The Department of Chemistry welcomes its undergraduates to participate in ongoing research in the Department. For academic credit to be awarded for such research, however, the guidelines set up by the Department must be adhered to.
Research opportunities in biochemistry, electrochemistry, or in analytical, organic, inorganic, physical, and polymer chemistry are available. Students interested in obtaining academic credit for research must enroll in Courses 84.407/408 (Undergraduate Thesis I and II). Both courses must be taken, and no more than six credits may be applied towards meeting degree requirements. Written progress reports are required, as well as the preparation and presentation of a written thesis. Permission of the Department Chairperson and of the faculty member who will be supervising the research is required.
Credit for courses 84.407/408 may be used by chemistry majors for credit and as a chemistry elective only when the thesis is under the direction and direct supervision of a member of the chemistry department faculty. Interdisciplinary research may be used for chemistry credit only when the thesis is under the direct supervision of a member of the chemistry faculty, with the second department involved in an advisory role or supportive role.
Current Faculty Undergraduate Research Projects
Below are faculty-led research projects in which undergraduates can participate:
Professor Eugene F. Barry
Professor Ruxanda Dima
Professor Daniel J. Sandman
PROFESSOR EUGENE F. BARRY
Computer-assisted predictions of high-speed gas chromatographic separations.
The gas chromatographic behavior of a mixture is represented by the retention times corresponding to the different sample components. Optimizing separations can be done by altering column parameters such as column length, column internal diameter, stationary phase polarity and stationary phase film thickness as well as operational parameters such as carrier gas flow, and column temperature. A complete understanding of how these parameters affect the separation is very useful in column selection and method development. Frequently column selection and operating conditions are based on previous knowledge, information from literature and trial-and-error which is usually time consuming. Computer simulation, on the other hand, has emerged as a useful tool for separation optimization. Many reviews demonstrate satisfactory accuracy in prediction and optimization of various separations with computer assistance [1-5].
Method development can be somewhat tedious for the case of temperature programming separation which is a major mode of capillary gas chromatography. Resolution and retention time depend on heating rate, starting temperature and temperature programming profile (linear or multi-linear). Thus, a large number of experiments may be required to adequately explore the various separation options. Computer simulation can greatly reduce the time and effort required for method development in gas chromatography while achieving a satisfactory separation. DryLab (LC Resources, Lafayette, CA) is one type of software that simulates a separation based on experimental data. Initially, two experimental runs at different heating rates are performed. The retention data is then entered into the software, after which, a separation under any other condition can be simulated. Predictions of separations can be made for (i) isothermal runs at any temperature, (ii) linear temperature programming runs for any starting temperature and heating rate and (iii) multi-linear temperature programming runs. Both expert and novice chromatographers can benefit from this software. Those who are new to chromatography can gain an understanding of separation variables without occupying instrument time or consuming chromatography materials. Experts can use the program to drastically reduce the time typically involved in getting a satisfactory separation or developing a complete method. Moreover, in-depth studies on the effects of separation variables can be applied.
Although other workers have reported on the use of computer simulation to predict and optimize gas chromatographic separations, their applications are analyzed using conventional gas chromatographic conditions [6-10]. In this chapter, the use of DryLab software to predict and optimize separation under high-speed gas chromatographic conditions is described. The accuracy of DryLab was first evaluated under conventional gas chromatographic conditions for separation of polycyclic aromatic hydrocarbons (PAHs) and fatty acid methyl esters (FAMEs). Then predictions of separations under high-speed gas chromatographic conditions were studied. Predicted and experimental separations are compared and examined.
PROFESSOR R. DIMA
(1) application of database mining approaches and other bioinformatics methods to the determination of binding motifs at interfaces between various biological molecules; the goal of this research is to build a repository of specific and non-specific interactions between macromolecules which can be used for targeted drug-design.
(2) development of methods that detect evolutionary relationships between proteins or RNA molecules with special focus on interacting partners.
(3) study of the conformational space in proteins using simplified methods that encode specific characteristics of the polypeptide chain; this project targets especially the metastable states that represent obligatory intermediates on the pathway of folding of a protein from a fully unfolded state to its native functional form.
(4) study of proteins associated with amyloid diseases to reveal the initial steps in the association process.
PROFESSOR DANIEL J. SANDMAN
In general, my research interests involve the synthesis and physico-chemical study of organic, organometallic, and polymeric materials, especially those involving conjugated electronic structures of interest for potential optical and electronic properties. Current research activities involve two kinds of projects involving conjugated polymers, namely approaches to such materials using solid-state polymerization and the use of sugar reagents to synthesize conjugated polymers.
Approaches to Conjugated Polymers Using Sugar Reagents
It is desirable to use sugar reagents to bring about synthesis because of their ready availability from renewable sources, low cost, and water solubility. An undergraduate student initiated our work in sugars, and we have demonstrated the advantages of the use of unprotected sugars in reactions of dicyanoalkenes and –arenes to form conjugated polymers and the well-known molecular cyclotetramers, phthalocyanines. This work involves the use of sugars as either reducing agents or nucleophiles and has been reviewed. (1) Our current focus involves the use of sugars as electrophilic and oxidizing reagents, and we are the first to use such reagents. (2) We have shown that selective functionalization of the primary hydroxyl group in glucopyranoses with halide or sulfonate allows polymerization of ethynylpyridines leading to polymers that are water-soluble. We are interested in optimizing these polymers to obtain high molecular weight materials and to understand mechanistic aspects of these reactions. In addition, we are interested in the use of Cu (II) and Fe (III) complexes of sugars to initiate the oxidative polymerization of electron-rich compounds such as aniline and thiophenes under mild aqueous conditions. (2) The Fe (III) complexes require detailed characterization as current samples are structurally amorphous and may be polymeric.
Approaches to Conjugated Polymers via Solid State Polymerization
While the overwhelming majority of polymers are not crystalline, it is possible in certain cases such as diacetylene polymerization to obtain macroscopic single crystalline specimens of polymers. These polymer crystals have properties that have a higher degree of definition than noncrystalline specimens. We are interested in the study of diacetylene polymers for details such as understanding the role of lattice mechanical strains in the thermochromic phase transition of urethane substituted diacetylene polymers (3) and the extension of the discovery of charge-transfer spectra (4) to new conductive systems. We are also interested in expending the scope of lattice controlled solid-state polymerizations to monoacetylenes. (5)
All facilities of the Center for Advanced Materials will be available to undergraduate students involved in these projects.
D.J. Sandman, et al., "Conjugated Materials: Problems and Prospects for Synthesis Using Carbohydrate Reagents" Synthesis, 1147-1156 (2002).
M. Keddy, R. Gurney, B. Tran, and D.J. Sandman, "Approaches to Conjugated Polymers via Electrophilic Carbohydrate Reagents", Polymer Preprints, 46 (1), 601-602 (2005). 2. D.-C. Lee, S.K. Sahoo, A.L. Cholli,and D.J. Sandman, "Structural Aspects of the Thermochromic Transition in Urethane Substituted Polydiacetylenes", Macromolecules, 35, 4347-4355 (2002).
J.L. Foley, L. Li, D.J. Sandman, M.J. Vela, B.M. Foxman, R. Albro, C.J. Eckhardt, "Side Chain Interactions in a Polydiacetylene Single Crystal", J. Am. Chem. Soc., 121, 7262-7263 (1999).
J.M. Njus, L. Yang, B.M. Foxman, and D.J. Sandman, "Thermal Solid State Polymerization of 4-Ethynylbenzoic Acid", Polymer Preprints, 44 (1), 905-906 (2003).