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ARS Home » Midwest Area » Peoria, Illinois » National Center for Agricultural Utilization Research » Renewable Product Technology Research » Research » Research Project #427993

Research Project: Technologies for Producing Biobased Chemicals

Location: Renewable Product Technology Research

2018 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 Report
Progress was made on the three project objectives, all of which fall under National Program 306, Component 2.2, Product Quality and New Uses: Non-Food. Progress made on Objective 3 also contributed to National Program 306, Component 2.3, Product Quality and New Uses: Biorefining. The progress made this year focuses on Problem 2.B, the need to develop new, marketable, non-food, bio-based products and processes derived from agricultural products and byproducts and contributes to solving Problem 2.C, collaborating with production researchers to develop new crops and byproducts for conversion into non-food, biobased products. Under Objective 1.A, significant progress was made in evaluating the effectiveness of ARS patented soy-based active ingredients under conditions of use. In order to increase market penetration of the soy-based ingredients into the personal care and health and beauty industries, ARS scientists demonstrated that our soy-based ingredients have the same or better ultraviolet (UV) absorbing capacity, photostability, broad UV spectrum absorbance, and antioxidant capacity as commercially used, petroleum-based active ingredients. Results from this research are essential for end user evaluation of our soy-based ingredients for use in their products. Under Objective 1.B, progress was made to scale the microbial production of mono-, di-, and triacylglycerol polyols and fatty acid polyols from the microgram scale to 100-g scale. Microbial cultures (15) were screened and the fermentation conditions (e.g. culture medium, temperature, pH, time) continue to be optimized for the conversion of soybean oil to polyol oil products. The polyol products were determined to be unique in carbon chain length and hydroxyl group positioning on the fatty acid chains compared to polyol oils obtained through traditional chemical processes. These bio-based polyol oils produced using ARS technology can be used in industrial polymer chemistry, functioning as both building block chemicals and crosslinking agents for films, foams, coatings, and plastics. Progress with international collaborators indicates that some of the polyol oils may possess medicinal qualities as anti-diabetic, antimicrobial, anti-inflammatory, and antitumor agents. Under Objective 2, progress was made in optimizing and scaling up highly stable soy-based micellar encapsulation systems developed using ARS technology to deliver bio-based active ingredients for food and non-food applications. Physical characteristics of the lipid matrix systems (e.g. surface charge, pH, micelle size) were examined and optimized for encapsulation of model compounds for which controlled release can be studied by fluorescence spectrometry. Progress was also made in developing biobased, water insoluble, sugar polymers that aggregate into nanoparticles. The aggregation conditions (e.g. concentration, pressure, pH, temperature) and the physical characteristics (e.g. size, density, morphology) of the nanoparticles are being determined. The sugar particles are being investigated for their ability to encapsulate and deliver bioactive ingredients. Under Objective 3, significant progress was made in developing integrated pretreatment-thermochemical conversion processes to convert biomass into industrial chemicals. A method was developed and continues to be optimized for breaking down corn cobs with a thermochemical method and then converting the resultant chemical precursors with catalysts into a useful industrial building block chemical, hydroxypentanone. Progress was also made with collaborating producers of the new row crop, Cuphea, in developing a thermochemical method to covert its medium, carbon chain length see oil to fatty acid amines for use as mild, biobased surfactants in detergents. Related to Objective 1.B., progress was made on improving a process for converting polyol oils to conjugated, polyunsaturated fatty acids. Collaborators are making progress incorporating these modified fatty acids into pectin for use as nutraceutical ingredients. Progress was made with collaborators to evaluate a class of antibiotics called tunicamycins using solid acid catalysts to produce new antibiotics that are less toxic to mammals and more effective against pathogens.

