Progress 09/01/08 to 08/31/13
Outputs
Target Audience:
Nothing Reported
Changes/Problems:
Nothing Reported
What opportunities for training and professional development has the project provided?
Nothing Reported
How have the results been disseminated to communities of interest?
Nothing Reported
What do you plan to do during the next reporting period to accomplish the goals?
Nothing Reported
Impacts
What was accomplished under these goals?
We made efforts to develop new applications of fully renewable resources to produce additional functional molecules. Several techniques were developed, including one for the synthesis of aerogels based on soy proteins. Also, the use of CNCs for preparing Pickering emulsions was reported along with the evaluation of the morphology of the adsorbed layers via SEM with cryo-fracture techniques. In the area of saponins we developed thin films of phospholipds in quartz crystal microbalance sensors that were used to test the interaction of saponins with the bilayers. One student from the US spent 6 months in Finland working with aerogels and other one on the use of emulsions to stabilize nanocellulose. We also hosted one researcher from Chile who developed with us the work on saponins. Several reports were delivered in scientific meetings and invited talks in the US and around the world.
Publications
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Progress 09/01/11 to 08/31/12
Outputs
OUTPUTS: This year we concentrated in three main bio-based surface active molecules: saponins, functionalized cellulose nanocrystas and soy-derived hydrosoluble macromolecules. Soy work included the production of soy hydrolyzates that displayed relatively high surface activity. Despite the fact that related systems do not fulfill the classification of typical surfactants, we demonstrated that they are amphiphilic biomacromolecules that stabilize liquid-liquid, liquid-air and solid-liquid interfaces. As a result, we produced foams, xerogels and emulsions based on soy derivatives. In the area of cellulose nanocrystals (CNC), we modified the surface of CNCs via grafting-from methods (by using ATRP) and produced thermo-responsive nanoparticles that were effective to stabilize O/W emulsions (as Pickering emulsions). Finally we worked with Chilean researchers in the separation and characterization of saponins, which are amphipathic glycosides with a typical composition of one or more hydrophilic glycoside moieties combined with a lipophilic triterpene derivatives. PARTICIPANTS: Orlando Rojas (PI): He is overseeing all of the work proposed, contribute to the physical and chemical property analyses of the surfactants, and develop the models necessary to optimize the functionality of the surfactants. Lucian Lucia (co-PI). He has been involved in all of the synthetic aspects of this proposed effort and support the physical and chemical characterization of the surfactants. Tom Theyson (co-PI). He is contributing with information about the economics of the surfactant performance and their overall feasibility for inclusion in industrial applications. Niangui Wang: Postdoctoral fellow that worked on the synthesis of sugar-based surfactants. Youssef Habibi: Postdoctoral fellow worked in the deployment of the bio-based surfactants that have been synthesized Carlos Salas: PhD student working on the use of soy proteins as base for new surface active molecules. Juana Suseth Camac: visiting student who worked on the measurement of surface activity of alkylglucosides obtained from fructanes. Angelica Grandon Sanchez: visiting reseeracher who worked with saponins Julio Arboleda: PhD Student that worked with hydrolysis products of soy and aerogels Carlos Salas: PhD student who worked with surface activity of soy proteins Justin Zoppe: PhD student who worked with the use of CNC in Pickering emulsions TARGET AUDIENCES: Not relevant to this project. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
We made efforts to develop new applications of fully renewable resources to produce additional functional molecules. Several techniques were developed, including one for the synthesis of aerogels based on soy proteins. Also, the use of CNCs for preparing Pickering emulsions was reported along with the evaluation of the morphology of the adsorbed layers via SEM with cryo-fracture techniques. In the area of saponins we developed thin films of phospholipds in quartz crystal microbalance sensors that were used to test the interaction of saponins with the bilayers. One student from the US spent 6 months in Finland working with aerogels and other one on the use of emulsions to stabilize nanocellulose. We also hosted one researcher from Chile who developed with us the work on saponins. Several reports were delivered in scientific meetings and invited talks in the US and around the world.
Publications
- Zoppe, J.O., Venditti, R.A., Rojas, O.J. (2012) Pickering emulsions stabilized by cellulose nanocrystals grafted with thermo-responsive polymer brushes, Journal of Colloid and Interface Science, 369: 202-209.
- Salas, Carlos, Rojas, O. J., Lucia, L. Hubbe, M.A., Genzer, J. (2012) Adsorption of glycinin and beta-conglycinin on silica and cellulose:surface interactions as a function of denaturation, pH, and electrolytes, Biomacromolecules, 13: 387-396.
