Progress 10/01/08 to 09/30/13

Outputs
Target Audience: Academic and industrial research and development on bioproducts and bioenergy. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Three students have been trained as principal investigators of the 2012-2013 LSU College of Agriculture undergraduate research project (Analysis of Fire Retarded Cellulosic Samples). How have the results been disseminated to communities of interest? Results from this project were presented in publications and at a national conference. The investigations were also discussed at the annual meeting of the S-1041 participants. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? Nonwoven composite materials were made of bagasse fibers and cotton and sugar-derived poly (lactic acid), PLA, or poly(hydroxy alkanoates), PHA. The composites are completely biodegradable and may substitute similar petroleum-based products. The bagasse bio-based nonwovens composites were treated with fire retardants and hydrophobized by covering with a hydrophobic PHA film. Nylon-like materials were synthesized by substituting the diacid with sugar bio-derived diacids in the polycondensation reaction with diamines. To this aim, ethyl bis-ketal galactarates were reacted with 1,6-hexamethylene diamine to yield tetrahydroxylated nylon 6,6 type materials. Solutions of these green bio-derived polyamides in amino-oxides and ionic liquids exhibit intriguing tree-like morphologies still under scrutiny. Attention has been paid also to the use of biobased polymers in nanomedicine which were reviewed for further examination.

Publications

• Type: Journal Articles Status: Published Year Published: 2013 Citation: Rosu, Cornelia; Negulescu, Ioan I.; Cueto, Rafael; Laine, Roger; Daly, William H. Synthesis and Characterization of Complex Mixtures Consisting of Cyclic and Linear Polyamides from Ethyl Bis-Ketal Galactarates. Journal of Macromolecular Science, Part A: Pure and Applied Chemistry. 50(9), 940-952.
• Type: Book Chapters Status: Published Year Published: 2013 Citation: Negulescu, I. and Uglea, C.V. Polymeric Micelles, Chapter 7 in M. Popa and C.V. Uglea (eds), Polymeric Nanomedicines. Bentham Science Publishers, Sharjah, UAE, p. 251-292.
• Type: Book Chapters Status: Published Year Published: 2013 Citation: Negulescu, I., Uglea, C.V. and Popa, M. Polymeric Nanomedicines: Between Tradition and Innovation, Polymeric Nanomedicines, Chapter 21 in M. Popa and C.V. Uglea (eds), Polymeric Nanomedicines. Bentham Science Publishers, Sharjah, UAE, p. 783-790.
• Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: McNeel, Kelsey E., Das, Susmita, Negulescu, Ioan, Warner, Isiah. Effects of sodium deoxycholate hydrogel modification on drug release and size of templated nanoGUMBOS. Abstract of Papers, 245th ACS National Meeting & Exposition, New Orleans, LA, United States, April 7-11, 2013, ANYL-303.

Progress 01/01/12 to 12/31/12

Outputs
OUTPUTS: Results from this project have been published in one paper and one book chapter. This information has been presented at one meeting and in the Seminar class (HUEC 7043) at Louisiana State University, Baton Rouge, Louisiana. The investigations were also discussed at the 2012 annual S-1041 meeting. PARTICIPANTS: Ioan I. Negulescu, (PI), LSU AgCenter; Roger A. Laine, William H. Daly, Paul S. Russo, Isiah M. Warner, Kelly Rusch, Teresa Gutierrez-Wing, Alexandra Gagnier, Maegan Campbell, Jenna Schumann, Crystalline Thermal, Ashley Jacobs, Cornelia Rosu, Louisiana State University. TARGET AUDIENCES: Academic, faculty and industrial research and development scientists interested in bioproducts and bioenergy. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Sugarcane is both a source of sugar and bagasse from which lingo-cellulosic fibers can be separated. The nonwoven composite materials (bagasse fibers, cotton, sugar-derived polylactic acid (PLA), or polyhydroxy alkanoates (PHA), are completely bio-based, biodegradable, and may substitute for similar petroleum-based products. Thermal transitions of PLA were investigated both in dry and wet states by calorimetry and thermomechanical analysis to understand the behavior of this polyester during coloration when used for textile purposes. Thermal transitions have been evaluated for a new class of nylon-like materials by substituting the diacid with green sugar bio-derived diacids with diamines in the polycondensation reaction. The glass transition and the melting characteristics have been considered for two new polyhydroxypolyamides, with 6 and 12 carbon atoms in the diamine rest. Also, formation and rheology of the LSU nanoscale Group of Uniform Materials Based on Organic Salts (nanoGUMBOS) gels was investigated.

