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Green Chemistry

• Green chemistry is defined as "the use of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products." It's kind of the Hippocratic Oath for chemists, a thought process for practicing chemists and a link to the goals of sustainability.
• Green chemistry and our expertise with supercritical fluid technology provide the basis for our research program. At elevated temperatures and pressures (i.e., above the critical point), compounds become supercritical fluids and possess properties intermediate between gases and liquids. These fluids dissolve solutes, yet have gas-like diffusivity and surface tension. Importantly, these properties can be varied as a function of temperature and pressure. Resulting chemical processes in supercritical fluids can have advantages of being faster and more selective with minimal use of hazardous organic solvents.
• Specifically, our research falls into three major areas, including green chemistry:
  • Analytical separations. Virtually all laboratory samples require some type of separation prior to analysis. We are interested in analytical sample preparation (i.e., extraction) and high-resolution chromatography methods. In the extraction area, we use supercritical fluid extraction and a related technique, accelerated solvent extraction, for the isolation of selected organic compounds from a variety of sample types. Areas of active interest include studies on the role of diffusion in the extraction of solid samples, the isolation of additives (antimicrobials and growth hormones) from animal feeds and tissues and the determination of chemical contaminants that may migrate into foods during cooking. Another project is exploring the use of green solvents and chelating agents in separation processes. Our interests in high-resolution chromatography are in the use of supercritical fluid chromatography and high-temperature liquid chromatography for the characterization of complex samples.
  • Bioprocessing. The next generation of biofuels includes cellulosic ethanol, but first the lignin sheath that surrounds the cellulose fibers must be isolated from the carbohydrate components. We are exploring the use of supercritical fluids, microwave irradiation and ionic liquids for the fractionation and hydrolysis of native grasses, distillers dried grain with solubles and soybeans. A major effort has just been initiated to use ionic liquids in the pyrolysis of prairie cordgrass into military jet fuel. We have used supercritical fluid extraction to isolate a biodegradable polymer from the fermentation of distillers dried grain with solubles. Finally, supercritical carbon dioxide is being utilized in refining beeswax and tanning leather.

• Doolittle, J., Gonzales, J., Moutsoglou, A., Raynie, D. and Menesh A. "Next-Generation Bio-JP-8 Fuel." U.S. Army Research Laboratory, Oct. 1, 2009-Oct. 31, 2010, $289,445.
• Gibbons, W.R., Gonzales, J., Twedt, M., Raynie, D., Julson, J. and Muthukumarappan, K. "Developing a Sustainable Feedstock and Next-Generation Processing Technologies for Biofuels Production." U.S. Department of Transportation (via Sun Grant Initiative), July 1, 2007-June 30, 2012, $99,008.
• Ruan, R., Gibbons, W., Muthukumarappan, K. and Raynie, D. "Develop Sustainable Energy Systems for Practical Utilization of Bulky Biomass." U.S. Department of Transportation (via Sun Grant Initiative), July 1, 2007-June 30, 2012, $145,500.
• Gibbons, W., Owens, V., Boe, A., Gonzales, J., Muthukumarappan, K., Raynie, D., Twedt, M., Julson, J., Bassett, K. and Moutsoglou, A. "Developing a Prairie Biorefinery." U.S. Department of Transportation (via Sun Grant Initiative), Feb. 1, 2007-Jan. 31, 2011, $88,500.
• Winter, R., Gibbons, W.R., Muthukumarappan, K., Raynie, D. and Twedt, M. "Center for Bioprocessing Research and Development." State of South Dakota, July 1, 2006-June 30, 2011, no direct funding.
• Thiex, N. and Raynie, D.E. "Development of Innovative Regulatory Inspection Methods: The Assessment of Aminoglycoside Antimicrobials in Animal Feeds." U.S. Food and Drug Administration (via South Dakota Department of Agriculture), Oct. 1, 2002-Sept. 30, 2003, $45,927.70.
• Raynie, D., Gibbons, W.R., Muthukumarappan, K., Julson, J., Krishnan, P., Wang, C. Y., Nelson, R. and Martin, R. "Fermentation of Soybean Meal to Make Ethanol and Value-Added High Protein Products." United Soybean Board, Oct. 1, 2008-Jan. 31, 2010, $14,417.
• Gibbons, W.R., Raynie, D., Muthukumarappan, K., Julson, J., West, T., Dalaly, B., Schmidt, C., Krishnan, P. and Owens, V. "Extrusion/Extraction-Based Biorefinery." U.S. Department of Energy (via Sun Grant Initiative), Aug. 1, 2005-July 31, 2008, $132,000.

