Progress 09/01/06 to 08/31/10
Outputs
OUTPUTS: Activities accomplished consist of conducting and analyzing experiments related to designing bioreactor systems for the solvent-free enzymatic synthesis of biobased surfactants and understanding the formation, stability, and role of micron-sized aggregates of sugars suspended in solvent-free media for the enzymatic conversion. A PhD student (Mr. Ye Ran) was mentored for this portion of the project. In addition, small-angle neutron scattering experiments were performed to analyze the effect of proteins on phase behavior relating to the development of protein extraction using 3-phase microemulsions. Additional experimentation was performed to better understand the effect of time and methodology for mixing the aqueous and oil-based solutions to form the 3-phase systems Research related to this grant was disseminated through presentations at several major symposia and several publications (given below) Regarding services, the proposed research has facilitated the lead investigator to organize a symposium on Biobased Surfactants for the American Oil Chemists' Society Annual Meeting in Phoenix, AZ, May, 2010 Products developed For biocatalytic synthesis of biobased surfactants, bioreactor prototypes for the solvent-free lipase-catalyzed synthesis of biobased surfactants were further developed and improved. Also, a mathematical model to describe the kinetics observed in the bioreactor system was initiated. Small-angle neutron scattering data was obtained to better understand the nanostructural changes occurring in microemulsion phases due to incorporation of proteins. PARTICIPANTS: Mr. Ye Ran, graduate PhD student worked on this project, under the advisement of the Project Director (PD), Dr. Douglas G. Hayes. Mr. Ran (under the advisement of the PD) has completed 1 publication, has submitted 2 manuscripts currently under review, and is expected to complete a fourth manuscript next Spring. Mr. Ran will complete his PhD dissertation in the Winter of 2011. Dr. Javier Gomez del Rio, a former advisee of the PD, was supervised by the PD during January, 2010, to help complete small-angle neutron scattering experiments at Oak Ridge National Laboratory TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
Bioreactor designs are being developed and assembled that will produce saccharide-fatty acid monoesters, biodegradable and biocompatible emulsifiers that are value-added and biobased products, at high yields and purity employing environmentally-friendly processing (low temperature, atmospheric pressure, no solvents), to obtain an 85-90% yield (of which 85% is monoester and the remainder diester), and productivity of 0.297 mmol per hour per gram of lipase, starting with acyl donor / monoester, the latter at 5-25 wt%. The final product may not need of further purification; moreover, it would serve as a technical-grade product. The key technical development is to make use of the enhanced miscibility of the two feedstocks which occurs in the presence of the bioemulsifiers and to employ stable, micron-sized, suspensions of sugar crystals. Novel 3-phase micro-emulsion systems featuring a unique pH-degradable detergent can potentially purify proteins as value-added products from agricultural sources rapidly, economically, and selectively.
Publications
- Douglas G, Hayes, 2010, Bioprocessing Approaches to Synthesize Biobased Surfactants and Detergents, in Food and Industrial Bioproducts and Bioprocessing, N.T. Dunford, Ed., Ames, IA, Wiley-Blackwell, in review.
- Ran Ye and Douglas G. Hayes, 2010, Optimization of Solvent Free Lipase Catalyzed Synthesis of Saccharide Fatty Acid Esters through Control of Water Concentration, submitted to J. Am. Oil Chem. Soc.
- Ran Ye and Douglas G. Hayes, 2010, Effect of Acyl Donor and Acceptor for the Lipase Catalyzed Solvent Free Synthesis of Saccharide Fatty Acid Esters in a Bioreactor System, submitted to J. Am. Oil Chem. Soc.
- Javier A. Gomez del Rio, Douglas G. Hayes, and Volker S. Urban, 2010, Partitioning Behavior of an Acid-Cleavable, 1,3-Dioxolane Alkyl Ethoxylate, Surfactant in Single and Binary Surfactant Mixtures for 2 and 3 Phase Microemulsion Systems According to Ethoxylate Head Group Size, J. Colloid Interface Sci. 352: 424 435 (and Supporting Information)
- Ran Ye, Sang-Hyun Pyo, and Douglas G. Hayes, 2010, Lipase Catalyzed Synthesis of Saccharide Fatty Acid Esters Using Suspensions of Saccharide Crystals in Solvent Free Media, J. Am. Oil Chem. Soc. 87:281 293 and Electronic Supplementary Materials.
