Progress 07/01/08 to 06/30/10
Outputs
Progress Report Objectives (from AD-416) Scale up of ARS� proprietary purification process. Develop a biodegradable zein-based injection molded bioplastic for use in credit cards and products for human and/or food contact. Develop a zein based film for food and pharmaceutical packaging. Develop zein-based paper coating for fast food packaging. Develop NMR method for distinguishing native and denatured zein. Approach (from AD-416) All work under this CRADA will be performed using proprietary zein provided by GPP. Scale-up of the zein purification process will be based on the use of molecular sieves and zeolite resins, alone or in combination with activated carbon, based on U.S. Patent Application SN 11/728,700. Efficiency, optimization and economics of operation will be investigated to stream-line the pilot scale process for commercial scale production. Melt blending of zein with synthetic biodegradable polyesters such as polycaprolactone, polybutylene succinate, polylactic acid will be investigated to enhance the flow properties and the ductility of zein based bioplastics and packaging materials to be subjected to injection molding and film blowing. Other melt blending reaction chemistries will involve either chain lengthening zein with carbodiimide or mild cross linking zein with glutaraldehyde, dimethyl suberimidate dihydrochloride, dialdehyde starch, succinic acid derivatives known to react with primary amines, or isocyanate derivatives known to react with hydroxyl groups to enhance tensile strength and ductility. Formulations of those bioplastics will be evaluated for use in credit cards and injection molded plastic for human and/or food contact. Melt processing using glyoxal and base (U.S. Patent Application SN 11/893,463) developed by ARS will NOT be used in this CRADA. Film blown zein products will be adapted for food and pharmaceutical packaging. Zein emulsions and zein composites or blends with polysaccharides, inorganic and organic components will be evaluated as paper coatings for fast food packaging. Spray, dipped applications and roller coatings processing techniques will be applied. Physical evaluations of coatings for conductivity, surface activity, adhesion characteristics and resistance to grease and creasing will be investigated. An NMR method involving hydrogen/deuterium exchange will be used to provide detailed information on the structural and functional differences between native and denatured zein protein. 1) Scale-up of the zein purification process involves use of three 4� x 5� columns packed with Zeolite 5A and a fourth column packed with an activated carbon hard enough to withstand a flow rate of 4gal/min. Coconut hull carbon or extruded plant material carbon proved satisfactory with limited breakdown or erosion of the carbon. Zein produced from DDG (dry milled ethanol process) was found to possess high amounts of �-zein which leads to gelation. �-zein can be removed by the pilot process. However, that component fouls the Zeolite packing. On the other hand, Freeman zein produced from corn gluten meal, generated from wet milled ethanol process, possesses only trace amounts of �-zein. That commercial zein with 88-90% protein will yield a 100% pure protein product. Depending on the purity of the starting product, recovered yield of high purity a-zein can vary from 45-70%. Column media can be regenerated by flushing with ethanolic acid or base. 2) Methodologies to determine zein purity from the column filtration process involves a combination of UV and visible spectroscopies, FTIR, and SDS-PAGE. The ratio of 280nm/325nm is used to assess removal of odor causing components, visible spectra at 450nm measures removal of yellow color, subtle shifts of wavenumbers attributed to Amide I, Amide II and Amide III and ratios of their peaks can be used to establish purities of zein samples. Circular dichroism confirmed FTIR data that demonstrated high helical content of the a-zein species in the highly purified zein product. 3) Freeman zein that was melt-processed on a single screw extruder with polyvinylpyrrolidones of varying molecular weights from 55K to 1.3M forms a compatible blend where compatibility was based on results from thermal analyses and morphology by SEM. Extruded material was ground and compression molded into tensile bars. Mechanical properties of tensile bars stored at 50% RH showed small to moderate increases in tensile strength and % elongations. Bars stored at 70% RH showed diminished tensile strength and an increase in elongation by 10-15%. This compatible blend of zein with a variety of molecular weight polyvinylpyrrolidones is a new finding of high impact. This combination can be used as a building block to generate a new series of bio-based polymers from zein. For example, zein that is melt-processed with a combination of polyvinylpyrrolidones and 5% of the nanoclay, Cloisite Na+, will generate a blend that showed a 10-15% increase in tensile strength. The Authorized Departmental Officer's Designated Representative monitored progress through the annual progress report.
Impacts
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Progress 10/01/08 to 09/30/09
Outputs
Progress Report Objectives (from AD-416) Scale up of ARS� proprietary purification process. Develop a biodegradable zein-based injection molded bioplastic for use in credit cards and products for human and/or food contact. Develop a zein based film for food and pharmaceutical packaging. Develop zein-based paper coating for fast food packaging. Develop NMR method for distinguishing native and denatured zein. Approach (from AD-416) All work under this CRADA will be performed using proprietary zein provided by GPP. Scale-up of the zein purification process will be based on the use of molecular sieves and zeolite resins, alone or in combination with activated carbon, based on U.S. Patent Application SN 11/728,700. Efficiency, optimization and economics of operation will be investigated to stream-line the pilot scale process for commercial scale production. Melt blending of zein with synthetic biodegradable polyesters such as polycaprolactone, polybutylene succinate, polylactic acid will be investigated to enhance the flow properties and the ductility of zein based bioplastics and packaging materials to be subjected to injection molding and film blowing. Other melt blending reaction chemistries will involve either chain lengthening zein with carbodiimide or mild cross linking zein with glutaraldehyde, dimethyl suberimidate dihydrochloride, dialdehyde starch, succinic acid derivatives known to react with primary amines, or isocyanate derivatives known to react with hydroxyl groups to enhance tensile strength and ductility. Formulations of those bioplastics will be evaluated for use in credit cards and injection molded plastic for human and/or food contact. Melt processing using glyoxal and base (U.S. Patent Application SN 11/893,463) developed by ARS will NOT be used in this CRADA. Film blown zein products will be adapted for food and pharmaceutical packaging. Zein emulsions and zein composites or blends with polysaccharides, inorganic and organic components will be evaluated as paper coatings for fast food packaging. Spray, dipped applications and roller coatings processing techniques will be applied. Physical evaluations of coatings for conductivity, surface activity, adhesion characteristics and resistance to grease and creasing will be investigated. An NMR method involving hydrogen/deuterium exchange will be used to provide detailed information on the structural and functional differences between native and denatured zein protein. Significant Activities that Support Special Target Populations Fourier Transform Infrared (FTIR) spectroscopy of zein samples with varying levels of purity in combination with circular dichroism of those samples proved to be accurate methods to determine relative protein purity. Zein that was melt processed with polyvinylpyrrolidones (PVPs) of different molecular weights produced composites that exhibited 10% increases in tensile strength over that of zein controls, which findings suggest compatibility of zein/PVP blends. A pilot scale process (patent pending) using a multi-columnar system packed with combination of zeolites (clay) and activated carbon proved successful for purifying commercial yellow zein to generate a white product with no odor and little yellow coloration. The Authorized Departmental Officer's Designated Representative monitored the activities of this agreement via phone calls, e-mails, and meetings.
Impacts
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