Publications

• Negulescu, I., Ailincai, D. and Uglea, C.V. 2012. Biological Activity of Natural Polysaccharides In: Medical Applications of Polymers., Chapter 1 In M. Popa, C.V. Uglea and R.M. Ottenbrite (eds), Macromolecular Drugs, Volume 1. American Scientific Publishers, Valencia, California, USA, p. 1-33.
• Susmita, D., De Rooy, S.L., Jordan, A.N., Chandler, L., Negulescu, I.I., El-Zahab, B. and Warner, I.M. (2012). Tunable Size and Spectral Properties of Fluorescent NanoGUMBOS in Modified Sodium Deoxycholate Hydrogel, Langmuir, 28: 119-124.
• McNeel, K.E.; Susmita, D., Negulescu, I.I. and Warner, I.M. 2012. Modified sodium deoxycholate hydrogels for templating tunable nanoGUMBOS. Abstracts, 68th Southwest Regional Meeting of the American Chemical Society, Baton Rouge, LA, United States, November 4-7 SWRM-12.

Progress 01/01/11 to 12/31/11

Outputs
OUTPUTS: Results from this project were presented in two peer-reviewed journal papers and at an international conference. The investigations were also discussed in a poster presentation at the annual meeting of the Regional Project S-1041 participants where a poster. PARTICIPANTS: Ioan I. Negulescu, (PI), M.P. Mailander, Grace Aluko, Aja Hite, Elizabeth Ann Bertrand, and Ashley Jacobs, LSU AgCenter; Roger A. Laine, William H. Daly, Paul S. Russo, Kelly Rusch, Teresa Gutierrez-Wing, Louisiana State University, Baton Rouge, Louisiana; Yan Chen, Texas A&M University, Austin, Texas. TARGET AUDIENCES: Academic and industrial research and development on bio-products and bio-energy. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Sugarcane is not only a source of sugar, but also fibers (bagasse) and specific organic derivatives such as aconitic acid (extractable from the green leaves). The nonwoven composite materials made of plant fibers (bagasse) and sugar-derived polyesters, such as poly(lactic acid), PLA, and poly(hydroxy alkanoates), PHA, are completely bio-based and biodegradable and can substitute similar petroleum-based products. In order to set the temperature limit of using composite fiber materials, the thermal stability and degradation of cotton and bagasse have been investigated both in air and inert atmosphere in view of the determination of the energy of activation at the setting of the degradative process. A new class of nylon-like materials was obtained by substituting the diacid with green bio-derived aldaric acids in the polycondensation reaction with diamines. These new polyhydroxypolyamides are called glylons, similar to classic nylons. At the same time, a new research avenue which can impact Louisiana economy is the production of both PHA and lipids (bio-fuel) from native micro-algal cultures.

Publications

• Gutierrez-Wing, M.T., Stevens, B.E., Theegala, C.S., Negulescu, I.I., Rusch, K.A. 2011. Aerobic Biodegradation of Polyhydroxybutyrate (PHB) in Compost. Environmental Engineering Science 28:477-488.
• Liangfeng Sun, Jonathan Y. Chen, Ioan I. Negulescu, Mary A. Moore and Billie J. Collier. 2011. Kinetics Modeling of Dynamic Pyrolysis of Bagasse Fibers. Bioresource Technology 102:1951-1958.
• Silaban, A. G., Gutierrez-Wing, M.T., Negulescu, I., Rusch, K.A. 2011. Effect of Light and Nutrients on Biomass and Lipid Production of a Louisiana Native Microalgal Co-Culture Selected for Biofuel Production. World Aquaculture Society Conference AQUACULTURE AMERICA 2011, March 1, New Orleans, LA.
• Cornelia Rosu, Ioan Negulescu, Paul Russo, Roger Laine and William Daly. A New Approach to Self-Assemble Glylon -6,6 Solutions into Tree Rings Patterns. The 2011 S1041 Meeting and Symposium August 1-2, Stillwater, OK.

