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ARS Home » Midwest Area » Peoria, Illinois » National Center for Agricultural Utilization Research » Plant Polymer Research » Research » Research Project #428704

Research Project: Conversion of Polysaccharides and Other Bio-based Materials to High-Value, Commercial Products

Location: Plant Polymer Research

2018 Annual Report

The overall goal is to produce novel bio-based materials from agricultural commodities to increase the market demand and value of U.S. non-food agricultural products and by-products, as well as to reduce the environmental impact from the plastics industry. Objective 1. Enable, from a technological standpoint, the commercial production of new bio-based polymers, graft-copolymers, composites, and blends from polysaccharides. Sub-Objective 1A. Selectively modify polysaccharides to provide higher product value using state-of-the-art, chemical methods and physical techniques, such as microwave, ultrasound, supercritical fluids, and on-line monitoring to produce materials suitable for coatings, personal care, food, and pharmaceutical applications. Sub-Objective 1B. Synthesize and evaluate bio-based polymers, polymer blends and polymer composites for environmentally responsive plastics, controlled release materials, and composite materials using industrial, continuous production methods such as extrusion.

Environmental concerns over the production and disposal of polymeric materials have prioritized the creation of new bio-based materials from agricultural feedstocks. Sustainable processing technologies are also needed to replace industrial and consumer products made from petroleum based feedstock. This project focuses on making bio-based polymeric materials with useful applications from agricultural products such as starch and associated low cost corn processing and harvesting co-products. Modified biopolymers with new properties will be prepared using the latest technologies available. Specific objectives for this project include: 1) Develop novel carbohydrate-based materials, such as starches, celluloses, and chitosan, with novel structures and/or through the use of microwaves, autoclave heating, reactive extrusion, jet cooking, and other green chemical methods; and 2) Demonstrate that the biobased polymeric materials can be used in high-value applications such as composite materials, packaging, controlled release devices, and environmental responsiveness. As an example, starch-based copolymers with novel and unique properties will be compounded by reactive extrusion, characterized, and processed into films or fibers and then evaluated for targeted properties and specific applications. Overall, this research will lead to bio-based polymer products with new or improved properties, have lower cost, are more environmentally friendly, and thus more acceptable to consumer markets. It will also generate new bio-based technologies enabling new market opportunities for agricultural products while reducing the environmental footprint relative to polymeric materials based on non-renewable resources.

Progress Report
Metal chloride catalyzed acetylation of starch. Acetylated starch is a useful product commonly catalyzed by strong mineral acids. This led to improving the synthesis of acetylated starch by using metal chlorides as catalysts. These catalysts are desirable as they will minimize the chemical hazards associated with using strong mineral acids. Took a more comprehensive look at several metal chlorides in order to observe trends and their chemical reactivities. Iodine was also included for comparison. Interestingly, a range of reactivities were obtained depending on the metal chloride chosen and the reaction conditions. Thus, it is possible to customize the reaction conditions as needed for a particular situation. This work would enable industrial chemical starch ester manufacturers to minimize chemical hazards by replacing strong mineral acids with metal chloride catalysts. Starch acetates are used for food additives, adhesives, and coating applications. Preparation and characterization of carboxymethyl cellulose films with embedded essential oils (EO). Producing food packaging materials that can increase the shelf-lives of fruits and vegetables, minimize food spoilage in supermarkets and, at the same time, not generate plastic waste that causes long-term disposal and environmental consequences are needed. One solution is to use edible and biodegradable packaging films based on polysaccharides, such as carboxymethyl cellulose (CMC). In this work, films were produced from two CMC materials with different degrees of substitution (DS) and encapsulated with four different essential oils (eugenol, rosemary oil, coriander oil, and nutmeg oil). These EO's are known to have antimicrobial properties. The mechanical properties, opacity, and water vapor permeation of the films were evaluated. This research is important as it presents a new generation of films which will benefit food packaging or edible film manufacturers and reduce plastic waste. A new biosensor for Salmonella Typhimurium detection in milk. Salmonella spp. is the major cause of food-borne diseases worldwide and its prevention is of high importance. An efficient amperometric biosensor for Salmonella Typhimurium detection was developed. The performance of this device is advantageous because it does not require a pre-enrichment step and takes a short time to obtain the results. This aspect is very important for food suppliers that need constant monitoring of food quality. The applicability of this method in milk samples was proven with skim and whole milk. This research will help the food industry, especially those who can be potentially affected by Salmonella. Permeability studies were conducted for amylopectin/poly(lactic acid) packaging materials to determine the rates of diffusion and thus the release of essential oils, primarily cinnamaldehyde. Diffusion rates in and out of the films will impact the antimicrobial activity when in contact with food products. Poly(lactic acid) (PLA) was combined with waxy corn starch (100% amylopectin) or hydroxypropyl waxy corn starch and then impregnated with cinnamon essential oil (75% cinnamaldehyde). Cinnamon EO was chosen because of its low cost and availability. The derivative starch provides more interaction with the matrix polymer which affects the release rates of the blend. The release rate for neat PLA was much slower than either blend. In the case of packaging for fresh food products, however, a quicker release is needed to control food-borne pathogens. Blending PLA with waxy corn starch or hydroxypropyl waxy corn starch changed the release rates by providing more surface area and sequestering the EO at higher concentrations into the PLA-starch interface which allows release into the atmosphere. Over the first 5 days, around 50% of the EO was released from the polymer blends. In contrast, neat PLA released only 25%. Over the next 25 days, the diffusion slowed down. After 30 days, the blends retained approximately 25% of the EO. In the case of starch-based materials, atmospheric moisture (water) must be taken into account. Water absorption and desorption (hysteresis) was measured and compensated for the calculations.