- Javier A. Gomez del Rio and Douglas G. Hayes, 2010, Protein Extraction by Winsor-III Microemulsion Systems, submitted to Biotechnology Progress.
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Progress 09/01/09 to 08/31/10
Outputs
OUTPUTS: Activities accomplished consist of conducting and analyzing experiments related to designing bioreactor systems for the solvent-free enzymatic synthesis of biobased surfactants and understanding the formation, stability, and role of micron-sized aggregates of sugars suspended in solvent-free media for the enzymatic conversion. In addition, a PhD student (Mr. Ye Ran) and one postdoctoral associate (Dr. Sang-Hyun Pyo) were mentored. Research related to this grant was disseminated through presentations at several major symposia and several publications (given below) Regarding services, the proposed research has facilitated the lead investigator to serve as lead editor the book "Biobased Surfactants, which appeared in print in May, 2009, and to organize a symposium on the same topic for the American Oil Chemists' Society Annual Meeting (2007-2011, respectively). Products developed consist of new fundamental and applied knowledge: bioreactor prototypes for the solvent-free lipase-catalyzed synthesis of biobased surfactants, the relationship between water content and the reaction rate and conversion and the distribution of mono- and di-ester products, and that stable, micron-sized, suspensions of sugar crystals can be formed in solvent-free media which produce a more rapid rate of reaction for lipase-catalyzed biobased surfactant synthesis (and the methodology for their formation). Also, new information on the adsorption of sugars from packed columns to solvent-free liquid phases, specifically, the applicability of the Freundlich isotherm equation, was also obtained by experimentation. A mathematical model to describe the kinetics observed in the bioreactor system is currently being developed PARTICIPANTS: Dr. Sang-Hyun Pyo, postdoctoral research associate, and Mr. Ye Ran, graduate PhD student (Biosystems Engineering, beginning 2008) worked on this project, under the advisement of the Project Director (PD), Dr. Douglas G. Hayes. A special training opportunity was provided from this project for Dr. Pyo. Under the advisement of the PD, Dr. Pyo wrote a review chapter for a book on "Biobased Surfactants" prepared by the PD, on saccharide-fatty acid ester biobased surfactants. Mr. Ran (under the advisement of the PD) has completed 1 publication, has written 1 manuscript currently under review, is preparing a third manuscript, and is expected to complete a fourth manuscript next Spring. Mr. Ran will complete his PhD dissertation in the Winter of 2011. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: The Project Director and co-workers discovered that the use of a packed-bed column as a means of delivering saccharides to a solvent-free liquid phase consisting of fatty acid and saccharide-fatty acid ester yielded too low of liquid-phase saccharide concentrations (manuscript in preparation). It was subsequently discovered that small, approx. 100 micron-sized saccharide aggregates suspended in solvent-free media, formed by rapid stirring of a slurry, produced a more effective reaction medium. Recently, it was discovered that an in-line filter of nominal size 100 microns was effective in preventing larger aggregates to be transported through the bioreactor system. The final objective, developing a mathematical model, was started but not completed within the grant's duration. However, this work is in progress, and anticipated to be completed in early 2011.
Impacts
Bioreactor designs are being developed and assembled that will produce saccharide-fatty acid monoesters, biodegradable and biocompatible emulsifiers that are value-added and biobased products, at high yields and purity employing environmentally-friendly processing (low temperature, atmospheric pressure, no solvents), to obtain an 85-90% yield (of which 85% is monoester and the remainder diester), and productivity of 0.297 mmol per hour per gram of lipase, starting with acyl donor / monoester, the latter at 5-25 wt%. The final product may not need of further purification; moreover, it would serve as a technical-grade product. The key technical development is to make use of the enhanced miscibility of the two feedstocks which occurs in the presence of the bioemulsifiers. Stable, micron-sized, suspensions of sugar crystals can be formed in solvent-free media which produce a more rapid rate of reaction for lipase-catalyzed biobased surfactant synthesis. Optimal performance occurs when the water content of the liquid phase is maintained near 4 wt %. The bioreactor system has successfully utilized several acyl donors (oleic acid, lauric acid, myristic acid, and caprylic acid) and acceptors (fructose, glucose, sucrose, xylose).
