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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

2020 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
This is the final report for this project which terminated April 2020. See the report for the replacement project, 5010-41000-184-00D. “Technologies for Producing Marketable Bioproducts,” for additional information. Progress was made on the three project objectives, all of which fall under National Program 306, Component 2, Quality and Utilization of Agricultural Products: Non-Food. Under Objective 1, significant progress was made to enable commercially viable enzymatic and chemical processes to produce commercial products from vegetable oils. Progress was made in development of the enzymatic, bioreactor production of two compounds that are found naturally in plants in very low quantities. These natural compounds, feruloyl glycerol and diferulyol glycerol, are known to have antioxidant, ultraviolet absorbing, and potential antimicrobial activities that would be useful in the personal care and agricultural industries if they can be produced in large enough quantities. The natural compounds were produced, characterized, and isolated using a newly developed method on larger scales and in higher purity than previously reported when isolated from plants. The compounds were enzymatically made from a natural plant component and vegetable oil glycerol and are currently being tested for antioxidant capacity, total ultraviolet absorbance capacity, insecticide activity, and antifungal activity. Under Objective 2, significant progress was made to enable new commercial encapsulation systems for controlled release of bioactive molecules. A new encapsulation system was made from a polysaccharide enzymatically synthesized using microbes. The natural polysaccharide was shown to form an encapsulation system through a homogenization process and remained highly stable for several months. The polysaccharide encapsulation particles were produced at liter-sized batches. Combining the polysaccharide with phytochemically modified vegetable oil showed great promise as a distinct encapsulation system with unique properties. Additionally, the phytochemically modified vegetable oil itself was shown to form a stable encapsulation system. Currently, all three encapsulation systems are being tested for controlled release of bioactives. Under Objective 3, significant progress was made in developing chemocatalytic conversion processes to convert crop residues and new row crops to industrial chemicals. Several catalysts were tested and the most efficient identified for converting the seed oil of new row crop Cuphea into biobased, sustainable surfactants. Direct conversion of corn cobs to marketable products was shown to be a promising approach to new marketable compounds; the 1-hydroxy-2-pentanone was prepared in high yield in terms of kg of compound per acre of corn. This compound was readily converted to 1,2-dihydroxypentane, which is used in cosmetics and is sold under the common name pentylene glycol. Over the lifetime of the project, commercially viable enzymatic processes were developed to produce new, naturally based commercial products from vegetable oils. Pilot-scale bioreactor methods were developed to produce soybean oil and coconut oil derivatives that are currently used as active ingredients in personal care products. These efforts included developing analytical methods and protocols to identify, characterize, and assess the efficacy of the biobased vegetable oil derivatives. More than three dozen functionalized acylglycerols and fatty acids compounds from vegetable oils such as, soybean, mushroom, castor were microbially produced in up to liter fermentations. The isolated and characterized functionalized acylglycerols and fatty acids were evaluated and several showed promising antimicrobial, antifungal, and antitumor activities for use in pharmaceutical and agricultural applications. The vegetable oil based bioproducts developed under this objective has provided marketable alternatives to petroleum-based chemical products and have expanded the use of agrimaterials into non-traditional markets and industries. A lipid-based system (liposome) was demonstrated to readily encapsulate vegetable oil-based antioxidant active ingredients used in personal care and nutraceutical applications. Methods were demonstrated to combine olive oil antioxidant ingredients with soybean oil resulting in a biobased antioxidant lipid that formed a spherical encapsulation system with antioxidant capability. An encapsulation system made of natural lipids which was comprised of large liposomes inside of giant liposomes was determined to be capable of controlled release of a single bioactive ingredient. Natural water-insoluble sugar polymers were converted into a long-term stable encapsulation system. Combining the water-insoluble sugar polymers with feruloyl soy glyceride, a soybean oil derivative, formed an ultraviolet-absorbing encapsulation system. Water-soluble sugar polymers from frost grapevines and feruloyl soy glyceride were demonstrated to form individual encapsulation systems with great potential of high stability for use in pharmaceutical and agricultural applications. In cooperation with an industry partner, the production of the antibiotic tunicamycin at a commercially relevant scale has been achieved. As isolated, tunicamycin is an antibiotic that enhances the antimicrobial activity of penicillins, but it is too toxic to be used clinically; however, methods were developed to convert tunicamycin to a safer version for clinical use. Chemocatalytic technology was selected to modify tunicamycin into a less toxic derivative that still retains its antimicrobial action. This conversion of tunicamycin to a derivative known as TunR2 has also been achieved at commercial scale. This has allowed for the expansion of ARS research into the use of TunR2 to address other agricultural problems. ARS colleagues are testing the tunicamycin derivatives against the causative agents of some specific animal and plant diseases. Real progress was made in the catalytic conversion of agricultural residues to new and useful chemicals. Xylose from corn cob was converted to two different compounds depending on reaction conditions. Furfural, which can be made from xylose, was efficiently converted to furfuryl alcohol using an inexpensive copper catalyst, and 2-undecanone prepared from Cuphea seed oil was shown to be amenable to reductive amination chemistry leading to new biobased surfactant molecules.