Progress 01/01/10 to 12/31/10

Outputs
OUTPUTS: Results from this project were presented in three peer reviewed journal papers, and one published in conference proceedings. PARTICIPANTS: Ioan I. Negulescu, Professor, School of Human Ecology, Louisiana State University. Dorin Boldor, Assistant Professor, Department of Bioagricultural Engineering, Louisiana State University. COLLABORATORS: Roger A. Laine, Professor, LSU AgCenter and Department of Biochemistry, Louisiana State University, Baton Rouge, Louisiana; William H. Daly, Professor, Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana; Kelly Rusch, Professor, Department of Civil and Environmental Engineering, Louisiana State University, Baton Rouge, Louisiana; Teresa Gutierrez-Wing, Assistant Professor Research, Department of Civil and Environmental Engineering, Louisiana State University, Baton Rouge, Louisiana; TRAINING UNDERGRADUATE STUDENTS PIs and Undergraduate Research Projects supported by the College of Agriculture, Louisiana State University, Baton Rouge, LA as follows. Grace Aluko, Aja Hite and Elizabeth Ann Bertrand, School of Human Ecology, College of Agriculture, Louisiana State University, Baton Rouge, Louisiana. Adding Value to Louisiana Natural Products, Reaction of Aconitic and Related Acids Present in Sugar Cane and Energy Plants and Molases towards Preparation of Sustainable Polymeric Materials, 07/01/10-06/30/11; Erin Brunson, School of Human Ecology, College of Agriculture, Louisiana State University, Baton Rouge, Louisiana: New Biobased Polyhydroxylated Nylons: Chemistry and Morphology, 07/01/09-06/30/10. TRAINING GRADUATE STUDENTS: Xiaoqun Zhang, School of Human Ecology, Louisiana State University, Baton Rouge, Louisiana; Cristina Martinas Stefanescu, Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana. TARGET AUDIENCES: Academic and industrial research and development on bioproducts and bioenergy. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Bio-degradation investigations of nonwoven composites made of bagasse and cotton with aliphatic plant-derived polyesters, such as poly(hydroxy butyrate) (PHB) and polylactic acid (PLA), confirmed that PHB materials biodegraded both in aerobic (compost) and anaerobic conditions under the attack of specific microorganisms and that polylactic acid biodegrades only in an aerobic environment. The use of these biopolymers has been further investigated as drug delivery microspheres. Solvent and continuous microwave-assisted extractions of oil from crude algae and algal paste, respectively, have been performed in line with the program of obtaining biofuels from algae, while adding value to sugar cane biomass has been initiated by considering the extraction and use of aconitic acid in polymer composites.

Publications

• Gutierrez-Wing, M.T., Stevens, B.E., Theegala, C.S., Negulescu, I.I., Rusch, K.A. 2010. Anaerobic Biodegradation of Polyhydroxybutyrate (PHB) in Municipal Sewage Sludge. Journal of Environmental Engineering. Vol. 136 No. 7 pp 709-718.
• Eduard A. Stefanescu, Cristina Stefanescu and Ioan I. Negulescu. 2010. Biodegradable Polymeric Capsules Obtained via Room Temperature Spray Drying: Preparation and Characterization. Journal of Biomaterials Applications. DOI: May 28 10.1177 0885328210366489
• Balasubramanian, S., J.D. Allen, A. Kanitkar and D. Boldor. 2010. Oil Extraction from Scenedesmus obliquus using a Continuous Microwave System Design, Optimization and Quality Characterization. Bioresource Technology. Vol. 102 No. 3 pp. 3396-3403.