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Progress 09/01/10 to 08/31/11
Outputs
OUTPUTS: The project "Sugar Surfactants as High Value Biobased Products" have been carried out according to our proposed objectives and timely reports have been discussed with the research fellows involved in efforts. The project has involved one graduate student who has been employed full time and two postdoctoral fellows, who were hired during different periods. During the first part of the project Research Fellow Dr. Niangui Wang was employed but later returned to China. Thereafter, Dr. Youssef Habibi was hired. During the last year the team has worked on surface active molecules derived from soy. The focus was to unveil details about the adsorption of such natural materials onto the surface of hydrophobic and hydrophilic surfaces. In the case of hydrophobic fibers, for example, the surfaces can be changed to display hydrophilic functionalities which are otherwise produced by very costly approaches. The surface modifications developed depend highly on a deep understanding of molecules features. During this year we separated and purified glycinin and conglycinin as surface active moclecule and evaluated their interactions with hydrophobic surfaces (ODTS, Alkylthiols) as well as forest-based biopolymers (cellulose and lignin). We also intiaited work on the surface activity of bio-based products from alkyloligofructosides. We participated in a number of activities and presentations. These include: -Adsorption of soy glycinin onto silica and ultrathin cellulosic films studied by quartz crystal microgravimetry. Salas C. Rojas, O.J., Lucia, L., 241st ACS National Meeting, Anaheim CA. March 2011. - Applications of proteins in the wet-end. TAPPI Intl Conference on Nanotechnology for Renewable Materials. Salas, C., Rojas, O.J. Lucia, L.,Washington DC, June 2011. - Soy proteins as surface modifiers. Salas C. Rojas, O.J., Lucia, L., TAP meeting, United Soy Board. Raleigh, NC. PARTICIPANTS: Orlando Rojas (PI): He is overseeing all of the work proposed, contribute to the physical and chemical property analyses of the surfactants, and develop the models necessary to optimize the functionality of the surfactants. Lucian Lucia (co-PI). He has been involved in all of the synthetic aspects of this proposed effort and support the physical and chemical characterization of the surfactants. Tom Theyson (co-PI). He is contributing with information about the economics of the surfactant performance and their overall feasibility for inclusion in industrial applications. Niangui Wang: Postdoctoral fellow that worked on the synthesis of sugar-based surfactants. Youssef Habibi: Postdoctoral fellow worked in the deployment of the bio-based surfactants that have been synthesized Carlos Salas: PhD student working on the use of soy proteins as base for new surface active molecules. Juana Suseth Camac: visiting student who worked on the measurement of surface activity of alkylglucosides obtained from fructanes. Collaborators: Guillermo Toriz Gonzalez, Research Professor, University of Guadalajara Ezequiel Delgado Fornue, Research Professor, University of Guadalajara Martin Hubbe, Natural Resources, NCSU Jan Genzer, Chemical engineering, NCSU Wendy Krause, College of Textiles, NCSU Ingrid Hoeger, Natural Resources, NCSU John Heitmann, Natural Resources, NCSU Xavier Turon, Institut Quimica Sarria, Universitat Ramon Llull, Spain Janne Laine, Helsinki University of Technology, Finland Formal classroom instruction that benefit from the present project: WPS 595B: Biomaterials Characterization WPS 595I: Interfacial Phenomena in Dispersed Systems Laboratory instruction to graduate and undergraduate students to become instrumental in the use of the following instruments: XPS, SEM, TEM, XRD, DSC, TGA, DMA, FTIR. TARGET AUDIENCES: Not relevant to this project. PROJECT MODIFICATIONS: Not relevant to this project.
Impacts
No identifiable change in societal conditions can be identified during the year of operation. However, we think we have increased the awareness on the use of bio-derived systems in new disciplines of knowledge. We have also contributed with the development of human resources and contributed to prospects for sustainable use of resources.