Publications
- Ran Ye and Douglas G. Hayes, 2010, Optimization of Solvent-Free Lipase-Catalyzed Synthesis of Saccharide-Fatty Acid Esters through Control of Water Concentration, submitted to J. Am. Oil Chem. Soc. (revised manuscript returned to the journal).
- Ran Ye and Douglas G. Hayes, 2010, Effect of Acyl Donor and Acceptor for the Lipase-Catalyzed Solvent-Free Synthesis of Saccharide-Fatty Acid Esters in a Bioreactor System, in preparation.
- Sang-Hyun Pyo, Douglas G. Hayes, 2008, Desorption of Fructose from a Packed Column to an Oleic Acid / Fructose Oleate Mixture for Employment in a Bioreactor System, J. Am. Oil Chem. Soc.85:1033 1040.
- Sang-Hyun Pyo and Douglas G. Hayes, 2009, Designs of Bioreactor Systems for Solvent-Free Lipase-Catalyzed Synthesis of Fructose-Oleic Acid Esters, J. Am. Oil Chem. Soc. 86:521 529.
- Douglas G. Hayes, 2009, Biobased Surfactants, Overview and Industrial State-of-the-Art, in Biobased Surfactants and Detergents: Synthesis, Properties, and Applications, edited by D. G. Hayes, D. Kitamoto, D. Solaiman, and R. Ashby, AOCS Press / Taylor and Francis, pp. 3 25.
- Sang-Hyun Pyo and Douglas G. Hayes, 2009, Synthesis of Saccharide-Fatty Acid Ester Biosurfactants via Lipase, in Biobased Surfactants and Detergents: Synthesis, Properties, and Applications, edited by D. G. Hayes, D. Kitamoto, D. Solaiman, and R. Ashby, AOCS Press, pp. 323 350.
- Ran Ye, Sang-Hyun Pyo, and Douglas G. Hayes, 2009, Lipase-Catalyzed Synthesis of Saccharide-Fatty Acid Esters Using Suspensions of Saccharide Crystals in Solvent-Free Media, J. Am. Oil Chem. Soc. 86:521 529 and Electronic Supplementary Materials.
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Progress 09/01/08 to 08/31/09
Outputs
OUTPUTS: 41. Outputs Activities accomplished consist of conducting and analyzing experiments related to recovering proteins from aqueous broths using 3-phase microemulsion systems, characterizing the microemulsion systems by phase diagrams and small-angle neutron scattering (the latter performed with a collaborator at Oak Ridge National Laboratory, ORNL), and designing bioreactor systems for the solvent-free enzymatic synthesis of biobased surfactants. In addition, MS students (Ms. Oriana Obiri), PhD students (Dr. Mayson H. Alkhatib, Dr. Javier Gomez del Rio, and Mr. Ye Ran) and one postdoctoral associate (Dr. Sang-Hyun Pyo) were mentored. Events at which research related to this grant were disseminated include the USDA-NRI "Genes to Products" Conference, Bethesda, MD, 04/08 & 04/09, the American Oil Chemists Society (AOCS) Annual Meeting: Salt Lake City (05/05), St. Louis (05/06), Quebec City (05/07) Seattle (05/08), Orlando (05/09), the American Chemical Society Colloid and Surface Science Division Annual Meeting: Boulder, CO (05/05), Newark, DE (06/07), Raleigh (06/08), New York City (06/09), Oak Ridge National Laboratory's Neutron Science Divisions (05/05), American Cehmical Society (03/05), American Crystallography Association Annual Meeting, Knoxville, TN (06/08), and the Consumer Specialty Products Association "New Horizons" conference, Denver, 10/08. Regarding services, the proposed research has facilitated the lead investigator to serve as lead editor the book "Biobased Surfactants, to appear in print (2009), and to organize a symposium on the same topic for the AOCS Conferences in 2007-2010. Dissemination consisted of preparing proposals for instrumentation time for the Small-Angle Neutron Scattering facilities at National Institute of Standards, NIST, or ORNL with collaborator Dr. Volker S. Urban of ORNL to analyze the nanostructure of microemulsion systems. Proposals were accepted and the data collected in 06/06 (NIST), 09/06 (NIST), 12/07 (ORNL), and 06/08 (ORNL) An additional proposal was accepted in 09/09; however, due to scheduling problems with the investigators, the instrumentation time was not enacted. PARTICIPANTS: Nothing significant to report during this reporting period. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
42. Expected Impact. Novel 3-phase micro-emulsion systems featuring a unique pH-degradable detergent can potentially purify proteins as value-added products from agricultural sources rapidly, economically, and selectively. Bioreactor designs are being developed and assembled that will produce saccharide-fatty acid monoesters, biodegradable and biocompatible emulsifiers that are value-added and bio-based products, at high yields and purity employing environmentally-friendly processing (low temperature, atmospheric pressure, no solvents). An immobilized lipase was determined to catalyze biobased surfactant formation during a 1-month period without loss of catalytic activity. Stable, micron-sized, suspensions of sugar crystals can be formed in solvent-free media which produce a more rapid rate of reaction for lipase-catalyzed biobased surfactant synthesis. A newly-developed method for the rapid fractionation of fatty acids according to the number of double bonds per molecule via urea inclusion compounds is comparably selective to the traditionally-employed, slower, method. The developed technology is applicable to producing nutraceuticals from agriculturally-derived fats and oils that are enriched in omega-6 unsaturation and contain less saturated fats, and to optimizing the composition of fatty acid feedstocks for biodiesel.
