Progress 09/01/05 to 08/31/09
Outputs
OUTPUTS: A presentation was made to academic and industrial colleagues at the Starch Round Table, September 11, 2009 in Baltimore, MD. A presentation was made to the Annual Grantees' Workshop, September 27, 2009 in Santa Fe, NM. The technology was discussed at a nanotechnology commercialization workshop held September 23, 2008 and at National Starch and Chemical Co. on October 6, 2008. An invited presentation was made at the 9th International Hydrocolloids Conference held June 15-19, 2008 in Singapore. Two seminars were presented at Kasetsart University, Bangkok, Thailand June 10-15, 2008. Information was also disseminated informally at the 2007 Starch Round Table, sponsored by the American Association of Cereal Chemists held in San Antonio, TX, October 4-6, 2007, and at the 2nd International Symposium on the Delivery of Functionality in Complex Food Systems. Results of the study were reported at the NRI 75.0 Grantees' Workshop, September 20-21, 2008 at the University of California-Davis, Davis, CA. These results have been disseminated at numerous venues including: the 8th International Hydrocolloids Conference in Trondheim, Norway (2006), the American Physical Society (2006), Institute of Food Technologists Annual Meetings (2006, 2007), as well as, the annual grantees workshops (2006, 2007). Seminars on the topic were presented at Kansas State University (2006), Iowa State University (2006), Procter and Gamble Company (2006) and National Starch and Chemical Company (2007). One Ph.D. student, J.A. Creek, was graduated in 2007. PARTICIPANTS: Dr. Greg Ziegler served as project director and immediate research supervisor. Dr. Rajesh Bhosale completed one year as a post-doctoral research associate on this project, taking over for Dr. John Creek who graduated with his Ph.D. in 2007. Dr. Jim Runt, Professor of Materials Science and Engineering at Penn State continues to serve as co-PI. During this project we collaborated with National Starch LLC and Dr. Rangrong Yoksan of Kasetsart University in Bangkok, Thailand who completed a brief sabbatical at Penn State summer of 2009. The project has supplied training opportunities to Ms. Kolika Chatterjee, Nuttanit Suwanayuen, and Srilatha Chittiprolu all who completed the M.S. degree. Erica Moore, Ph.D. candidate in MatSE at PSU and Erica Marden, honors student in MatSE at PSU have both contributed to and benefited from involvement in this project. TARGET AUDIENCES: The immediate target audience is the scientific community involved in starch research, including both academic and industrial scientists, businesses manufacturing starch-based materials, and food technologists in general. If the research is successfully commercialized, the target audience would be the general population. During the project period, the PIs met with industry representatives interested in novel non-food uses of starch polymers including Teijin Ltd and Metabolix, Inc. (Telles). Additionally, the potential for use of starch spherulites for controlled release has been discussed with representatives of Wm Wrigley. PROJECT MODIFICATIONS: Due to the graduation of John Creek midway through the project, and the need to hire a replacement, a no-cost extension was requested and approved for this project.
Impacts
Among the anticipated outcomes of this research was the development of new food ingredients and novel systems for the controlled release of flavors, fragrances or pharmaceuticals. This research has laid the foundation knowledge on which a new platform in starch technology can be built. Though not complete, sufficient basic knowledge has been discovered to begin a developmental stage. Furthermore, the fundamental research results on amylose crystallization have had an unanticipated impact on the commercialization of non-food starch materials. Technology transfer is on-going, and the further development of commercial products is expected. This project has led to a better understanding of spherulitic crystallization in starch and its relationship to starch granule initiation in vivo, the mechanism of which is still a mystery. With the phase diagrams roughly sketched out, process development and scale-up has begun. The product of such a process may be used as a novel delivery system for active ingredients such as drugs, flavors, fragrances, etc, or as a new texturizing agent for the food and cosmetics industries. The research group, including both PIs, have met with starch industry representatives to present the results of this research and discuss its commercial potential. As an example of the relevance of this project, Tate & Lyle, a major starch producer, recently filed for patent protection for an enzyme resistant starch product in spherulitic form. If commercialized, starch spherulites would contribute to improved human health.
Publications
- Bhosale, R.G. and G.R. Ziegler. 2009. Preparation of spherulites from amylose-palmitic acid complexes. Carbohydrate Polymers. http://dx.doi.org/10.1016/j.carbpol.2009.10.069
- Lay-Ma, U.V. and G. R. Ziegler. 2009. Starch: Its self assembly and potential as a controlled delivery system for bioactives, In "Applications of Nanoscience and Nanotechnology in Food Systems. H. Chen, Ed.. Wiley-Blackwell Publishing. (Accepted for Publication).
