroleum-based products, new processes and materials must be developed to convert sustainable, agricultural commodities to new, higher value materials with useful properties. ARS scientists in Peoria, Illinois, have expanded upon their patented enzymatic process to convert vegetable oils into higher-value, skin care ingredients. Commercial partners are manufacturing coconut oil-based compounds modified with a component of lignin to be sold as a high-value skin care active ingredient with antioxidant and broad ultra violet absorbing properties. This work directly contributes to ARS’ efforts to create new and expanded markets for agricultural commodities and to combat climate change by reducing our dependence on petroleum for the manufacture of industrial chemicals.

3. Lipid systems (liposomes) for delivering bio-based active ingredients. Companies continuously look for natural ingredients with the potential of delivering protective and energizing activity for improving health and appearance. ARS scientists in Peoria, Illinois, demonstrated vegetable oil-based antioxidant active ingredients can be incorporated into liposomal systems and maintain their antioxidant properties. These active ingredient-infused liposomal systems can be further encapsulated and used to deliver and enhance the controlled release of the active ingredients in personal care and nutraceutical applications. This work directly contributes to ARS’ efforts to create new and expanded markets for agricultural commodities and to combat climate change by reducing our dependence on petroleum for the manufacture of industrial chemicals.

None.

Review Publications
Ro, K.S., Lima, I.M., Reddy, G.B., Jackson, M.A., Gao, B. 2015. Removing gaseous NH3 using biochar as an adsorbent. Agriculture. 5:991-1002. doi: 10.3390/agriculture5040991.
Elkasabi, Y.M., Mullen, C.A., Jackson, M.A., Boateng, A.A. 2015. Characterization of fast-pyrolysis bio-oil distillation residues and their potential applications. Journal of Analytical and Applied Pyrolysis. 114:179-186.
Jackson, M.A., Appell, M., Blackburn, J.A. 2015. Hydrodeoxygenation of fructose to 2,5-dimethyltetrahydrofuran using a sulfur poisoned Pt/C catalyst. Industrial and Engineering Chemistry Research. 54(28):7059-7066. doi: 10.1021/acs.iecr.5b00766.
Lindquist, M.R., Lopez-Nunez, J.C., Jones, M.A., Cox, E.J., Pinkleman, R.J., Bang, S.S., Moser, B.R., Jackson, M.A., Iten, L.B., Kurtzman, C.P., Bischoff, K.M., Liu, S., Qureshi, N., Tasaki, K., Rich, J.O., Cotta, M.A., Saha, B.C., Hughes, S.R. 2015. Irradiation of Yarrowia lipolytica NRRL YB-567 creating novel strains with enhanced ammonia and oil production on protein and carbohydrate substrates. Applied Microbiology and Biotechnology. 99(22):9723–9743.
Elkasabi, Y.M., Boateng, A.A., Jackson, M.A. 2015. Upgrading of bio-oil distillation bottoms into biorenewable calcined coke. Biomass and Bioenergy. 81:415-423.
Doll, K.M., Walter, E.L., Bantchev, G.B., Jackson, M.A., Murray, R.E., Rich, J.O. 2016. Improvement of lubricant materials using ruthenium isomerization. Chemical Engineering Communications. 203(7):901-907.
Evans, K.O., Compton, D.L., Whitman, N.A., Laszlo, J.A., Appell, M., Vermillion, K.E., Kim, S. 2015. Octadecyl ferulate behavior in 1,2-dioleoylphosphocholine liposomes. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 153:333-343. doi: 10.1016/j.saa.2015.08.009.
Evans, K.O., Compton, D.L., Laszlo, J.A., Appell, M. 2015. Feruloyl glycerol and 1,3-diferuloyl glycerol antioxidant behavior in phospholipid vesicles. Chemistry and Physics of Lipids. 195:1-11. doi: 10.1016/j.chemphyslip.2015.11.001.
Kenar, J.A., Compton, D.L., Little, J.A., Peterson, S.C. 2016. Formation of inclusion complexes between high amylose starch and octadecyl ferulate via steam jet cooking. Carbohydrate Polymers. 140:246-252.
Biresaw, G., Compton, D., Evans, K., Bantchev, G.B. 2016. Lipoate ester multifunctional lubricant additives. Industrial and Engineering Chemistry Research. 55(1):373-383.
Johnson, E.T., Evans, K.O., Dowd, P.F. 2015. Antifungal activity of a synthetic cationic peptide against the plant pathogens Colletotrichum graminicola and three Fusarium species. Plant Pathology Journal. 31(3):316-321.
Appell, M., Jackson, M.A., Wang, L.C., Bosma, W.B. 2015. Determination of citrinin using molecularly imprinted solid phase extraction purification, HPLC separation, and fluorescence detection. Journal of Liquid Chromatography and Related Technologies. 38(20):1815-1819.
Dulay, R.M.R., Ray, K., Hou, C.T. 2015. Optimization of liquid culture conditions of Philippine wild edible mushrooms as potential source of bioactive lipids. Biocatalysis and Agricultural Biotechnology. 4(3):409-415. doi: 10.1016/j.bcab.2015.04.003.
Hou, C.T., Lin, J.T., Ray, K. 2015. Identification of molecular species of polyol oils produced from soybean oil by Pseudomonas aeruginosa E03-12 NRRL B-59991. Biocatalysis and Agricultural Biotechnology. 4(4):500-505. doi: 10.1016/j.bcab.2015.08.017.