Publications
- Mayson H. Alkhatib, Douglas G. Hayes, and Volker S. Urban, 2009, Characterization of Microemulsion Systems Formed by a Mixed 1,3-Dioxolane Ethoxylate / Octyl Glucoside Surfactant System, Journal of Surfactants and Detergents 12 (3) 277-283.
- 43. Publications Hung T. Dang, Oriana Obiri, and Douglas G. Hayes, 2005, Feed Batch Addition of Saccharide During Sacharide-Fatty Acid Esterification Catalyzed by Immobilized Lipase: Time Course, Water Activity, and Kinetic Model, Journal of the American Oil Chemists' Society 82: 487-493.
- Douglas G. Hayes, 2005. Purification of Free Fatty Acids via Urea Inclusion Compounds, in Handbook of Functional Lipids, edited by C. C. Akoh, Boca Raton, FL, CRC Press, pp. 77-88.
- April R. Kelly and Douglas G. Hayes, 2006, Lipase-Catalyzed Synthesis of Polyhydric Alcohol-Poly(Ricinoleic Acid) Ester Star Polymers, J. Appl. Poly. Sci., 101:1646-1656
- Douglas G. Hayes, 2006, Effect of Temperature Programming on the Performance of Urea Inclusion Compound-Based Free Fatty Acid Fractionation, Journal of the American Oil Chemists' Society 83:253-259.
- Maithili E. Rairkar, M. Elena Diaz, Mauro Torriggiani, Ramon L. Cerro, J. Milton Harris, Sarah E. Rogers, Julian Eastoe, Javier A. Gomez del Rio, and Douglas G. Hayes, 2007, Three-Component Microemulsions Formed Using pH-Degradable 1,3-Dioxolane Alkyl Ethoxylate Surfactants, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 301 (1-3), 394-403.
- Pyo, Sang-Hyun; Hayes, Douglas G.. Desorption of Fructose from a Packed Column to an Oleic Acid/Fructose Oleate Mixture for Employment in a Bioreactor System. Journal of the American Oil Chemists' Society (2008), 85(11), 1033-1040
- Sang-Hyun Pyo and Douglas G. Hayes, 2009, Designs of Bioreactor Systems for Solvent-Free Lipase-Catalyzed Synthesis of Fructose-Oleic Acid Esters, Journal of the American Oil Chemists' Society, 86:521-529.