- Ziegler, G.R., J.A. Creek, and J. Runt. 2005. Spherulitic crystallization in starch as a model for starch granule initiation. Biomacromolecules. 6(3):1547-1554
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Progress 09/01/07 to 08/31/08
Outputs
OUTPUTS: An invited presentation was made at the 9th International Hydrocolloids Conference held June 15-19, 2008 in Singapore. Two seminars were presented at Kasetsart University, Bangkok, Thailand June 10-15, 2008. Information was also disseminated informally at the 2007 Starch Round Table, sponsored by the American Association of Cereal Chemists held in San Antonio, TX, October 4-6, 2007, and at the 2nd International Symposium on the Delivery of Functionality in Complex Food Systems. Results of the study were reported at the NRI 75.0 Grantees' Workshop, September 20-21, 2008 at the University of California-Davis, Davis, CA. PARTICIPANTS: Dr. Greg Ziegler continues as project director and immediate research supervisor. Dr. Rajesh Bhosale has completed one year as a post-doctoral research associate on this project, taking over for Dr. John Creek who graduated with his Ph.D. in 2007. Dr. Jim Runt, Professor of Materials Science and Engineering at Penn State continues to serve as co-PI. We have initiated collaboration with National Starch LLC and Kasetsart University in Bangkok, Thailand. The project has supplied training opportunities to Ms. Kolika Chatterjee, who completed her M.S. degree this past year, and Ms. Nuttanit Suwanayuen who is currently pursuing her M.S. degree. TARGET AUDIENCES: The research group, including both PIs, have met with starch industry representatives to present the results of this research and discuss its commercial potential. PROJECT MODIFICATIONS: Due to the graduation of John Creek and the need to hire a replacement, a no-cost extension was requested and approved for this project.
Impacts
We have extended our understanding of the basis for spherulite formation in starch polymers to include the effects of starch architecture. The influence of the amylose-to-amylopectin ratio in both potato and high-amylose corn starch has been investigated. Potato amylopectin is unable to form spherulites, whereas the amylopectin from high-amylose maize can. It appears that despite that fact that both of these forms of amylopectin have longer branch chains than for example normal corn starch, some other factor, e.g. the branching pattern, is responsible for the difference in their behavior. We have also completed an investigation of the spherulite-forming ability of amylose-lipid complexes. Unlike the lipid-free systems, that require fast cooling, spherulites are only formed under conditions of slow cooling. Furthermore, heating to only 140 degrees C is required. We have delineated the heating and cooling conditions necessary for the formation of two types of amylose-lipid spherulites: spherical and torus-shaped. We have established the ability of amylose to form inclusion complexes with a number of functional compounds including pharmaceuticals, nutriceuticals and vitamins.
Publications
- Chatterjee, K. 2007. The Potential Role of Spherulitic Crystallization in Starch Granule Initiation in vivo. M.S. Thesis. The Pennsylvania State University, University Park, PA. 162 pp.
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Progress 09/01/06 to 08/31/07
Outputs
OUTPUTS: The phase-state diagrams for amylose-water systems have been developed for a range of degree of polymerization (DP) from 35 to 900. Generally, spherulites are formed at a starch concentration ranging from as low as 5 % by weight to about 60 % by weight, depending on the degree of polymerization. Outside this range either non-spherulitic precipitates or gels formed. The lowest molecular weight (low DP) amylose of DP 35 did not form spherulites below about 25% concentration by weight, and unlike higher DP fractions, formed A-type crystallinity rather than B-type. Spherulitic crystallization brought on by rapid quenching was shown to be hindered by the presence of lipids capable of forming amylose inclusion complexes. The nanostructure of starch spherulites was compared to that of native granular starch using scanning electron microscopy and atomic force microscopy. A nearly identical "blocklet" structure was observed in both granules and spherulites. The observed blocklets
were on the order of 50 to 100 nm in size. The kinetics of spherulite formation were followed using time-resolved static light scattering. Cloud point curves demonstrated that the mechanism of spherulite formation for the 35 DP sample differed from that of higher DP samples. These results have been disseminated at numerous venues including: the 8th International Hydrocolloids Conference in Trondheim, Norway (2006), the American Physical Society (2006), Institute of Food Technologists Annual Meetings (2006, 2007), as well as, the annual grantees workshops (2006, 2007). Seminars on the topic were presented at Kansas State University (2006), Iowa State University (2006), Procter and Gamble Company (2006) and National Starch and Chemical Company (2007). One Ph.D. student, J.A. Creek, was graduated in 2007.
PARTICIPANTS: The project was directed by Professor Gregory Ziegler of the Department of Food Science at Penn State University in collaboration with Dr. James Runt of the Department of Materials Science and Engineering also at Penn State. A majority of the research was conducted by John A. Creek, who earned his Ph.D. in 2007, and is now employed as an intellectual property scientist with Reckitt-Benckiser, Inc. Dr. Rajesh Bhosale, post-doctoral research associate, is presently collaborating in the effort.