Progress 01/01/09 to 12/31/09

Outputs
OUTPUTS: Results from this project were published in one peer-reviewed journal paper, one conference proceedings abstract and one extended peer-reviewed preprint. Presentations of research results were also delivered at one national conference and one international conference. The activities have also been submitted as a SunGrant report and are available via the US of Department of Transportation. These reports are submitted quarterly. They indicate progress since the last report and overall progress. PARTICIPANTS: PARTICIPANTS: INDIVIDUALS WHO WORKED ON THE PROJECT: Ioan I. Negulescu, Professor, LSU AgCenter and School of Human Ecology, College of Agriculture, Louisiana State University; Michael Mailander, Associate Professor, LSU AgCenter. COLLABORATORS: Chandra Theegala, Associate Professor, LSU AgCenter; Roger A. Laine, Professor, LSU AgCenter and Department of Biochemistry, Louisiana State University, Baton Rouge, Louisiana; Dharnid V. Parikh, Group Leader, USDA ARS Southern Regional Research Center, New Orleans, Louisiana; William H. Daly, Professor, Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana; Svetlana Oard, LSU AgCenter; Paul S. Russo, Professor, Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana; Kelly Rusch, Professor, Department of Civil and Environmental Engineering, Louisiana State University, Baton Rouge, Louisiana; Teresa Gutierrez-Wing, Research Associate, Department of Civil and Environmental Engineering, Louisiana State University, Baton Rouge, Louisiana; TRAINING: GRADUATE STUDENTS: Cristina Martinas Stefanescu and Cornelia Rosu, Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana. UNDERGRADUATE STUDENTS PIs and Undergraduate Research Projects supported by the College of Agriculture, Louisiana State University, Baton Rouge, LA: Elisabeth A. Wise, School of Human Ecology, College of Agriculture, Louisiana State University, Baton Rouge, Louisiana, Preparation of sustainable nonwoven composites using short bagasse fibers and corn derived polyesters, 07/01/08-06/30/09; Erin Brunson, School of Human Ecology, College of Agriculture, Louisiana State University, Baton Rouge, Louisiana Adding value to Louisiana natural products: Reactions and molecular orientation of sea food derived chitosan in ionic liquids 07/01/09-06/30/10. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
1. Anaerobic bio-degradation investigations of plant-derived aliphatic polyesters, i.e., poly(hydroxy butyrate), PHB, and of nonwoven composites, NWC, made of PHB and annual plants fibers, performed according to specific ASTM standard methods, have shown that both the polymer and NWC biodegraded both in aerobic (compost) and anaerobic conditions (in which methane was formed as the main carbonaceous component) under the attack of specific microorganisms. These findings are being used to assist large-scale biodegradation of plant-derived polymers indicating that if there is a choice it should be performed anaerobically in order to collect the biogas (methane) as a by-product to help improve the energetic balance related to their fabrication. Investigations were also made on chitosan, in order to aid value to this forgotten Louisiana seafood by-product. 2. Biomass analysis has established the desired outline of strategies for efficient biomass utilization in the farm and community. The temperatures achieved (600-1400 C) by the gasification of various feedstocks was determined to be adequate for most on-farm requirements. The development of electrical power from the combustion of the produced gas was not proven, due to the presence of contaminants that would foul the motor. The platform for the tallow harvester was straightened and strengthened and readied for installation of the boom. Testing established that a feasible harvesting method was a string blade mounted on the end of the arm. The boom has the capability to position the harvesting head to any position in a 10 meter sphere. 3. The algae growth experiments developed data on expected kinetics on the Chlamydomonas reinhardtii, under both complete and sulfur-deprived conditions. The algae produced an average of 5 mL/hour of hydrogen during the sulfur deprived stage. After about 50-60 hours the yield began to level off and by 90-100 hours the algae needed to be rejuvenated by going back to normal photosynthesis. Gas capture and analysis systems were tested; the replacement of conventional gas by nitrogen gas as the carrier gas in the gas chromatograph was verified as providing accurate measurements.

Publications

• Ioan I. Negulescu, March 2009, Natural Fibers/Biodegradable Polymers Tandem: Biocomposites and Sustainability, 43rd International Wood Composites Symposium & Technical Workshop on Natural Fibers: Their Role in the Carbon Economy, Seattle, WA
• Stefanescu, C., Daly, W. H. and Negulescu, I. I. 2009 Nucleophilic reactivity of chitosan in ionic liquids promoted by tert-amines. Polymer Preprints 51(2), 551-552.