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Progress 09/01/07 to 08/31/08
Outputs
OUTPUTS: Activities accomplished consist of conducting and analyzing experiments related to designing bioreactor systems for the solvent-free enzymatic synthesis of biobased surfactants and understanding the formation, stability, and role of micron-sized aggregates of sugars suspended in solvent-free media for the enzymatic conversion. In addition, a PhD student (Mr. Ye Ran) and one postdoctoral associate (Dr. Sang-Hyun Pyo) were mentored. Events at which research related to this grant were disseminated include the USDA-NRI "Genes to Products" Conference, Bethesda, MD, 04/08, the 99th American Oil Chemists Society (AOCS) Annual Meeting, Seattle, 05/08, and the Consumer Specialty Products Association "New Horizons" conference, Denver, 10/08. Regarding services, the proposed research has facilitated the lead investigator to serve as lead editor of the book "Biobased Surfactants", to appear in print (2009), and to organize a symposium on the same topic for the 99th AOCS Meeting. Products developed consist of new fundamental and applied knowledge: bioreactor prototypes for the solvent-free lipase-catalyzed synthesis of biobased surfactants, the relationship between water content and the reaction rate and conversion and the distribution of mono- and di-ester products, and that stable, micron-sized, suspensions of sugar crystals can be formed in solvent-free media which produce a more rapid rate of reaction for lipase-catalyzed biobased surfactant synthesis. Also, new information on the adsorption of sugars from packed columns to solvent-free liquid phases, specifically, the applicability of the Freundlich isotherm equation, was also obtained by experimentation. PARTICIPANTS: Dr. Sang-Hyun Pyo, postdoctoral research associate, and Mr. Ye Ran, graduate PhD student (Biosystems Engineering, 2008) worked on this project, under the advisement of the Project Director (PD), Dr. Douglas G. Hayes. A special training opportunity was provided from this project for Dr. Pyo. Under the advisement of the PD, Dr. Pyo wrote a review chapter for a book on "Biobased Surfactants" being prepared by the PD, on saccharide-fatty acid ester biobased surfactants. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: The Project Director and co-workers discovered that the use of a packed-bed column as a means of delivering saccharides to a solvent-free liquid phase consisting of fatty acid and saccharide-fatty acid ester yielded too low of liquid-phase saccharide concentrations (manuscript in preparation). It was subsequently discovered that small, approx. 100 micron-sized saccharide aggregates suspended in solvent-free media, formed by rapid stirring of a slurry, produced a more effective reaction medium. Current research is focusing on the developing unit operations which will produce the suspensions, and re-examination of the other components of the bioreactor system being developed so that the suspension will be transported through the system, but larger aggregates will not be transported.
Impacts
Bioreactor designs are being developed and assembled that will produce saccharide-fatty acid monoesters, biodegradable and biocompatible emulsifiers that are value-added and bio-based products, at high yields and purity employing environmentally-friendly processing (low temperature, atmospheric pressure, no solvents) to obtain an 85-90% yield, without the need of further purification. The key technical development is to make use of the enhanced miscibility of the two feedstocks which occurs in the presence of the bioemulsifiers. Stable, micron-sized, suspensions of sugar crystals can be formed in solvent-free media which produce a more rapid rate of reaction for lipase-catalyzed biobased surfactant synthesis.
Publications
- Pyo, S., Hayes, D. 2007. Desorption of Fructose from a Packed Column to an Oleic Acid / Fructose Oleate Mixture for Employment in a Bioreactor System, submitted to the Journal of the American Oil Chemists Society.
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Progress 09/01/06 to 09/01/07
Outputs
A bioreactor prototype was formed and tested for the immobilized lipase-catalyzed synthesis of sugar-fatty acid monoesters, which are bio-based emulsifiers. The bioreactor employed no organic solvents. The system consisted of a reservoir open to the atmosphere that feeds a continuously recirculated closed-loop stream passing through a saccharide desorption column, to increase the medium's fructose content, and then a packed-bed bioreactor containing immobilized lipase, prior to its return to the reservoir. A reactor feed containing 30% monoester and 70% fatty acid was converted to 81% esters and 19% fatty acid. The change in bioreactor composition with time was predicted accurately by a mathematical model. Dr. S. H. Pyo will begin work on this project, serving as a postdoctoral research associate, beginning January, 2006. Ms. Brittany Swann, an Undergraduate Research Assistant, began work on this project in October, 2006. She is synthesizing sugar-fatty acid esters
needed for operation of the bioreactors.
Impacts
Bioreactor designs are being developed and assembled that will produce saccharide-fatty acid monoesters, biodegradable and biocompatible emulsifiers that are value-added and bio-based products, at high yields and purity employing environmentally-friendly processing (low temperature, atmospheric pressure, no solvents). An immobilized lipase was determined to catalyze monoester formation during a 1-month period without loss of catalytic activity. A mathematical model was developed which accurately predicted the change in composition of the reaction mixture in a bioreactor prototype as a function of time.
Publications
- No publications reported this period
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