TARGET AUDIENCES: The immediate target audience is the scientific community involved in starch research, including both academic and industrial scientists, businesses manufacturing starch-based materials, and food technologists in general. If the research is successfully commercialized, the target audience would be the general population.
PROJECT MODIFICATIONS: John A. Creek has obtained his Ph.D. with one year remaining on the project. He has been replaced by Dr. Rajesh Bhosale, a post-doctoral research associate. Therefore, the stipend and tuition originally requested to fund John Creek for the final year, is being used instead to fund Dr. Bhosale.
Impacts
Among the anticipated outcomes of this research was the development of new food ingredients and novel systems for the controlled release of flavors, fragrances or pharmaceuticals. This research has laid the foundation knowledge on which a new platform in starch technology can be built. Though not complete, sufficient basic knowledge has been discovered to begin a developmental stage. Furthermore, the fundamental research results on amylose crystallization have had an unanticipated impact on the commercialization of non-food starch materials. Technology transfer is on-going, and the further development of commercial products is expected.
Publications
- Creek, J. A. 2007. Nanoscale self-assembly of starch: phase relations, formation, and structure. Ph.D. Thesis. The Pennsylvania State University, University Park, PA. 235 pp.
- Creek, J. A., Benesi, A., Runt, J., and Ziegler, G. R. 2007. Potential sources of error in the calorimetric evaluation of amylose content of starches. Carbohydrate Polymers 68(3):475-471
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Progress 09/01/05 to 09/01/06
Outputs
Maize amylose, separated from granular starch by means of an aqueous leaching process, was used to investigate spherulite formation from concentrated mixtures of linear starch in water. Amylose, degree of polymerization 930, (10-20 % w/w) was found to form a spherulitic semi-crystalline morphology over a wide range of cooling rates (1-250 C/min.), provided it was first heated to >170 C. This is explained through the effect of temperature on chain conformation. A maximum quench temperature of approximately 70 C was required to produce spherulitic morphology. Quench temperatures between 70 and 110 C produced a gel-like morphology. This is explained based on the relative kinetics of liquid-liquid phase separation vis-a-vis crystallization. The possibility of the presence of a liquid crystalline phase affecting the process of spherulite formation is discussed. Leached amylose was hydrolyzed with acid to prepare eight fractions of varying degree of polymerization (DP).
Temperature-concentration phase diagrams have been constructed for maize amylose of varying degree of polymerization from 30 to 930. The influence of DP on spherulite formation at varying cooling rates, quench depths, and concentrations was investigated. Spherulites were formed between about 5 and 50% (w/w) of amylose, with the exception of the 30 DP fraction. A DP 30 fraction was unusual in that it required a concentration of >30% (w/w) starch, and crystallized in an A-type crystal allomorph. Above 50% (w/w), a gel-like precipitate was formed. The total percent crystallinity varied from 42 to 74 %, with a maximum for the 120 DP fraction. The melting point varied from 80-130 C depending on the DP and the cooling rate. At rapid cooling rates the spherulite size increased with DP. A low-cost laser light scattering device has been constructed using components and software readily available to interested investigators. This device will be used to establish whether spherulitic
crystallization follows phase separation by nucleation and growth, spinodal decomposition or both. The structure of the spherulites has been investigated by X-ray diffraction, optical microscopy (including polarized light microscopy), scanning electron microscopy and atomic force microscopy. The data from these studies are awaiting interpretation.
Impacts
This project will lead to a better understanding of spherulitic crystallization in starch and its relationship to starch granule initiation in vivo, the mechanism of which is still a mystery. With the phase diagrams roughly sketched out, process development and scale-up can begin. The product of such a process may be used as a novel delivery system for active ingredients such as drugs, flavors, fragrances, etc, or as a new texturizing agent for the food and cosmetics industries.
Publications
- Creek, J. A., Ziegler, G. R. and Runt, J. P. 2006. Amylose crystallization from concentrated aqueous solution. Biomacromolecules 7, 761-770
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Progress 09/01/05 to 08/31/06
Outputs
Temperature-concentration phase diagrams (Tamman's diagrams) have been constructed for amylose of varying average molecular weight. The differences between the A and B granules for wheat and barley starches in their ability to form spherulites has been investigated. Smaller B-type granules form spherulites whereas the larger A-type granules do not.
Impacts
This project will lead to a better understanding of spherulitic crystallization in polymers, and new insight into the formation of starch granules in vivo. Additionally, novel products like tailored drug or flavor delivery systems are possible, as are new texturizing agents for the food industry.
Publications
- No publications reported this period
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