1. L.N. Tenlep, N.S. Thiex and D.E. Raynie, "Compositional Analysis of Chemically Pretreated Biomass Samples," Journal of ASTM International (in press).
2. J.L. Driver, N.S. Thiex, D.E. Raynie, M. Ofitserova and M. Pickering, "Single-Laboratory Validation for the Quantification of Neomycin B and Neomycin C in Animal Feeds by Liquid Chromatography-Fluorescence Detection with Post-Column Derivatization," Journal of AOAC International 92, 34-41 (2009).
3. D.E. Raynie, "Modern Extraction Techniques," Analytical Chemistry 78, 3997-4004 (2006).
4. J.L. Driver and D.E. Raynie, "Method Development for Biomolecules," in HPLC Method Development of Pharmaceuticals, S. Ahuja and H. Rasmussen (editors), Elsevier, New York, pp. 425-440 (2007).
5. A.H. Ullman and D.E. Raynie, "Problem-Solving and Guidelines for Method Selection," in Comprehensive Analytical Chemistry, 47, 799-848, S. Ahuja and N. Jespersen (editors) (2006).
6. A. Dupay, N. Thiex, D. Ferris and D.E. Raynie, "Method Development for the Determination of Neomycin in Animal Feed," Proceedings of the South Dakota Academy of Science 83, 269 (2004). D.E. Raynie, "Modern Extraction Techniques," Analytical Chemistry 76, 4659-4664 (2004).
7. D.E. Raynie, "A Fundamental Understanding of the Chemical Extraction Process," Encyclopedia of Separation Science, I.D. Wilson, T.R. Adlard, C.F. Poole and M. Cooke (eds.), Academic Press (2000).
8. T.L. Chester, J.D. Pinkston and D.E. Raynie, "Supercritical Fluid Chromatography," Analytical Chemistry 70, 301R-319R (1998).
9. D.E. Raynie, "Meeting the Natural Products Challenge with Supercritical Fluids," ACS Symposium Series 670, 68-75 (1997).
10. T.L. Chester, J.D. Pinkston and D.E. Raynie, "Supercritical Fluid Chromatography and Extraction," Analytical Chemistry 68, 487R-514R (1996).
11. T.L. Chester, J.D. Pinkston and D.E. Raynie, "Supercritical Fluid Chromatography and Extraction," Analytical Chemistry 66, 106R-130R (1994).
12. D.E. Raynie and T.E. Delaney, "Effect of Entrained Helium on the Kinetics of Supercritical Fluid Extraction with Carbon Dioxide," Journal of Chromatographic Science 32, 298-300 (1994).
13. D.E. Raynie, "Warning Concerning the Use of Nitrous Oxide in Supercritical Fluid Extractions," Analytical Chemistry 65, 3127-3128 (1993).
14. D.E. Raynie, K.M. Payne, K.E. Markides and M.L. Lee, "Evaluation of Microbore and Packed Capillary Column Chromatography with an Ethylvinylbenzene-Divinylbezene Polymeric Packing Material and Supercritical Ammonia as the Mobile Phase," Journal of Chromatographic Science 638, 75-83 (1993).
15. H. Liu, L.M. Cooper, D.E. Raynie, J.D. Pinkston and K.R. Wehmeyer, "Combined Supercritical Fluid Extraction/Solid-Phase Extraction with Octadecylsilane Cartridges as a Sample Preparation Technique for the Ultratrace Analysis of a Drug Metabolite in Plasma," Analytical Chemistry 64, 802-806 (1992).
16. T.L. Chester, J.D. Pinkston and D.E. Raynie, "Supercritical Fluid Chromatography and Extraction," Analytical Chemistry 64, 153R-170R (1992).
17. D.E. Raynie, D.R. Nelson and K.T. Harper, "Alkaloidal Relationships in the Genus Arctomecon (Papaveraceae) and Herbivory in A. humilis," Great Basin Natural. 51, 397-403 (1991).
18. D.E. Raynie, K.E. Markides and M.L. Lee, "Boiling Range Distribution of Petroleum and Coal-Derived Heavy Ends by Supercritical Fluid Chromatography," Journal of Microcolumn Separations, Sept. 3, 423-433 (1991).
19. S.H. Page, D.E. Raynie, S.R. Goates, M.L. Lee, D.J. Dixon and K.P. Johnston, "Predictability and Effect of Phase Behavior of CO2/Propylene Carbonate in Supercritical Fluid Chromatography," Journal of Microcolumn Separations, Sept. 3, 355-369 (1991).
20. D.E. Raynie, M.L. Lee, D.R. Nelson, K.T. Harper, E.W. Mead and F.R. Stermitz, "Alkaloids of Arctomecon spp. (Papaveraceae). 12-Methoxyallocryptopine, a New Protopine-type Alkaloid," Biochemical Systematics and Ecology 18, 45-48 (1990).
21. D.E. Raynie, "In Praise of Microcolumn Abstracts," Journal of Microcolumn Separations, Sept. 2, 264-265 (1990).
22. D.E. Raynie, "Definition and Description of Supercritical Fluid Chromatography," "Historical Development of SFC," "Fluorescence Detection," "Variable Restriction for Flow Control" and "Preparation of Mixed Mobile Phases," Analytical Supercritical Fluid Chromatography and Extraction, M.L. Lee and K.E. Markides (eds.), Brigham Young University Press (1990).
23. D.E. Raynie, K.E. Markides, M.L. Lee and S.R. Goates, "Back-Pressure Regulated Restrictor for Flow Control in Capillary Supercritical Fluid Chromatography," Analytical Chemistry 61, 1178-1181 (1989).
24. D.E. Raynie, S.M. Fields, N.M. Djordjevic, K.E. Markides and M.L. Lee, "A Method for the Preparation of Binary Mobile Phase Mixtures for Capillary Supercritical Fluid Chromatography," Journal of High Resolution Chromatography 12, 51-52 and 409 (1989).
25. D.E. Raynie, S.A. Farnum and Y.R. Potts, "Gas Chromatographic Techniques for the Analysis of Hydrocarbons in Low-Rank Coal Liquefaction Products. Part II. Instrumental Aspects." Proceedings of the North Dakota Academy of Science 38, 70 (1984).
26. Y.R. Potts, S.A. Farnum and D.E. Raynie, "Gas Chromatographic Techniques for the Analysis of Hydrocarbons in Low-Rank Coal Liquefaction Products. Part I. Data Treatment." Proceedings of the North Dakota Academy of Science 38, 69 (1984).