1. Industrial chemicals from corn cobs. Falling farm incomes could be boosted by adding value to crop residues such as corn cobs and stover. Cobs are 15% of the weight of harvested corn so they represent a substantial potential resource stream for biorefineries and income stream for corn growers. ARS researchers in Peoria, Illinois, have developed a method to produce a unique industrial chemical using corn cobs collected during harvest. The carbohydrate mixture generated from pre-treated cobs are converted to hydroxypentanone using a thermochemical catalytic process. This compound possesses unique chemical functionality and has many potential industrial uses including as a polymer precursor and biofuel additive. Hydroxypentanone is currently produced using expensive, petroleum-based chemistries, and developing methods to produce it from corn cobs affords an opportunity to augment biorefinery profitability with an alternative, high value, non-fuel revenue stream while increasing the value of the corn producers waste byproduct.

2. Improved detection of fungal toxins in the food supply. Citrinin is a potential liver toxin and carcinogen produced by fungi that occasionally contaminate agricultural commodities, including corn and other grains. Citrinin detection is important to prevent exposure and remove contaminated commodities from the food supply. ARS researchers in Peoria, Illinois, discovered that certain surfactants can be used to enhance the fluorescence detection of citrinin. Experimental and computational methods were employed to improve the reliability of fluorescence detection methods of citrinin that are frequently applied to monitor citrinin contamination in grains. The chemical properties of citrinin were identified that influence the detection. These findings are important to scientists, the food industry, and regulators looking for more accurate and economical methods to detect citrinin contamination.

Review Publications
Jackson, M.A., White, M.G., Haasch, R.T., Peterson, S.C., Blackburn, J.A. 2017. Hydrogenation of furfural at the dynamic Cu surface of CuOCeO2/Al2O3 in vapor phase packed bed reactor. Journal of Molecular Catalysis. 445:124-132. doi: 10.1016/j.mcat.2017.11.023.
Price, N.P.J., Jackson, M.A., Vermillion, K.E., Blackburn, J.A., Li, J., & Yu, B. 2017. Selective catalytic hydrogenation of the N-acyl and uridyl double bonds in the tunicamycin family of protein N-glycosylation inhibitors. Journal of Antibiotics. 70:1122-1128. doi: 10.1038/ja.2017.141.
Appell, M., Evans, K.O., Compton, D.L., Wang, L.C., Bosma, W.B. 2018. Spectroscopic and time-dependent density functional investigation of the role of structure on the acid-base effects of citrinin detection. Structural Chemistry. 29(3):715-723.
Compton, D.L., Goodell, J.R., Evans, K.O., Palmquist, D.E. 2018. Ultraviolet absorbing efficacy and photostability of feruloylated soybean oil. Journal of the American Oil Chemists' Society. 95(4):421-431. doi: 10.1002/aocs.12047.
Vaughn, S.F., Dinelli, F.D., Kenar, J.A., Jackson, M.A., Thomas, A.J., Peterson, S.C. 2018. Physical and chemical properties of pyrolyzed biosolids for utilization in sand-based turfgrass rootzones. Waste Management. 76:98-105.
Bae, J.H., Kim, I.H., Lee, K.T., Hou, C.T., Kim, H.R. 2017. Molecular cloning and characterization of a novel cold-active lipase from Pichia lynferdii NRRL Y-7723. Biocatalysis and Agricultural Biotechnology. 11:19-25. doi: 10.1016/j.bcab.2017.05.008.
Elsayed, I., El Taweel, F., Mashaly, M., Jackson, M.A., Hassan, E.B. 2018. Dehydration of glucose to 5-hydroxymethylfurfural by a core-shell Fe3O4@SiO2-SO3H magnetic nanoparticle catalyst. Fuel. 221:407-416. doi: 10.1016/j.fuel.2018.02.135.
Lin, J.T., Hou, C.T., Dulay, R.M., Ray, K.J., Chen, G.Q. 2017. Structures of hydroxy fatty acids as the constituents of triacylglycerols in Philippine wild edible mushroom, Ganoderma lucidum. Biocatalysis and Agricultural Biotechnology. 12/148-151.
Dasagrandhi, C., Kim, Y.S., Kim, I.H., Hou, C.T., Kim, H.R. 2017. 7,10-Epoxyoctadeca-7,9-dienoic Acid: A small molecule adjuvant that potentiates ß-Lactam antibiotics against multidrug-resistant Staphylococcus aureus. Indian Journal of Microbiology. 57(4):461-469. doi: 10.1007/s12088-017-0680-2.