1. Biodiesel as a natural renewable starting material for polymers. Biodiesel is increasingly being used as diesel fuel and heating oil, especially in Europe. Because of its availability and favorable environmental friendliness, it may be useful as a renewable starting material for new polymers. Modified it chemically by adding an epoxy group and reacted with epoxidized soybean oil to get polymers that ranged from liquids to solids. These polymers may find applications as lubricants, elastomers, coatings, etc.

2. Microwave-assisted synthesis of sucrose polyurethanes and their network with polycaprolactone and soybean oil. Because of the current interest in sustainability, environmental stewardship, and green chemistry, there has been a lot of interest in using agro-based raw materials for the design of polymeric materials. One of the most promising bio-renewable materials is sucrose, which is inexpensive and widely available. ARS scientists in Peoria, Illinois, have found that microwave-assisted synthesis significantly decreased the reaction time and saved energy relative to conventional heat in order to produce sucrose polyurethanes. The toluene diisocyanate (TDI)/sucrose ratios were determined in order to give the molecular weight and thermal properties needed for a given application. The chemical structures of the sucrose polyurethanes produced from conventional heat and from microwave were similar. The research also showed that the sucrose polyurethane is a convenient medium to produce semi-interpenetrating polymer networks (IPNs), demonstrated by successful incorporation of poly(lactic acid) and soybean oil into sucrose polyurethanes. It may be noted that the final materials are biodegradable and eco-friendly. Other semi-IPN’s involving different polymers may be made in a similar fashion. The novel processes disclosed in this work will benefit industrial chemical manufacturers by saving time and energy during the production of polyurethanes.

3. Microwave-assisted extraction of soluble sugars non-starch polysaccharides from banana puree with natural deep eutectic solvents (NADES). Over-ripe or rejected bananas serve as a good source for non-starch polysaccharides (NSP), which can be used as functional food ingredients and represent an opportunity for waste utilization. However, NSP contains a large amount of sugars that are undesirable and need to be removed. Traditional extraction methods using alcohol solvents have many drawbacks. This study conducted by ARS scientists in Peoria, Illinois, demonstrated that judicious mixtures of selected components can form natural deep eutectic solvents (NADES) at optimal ratios at a certain temperature range. Despite high viscosity, all NADES evaluated were liquids at room temperature. The physiochemical properties can be tailored in a controllable way when diluted with water. This work also shows the advantage of using the combination of NADES and microwave extraction as a useful method for food fragrance and flavor manufacturers to extract soluble sugars from fruits like bananas. The novel processes disclosed in this work will benefit industries by enabling them to extract fragrance and flavor selectively and faster from fruits in a more energy efficient way.