1. New biobased surfactants from sugars and seed oils. Much of the projected growth in food and non-food markets is driven by consumer demand for more natural, plant-based ingredients and products. Surfactants are surface-acting agents that are essential in many consumer products and are made by combining two chemical components, one that can dissolve in water (water soluble) and one that can dissolve in oil (oil soluble). ARS researchers in Peoria, Illinois, have developed new, biobased surfactants made from sugars and vegetable oils. A process was established to catalytically combine modified sugars (water soluble) with fatty acid groups made from Cuphea seed oil (oil soluble) to form biobased surfactants. These new compounds were shown to be effective in inhibiting microbial growth, forming foams, making micelles and can be used as ingredients in shampoos, detergents, pharmaceuticals, paints, foods, agricultural spray adjuvants, and soil remediation projects. The biobased surfactants have the potential to provide marketable alternatives to petroleum-based chemical surfactants and expand the use of the new crop Cuphea into non-traditional markets and industries.

2. Using artificial intelligence (AI) to identify agri-based antifungals. Antifungal compounds are often a strategy to reduce exposure to molds and toxins produced by fungi that sometimes contaminate agricultural commodities such as corn; however, resistance against commonly used fungicides has become a concern. Using artificial intelligence and self-improving computer modeling, ARS researchers in Peoria, Illinois, have developed software models to predict the antifungal properties of plant-based compounds (phenolics), including compounds related to phenolic vegetable oils and essential oils. This study identified the chemical properties of common, plant-based phenolic compounds to reduce the contamination of toxins produced by fungal contaminants. These models serve as convenient, cost effective tools to screen potential antifungal compounds without the need of costly lab testing. The information obtained from this study will guide the development of novel agriculturally derived bioproducts with uses as antifungal agents to reduce exposure to the effects of fungal ear molds that produce toxins in corn that are harmful to people and animals.

Review Publications
Compton, D.L., Appell, M. 2020. Rapid Raman spectroscopic determination of 1-feruloyl-sn-glycerol and 1,3-diferuloyl-sn-glycerol. Spectrochimica Acta. 229:118020.
Compton, D.L., Appell, M., Kenar, J.A., Evans, K.O. 2020. Enzymatic synthesis and flash chromatography separation of 1,3-diferuloyl-sn-glycerol and 1-feruloyl-sn-glycerol. Methods and Protocols. 3(1):8.
Compton, D.L., Evans, K.O., Appell, M., Goodell, J.R. 2019. Protection of antioxidants, vitamins E and C, from ultraviolet degradation using feruloylated vegetable oil. Journal of the American Oil Chemists' Society. 96(9):999-1009.
Price, N.J.P., Jackson, M.A., Singh, V., Hartman, T.M., Dowd, P.F., Blackburn, J.A. 2019. Synergistic enhancement of beta-lactam antibiotics by modified tunicamycin analogs TunR1 and TunR2. Journal of Antibiotics. 72(11):807-815.
Elsayed, I., Jackson, M.A., Hassan, E. 2019. Hydrogen-free catalytic reduction of biomass-derived 5-Hydroxymethylfurfural into 2,5-bis(hydroxymethyl)furan using copper-iron oxides bimetallic nanocatalyst. ACS Sustainable Chemistry & Engineering. 8(4):1774-1785.
Hay, W.T., Fanta, G.F., Rich, J.O., Evans, K.O., Skory, C.D., Selling, G.W. 2020. Antimicrobial properties of amylose-fatty ammonium salt inclusion complexes. Carbohydrate Polymers. 230: 115666.