Publications
- No publications reported this period
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Progress 09/01/09 to 08/31/10
Outputs
OUTPUTS: Activities: We carried out the synthesis of the following biomass-based surfactants: (1) 2-hydroxydedecyl trimethylammonium chloride, (2) hydroxyldodecyl dihydroxyethylamine (HDDHEA) and its quarternary salt (HDDHEABBr), (3) hydroxyl dihydroxyethylamino sunflower oil acetate made from sunflower oil and, (4) ethyl oleate-based tertiary cationic surfactant. The obtained chemicals were characterized by FT-IR, 1H-NMR and surface tension. We started to investigate the use of soy proteins as base for additional bio-based surfactants. Events: Among the events realized during this period we can cite the attendance and presentation of our work in the 2010 National Meeting of the American Chemical Society, Division of Cellulose and Renewable Materials, which took place in San Francisco. Products include: The methods developed during the first year were further refined. Dissemination was accomplished via poster and oral presentations in various scientific meetings. Some of our results were used as illustrations of surface active properties of bio-based chemicals in the course WPS 516 Colloids and Surface Science of Forest Biomaterials. Also, editorial activities in the Journal of Surfactant and Detergents, of the American Oil Chemists' Society, were advanced further to bring the topic of our research and outputs to the attention of the scientific community. PARTICIPANTS: Orlando Rojas (PI): He is overseeing all of the work proposed, contribute to the physical and chemical property analyses of the surfactants, and develop the models necessary to optimize the functionality of the surfactants. Lucian Lucia (co-PI). He has been involved in all of the synthetic aspects of this proposed effort and support the physical and chemical characterization of the surfactants. Tom Theyson (co-PI). He is contributing with information about the economics of the surfactant performance and their overall feasibility for inclusion in industrial applications. Niangui Wang: Postdoctoral fellow that has worked on the synthesis of sugar-based surfactants. Youssef Habibi: Postdoctoral fellow working in the deployment of the bio-based surfactants that have been synthesized Carlos Salas: PhD student that joined the project to investigate the use of soy proteins as base for new surface active molecules TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
The major change in knowledge was the realization of the potential of soy beans in the production of a number of surface active molecules. Therefore, during the second year we have invested some of our efforts to unveil the potential application of fully renewable resources to produce additional functional molecules. We have studied soy protein technologies designed to modify the surface of materials (paper, textiles and nonwovens). We are developing protein based materials that will strongly absorb to the surface of hydrophobic fibers/fabrics and provide these materials with hydrophilic functionalities. This work was based on the observation that protein-based materials that have sufficient flexibility within their molecular motifs, adsorb to hydrophilic or hydrophobic surfaces by reorienting their structure to allow the like portion of the protein to strongly interact with the surface (hydrophobic amino acids interacting with hydrophobic surfaces or hydrophilic amino acids interacting with hydrophilic surfaces). This phenomenon tends to result in protein-treated hydrophobic surfaces becoming significantly more hydrophilic and protein-treated hydrophilic surface becoming significantly more hydrophobic. Such interactions can be very significant and lead to a protein layer that is very durable on the surface. As we transition to the third year we will focus on the development of cost effective sugar surfactants and soy protein-based surface active molecules, soy protein fragments for use in modifying the surface of hydrophobic and hydrophilic materials. The proposed platforms will potentially substitute traditional non-renewable products.
Publications
- Rojas, O.J., Lucia, L.A., Habibi, Y and Stubenrauch C. (2009), Interfacial Properties of Sugar-based Surfactants, in BioBased Surfactants and Detergents: Synthesis, Properties, and Applications (Hayes, Ashby, Solaiman, and Kitamoto, Eds.) AOCS Press ISBN = 978-1-893997-67-7.
- Liu, X., Rojas, O.J. Genzer, J. (2010) Amphiphile adsorption on ultrathin films of cellulose and textile polymers, 239th ACS National Meeting, San Francisco, CA, March 21-25, 2010.
- Spence, K., Venditti, R.A. and Rojas, O.J. (2009) Sugar Surfactants in Paper Recycling, Nordic Pulp and Paper Research Journal, 24(1), 107-111.
- Liu, X., Wu, D., Turgman-Cohen, S., Genzer, J., Theyson, T., Rojas, O.J. (2010) Adsorption of a Nonionic Symmetric Triblock Copolymer on Surfaces with Different Hydrophobicity, Langmuir, 26 (12), 9565-9577.
- Song, J. Yamagushi, T., Silva, D.J., Hubbe, M.A. and Rojas, O.J. (2010) Effect of Charge Asymmetry on Adsorption and Phase Separation of Polyampholytes on Silica and Cellulose Surfaces, Journal of Physical Chemistry B, 114, 719-727.