4. Release rates of active ingredient for antimicrobial packaging. The purpose of this work was to develop and study the effect of bioactive components towards the inhibition of microbial activities of food packaging films for foods that are extremely vulnerable to microbial growth, or directly used as a surface coating on perishable fruits and vegetables consecutively to augment their microbial safety and extend shelf stability of food products. This area of research holds considerable potential on food delivery systems. ARS scientists in Peoria, Illinois, combined polymer blends using poly(lactic acid) and corn starch with cinnamon essential oil (EO). The EO content was 12-18% depending on the blend. In the first 5 days of use, approximately 50% of the cinnamon essential oil (75% cinnamaldehyde) is released from the packaging. The release slows down during the next 25 days. After 30 days, approximately 25% of the EO is retained in the packaging. This new packaging will address the need to reduce or eliminate food-borne pathogens in fresh food products while adding a flavor/odor component to enhance the product.

Review Publications
Boddu, V.M., Costales-Nieves, C., Damavarapu, R., Viswanath, D.S., Shukla, M.K. 2017. Physical properties of select explosive components for assessing their fate and transport in the environment. In: Shukla, M.K., Boddu, V.M., Steevens, J.A., Damavarapu, R., Leszczynski, J., editors. Energetic Materials: From Cradle to Grave. Cham, Switzerland: Springer. p. 343-371.
Boddu, V.M., Viswanath, D.S., Ghosh, T.K. 2018. Emerging Energetic Materials: Synthesis, Physicochemical, and Detonation Properties. Dordrecht: Springer. 478 p.
Biswas, A., Kim, S., Gomez, A., Buttrum, M.A., Boddu, V.M., Cheng, H.N. 2018. Microwave-assisted synthesis of sucrose polyurethanes and their semi-interpenetrating polymer networks with polycaprolactane and soybean oil. Industrial and Engineering Chemistry Research. 57: 3227-3234.
Kim, S., Adkins, J.E., Biswas, A. 2017. Reinforcement of latex rubber by the incorporation of amphiphilic particles. Journal of Rubber Research. 20(2):87-100.
Liu, Z., Biresaw, G., Biswas, A., Cheng, H.N. 2018. Effect of polysoap on the physical and tribological properties of soybean oil-based grease. Journal of the American Oil Chemists' Society. 95(5):629-634.
Oliveira, M.A., Furtado, R.F., Bastos, M.R., Benevides, S., Leitao, R.C., Muniz, C.R., Biswas, A., Cheng, H.N. 2018. Performance evaluation of cashew gum and gelatin blend for food packaging. Journal of Food Packaging and Shelf Life. 17:27-64.
Biswas, A., Liu, Z., Furtado, R., Alves, C.R., Cheng, H.N. 2017. Novel polymeric products derived from biodiesel. In: Cheng, H.N., Maryanoff, C.A., Miller, B.D., Schmidt, D.G., editors. Stereochemistry and Global Connectivity: The Legacy of Ernest L. Eliel Volume 2. ACS Symposium Series 1258. Washington, DC: American Chemical Society. p. 207-220.
Kim, S., Biswas, A., Boddu, V.M., Hwang, H., Adkins, J.E. 2018. Solubilization of cashew gum from Anacardium Occidentale in aqueous medium. Carbohydrate Polymers. 199:205-209.
Alesandre, D.L., Melo, A.A., Furtado, R.F., Borges, M.F., Figueiredo, E.T., Biswas, A., Cheng, H.N., Alves, C.R. 2018. A rapid and specific biosensor for Salmonella typhimurium detection in milk. Food and Bioprocess Technology. 11(4):748-756.
Hojilla-Evangelista, M.P., Sutivisedsak, N., Evangelista, R.L., Cheng, H.N., Biswas, A. 2018. Composition and functional properties of saline-soluble protein concentrates prepared from four common dry beans (Phaseolus vulgaris L.). Journal of the American Oil Chemists' Society. 95:1001-1012. doi: 10.1002/aocs.12135.