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Progress 09/01/08 to 08/31/09
Outputs
OUTPUTS: Activities: We recruited the personnel to be involved in this project. We installed a Cahn balance device to measure surface tension of surfactant solutions. We also installed a Schlenk manifold setup. This set up is being used extensively in synthesis of surfactants based on carbohydrates. We also installed a spinning drop tensiometer and a foam column to be used with the Bikerman method for foam ability and stability. Training of the involved personnel included theoretical sessions and hands-on experiments on the use of instrumental techniques such as NMR, XPS, SEM, TEM, XRD, FTIR, DSA, TGA and DMA. Events: Among the events realized during this period we can cite the attendance and presentation of our work in the 2009 National Meeting of the American Chemical Society, Division of Cellulose and Renewable Materials, which took place in Salt Lake City. We also organized a symposium on "Biosurfactants and Other Novel Surfactants" (co-organized with Krister Holmberg, Chalmers University of Technology) in the 13th Intl. Association of Colloid & Interface Scientists Conference on Surface and Colloid Science and 83rd ACS Colloid and Surface Science Symposium, June 14-19, Columbia University, New York. The personnel involved in this project presented their work in seminars within our department. An undergraduate student joined our project and was tutored and trained by the lead researcher in a number of operations in the laboratory. All the researchers in our project met every week. We established an internal code of conduct and receive instruction and training in areas related to safety and toxic waste management. Products include: We developed methods to produce sugar surfactants from different raw materials. Dissemination was accomplished via poster and oral presentations in various scientific meetings. The scope of our work was used in the development of course content in the course entitled "Principles of Forest Biomaterials" and "Forest Biomaterials Characterization". We organized symposia to highlight our work and future perspectives: Organized and chaired the Symposium on "Environmental Applications of Colloids and Surfactants" 82nd Colloid and Surfaces Symposium, Raleigh, June 15-18, 2008. Organized with Prof. Pedro Fardim (Abo Academy, Finland) of the European Union-US Polysaccharides as a Source of New Materials: Prospective and Innovative Trends, ACS National Meeting, New Orleans, April 9, 2008. Organized the session on "Biosurfactants and Other Novel Surfactants" (with Krister Holmberg, Chalmers University of Technology) in the 13th Intl. Association of Colloid & Interface Scientists Conference on Surface and Colloid Science and 83rd ACS Colloid and Surface Science Symposium, June 14-19, Columbia University, New York. PARTICIPANTS: Principal investigators: Orlando J. Rojas (PI), NCSU Lucian Lucia, NCSU Tom Theyson, NCSU Collaborators and contacts: Martin Hubbe, Natural Resources, NCSU Jan Genzer, Chemical engineering, NCSU Ingrid Hoeger, Natural Resources, NCSU John Heitmann, Natural Resources, NCSU Janne Laine, Helsinki University of Technology, Finland TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
The major contribution in the change in knowledge was the development of methods to create sugar-base surfactants using hydrophobic chains consisting of natural and synthetic oils. We demonstrated the possibility of producing amphiphilic molecules using simple chemical routes and green chemistries. Results of these efforts have been showcased in a number of presentations and publications and invited seminars. Successful preparation of the following surface active species was carried out: 2-hydroxydedecyl trimethylammonium chloride with respective Gemini surfactant; hydroxyldodecyl dihydroxyethylamine (HDDHEA) and its quaternarium ammonium salt (HDDHEABBr) ; sunflower oil-based tertiary cationic surfactant and ethyl oleate-based tertiary cationic surfactant. All products were characterized by 1H-NMR, FT-IR and surface tension. Our ongoing contribution will help to create methods and industries to use abundant renewable agricultural byproducts such as saccharide fractions and natural oils as precursors for the production of value-added chemicals. Presentations: -Wang, Niangui; Lucia, Lucian A.; Rojas, Orlando J Synthesis and characterization of sugar-based surfactant, 237th ACS National Meeting, Salt Lake City, UT, March 22-26, 2009. -Key note talk "Viscoelasticity And Surface Forces In Systems with Alkyl Glucoside Surfactants", 13th Intl. Association of Colloid & Interface Scientists Conference on Surface and Colloid Science and 83rd ACS Colloid and Surface Science Symposium, June 14-19, Columbia University, New York. -Invited talk, Fenomenos Interfaciales y Nanotecnologia de Materiales Lignocelulosicos, IV Simposio Nacional y I Internacional de Surfactantes y Aplicaciones, Merida, Venezuela, October 27-30, 2008. -Polymer & Surfactant Interactions and Adsorption / Polyelectrolyte-Surfactant Interactions in the bulk and at Interfaces, SC Johnson and Sons, Racine, Wisconsin, June 5, 2008.
Publications
- No publications reported this period
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