Fullerene Chemistry:
An Integrated Laboratory Module
as a Component of a
Comprehensive New Curriculum for Advanced Chemistry Laboratories

Cover Page

A proposal to the Camille and Henry Dreyfus Foundation from

The Department of Chemistry, MS 60
Rice University
6100 Main Street
Houston, TX 77005-1892
Graham P. Glass, Chair

Phone: 713-527-4082
FAX: 713-285-5155
Email: chem@ruf.rice.edu

Project Director:
Kenton H. Whitmire, PhD
Professor of Chemistry
Phone: 713-737-5650
Fax: 713-737-5652
Email: whitmir@rice.edu
Website: http://www.ruf.rice.edu/~whitmir


The Department of Chemistry requests support to implement an innovative advanced, integrated laboratory program that results from a comprehensive restructuring of the entire undergraduate curriculum.. The support from the Dreyfus Foundation will be used to fund a module of this program focussing on fullerene chemistry. Based upon an integrated laboratory philosophy, this module will incorporate synthetic, analytical and physical chemistry into a single multifaceted project using state of the art instrumentation.

The Need

The Department of Chemistry of Rice University requests support from the Camille and Henry Dreyfus Foundation in order to implement an important part of a comprehensive restructuring of the undergraduate chemistry laboratory program. The contribution from the Dreyfus Foundation, when combined with university matching funds, would allow us to implement the entire first phase of a proposed new advanced undergraduate laboratory teaching program.

Rice University has recently constructed a new state-of-the-art facility, the Center for Nanoscale Science and Technology, which will house about one third of the chemistry department's faculty as well as all of our undergraduate teaching laboratories. This facility was funded in large part to foster interdisciplinary research in the emerging area of nanoscience as a logical outgrowth of the Nobel Prize-winning research conducted in our department by Professors Richard E. Smalley and Robert F. Curl. The prospect for utilizing this new facility, which we are scheduled to occupy beginning September 22, 1997, is very exciting. Besides enabling new fundamental research to be performed, it will allow us to finally face the challenge of providing the highest quality educational laboratory experience for our undergraduates. In preparation for our move, we began an intense study of the entire undergraduate chemistry curriculum more than a year ago, and have now formulated what we believe to be an innovative plan which will greatly improve our laboratory offerings. It will provide more flexibility and choice for our undergraduates, as well as provide for a program of continuous laboratory development and renewal. If funded, the new advanced undergraduate laboratory curriculum will be implemented beginning in the 1998-1999 academic year.

The Context

The entire laboratory curriculum from freshman year to graduation will be revised in what we envision to be an overarching and continuing reform process. The vision for the introductory years will be briefly presented here in order to give an understanding of our complete vision for the curriculum and to place the advanced laboratory sequence into perspective, although support from the Dreyfus Foundation is being requested only for the advanced program.

Changes in the Freshman and Sophomore Years: In the past there has been a single, one-semester introductory laboratory which has been heavily analytical and physical in nature. Beginning with the 1998-1999 academic year, the laboratory program will be folded into the lecture sequence and specific experiments will be chosen to track with the lecture material, thus providing reinforcement and physical substance to the concepts introduced in the lectures. We plan to choose project-oriented experiments as much as possible in a "discovery" context. Some of the experiments we intend to include are among those being developed by the MC2 consortium funded by the National Science Foundation (Dr. Susan Kegley, University of California at Berkeley, PI). Dr. Mary McHale, our new departmental undergraduate laboratory coordinator, will be visiting Berkeley later this fall to explore details of implementation and adoption of this program into our curriculum. The Department plans to seek funding from the Curriculum and Course Development Program of the Division of Undergraduate Education of the National Science Foundation in order to implement these changes.

In recent years, the introductory organic chemistry laboratory has relied heavily on microscale experiments developed in order to minimize chemical exposure problems due to inadequate numbers of fume hoods in the old facilities. While this type of laboratory has advantages in reducing the quantities of chemicals consumed and limits the amount of waste materials produced, we have concluded that it is too removed from the actual practice of organic chemistry in research labs and in industry to be a satisfactory experience for our students. With the new facilities it will be possible to reintroduce macroscale syntheses. In addition, given the fundamental importance of high field nuclear magnetic resonance spectroscopy (NMR) to modern organic chemistry, we plan to introduce experiments involving hands-on NMR studies into both the introductory organic course and into an advanced laboratory module specifically designed to teach modern NMR techniques. We intend to seek funding for an NMR spectrometer dedicated primarily to the undergraduate teaching laboratories. Another foundation will be approached for the funding of this instrument.

The Advanced Laboratory Program - A Modular Approach; Over the last two or three years, a number of modular labs have been successfully incorporated into the undergraduate curriculum of the biosciences at Rice. Since we have close ties to the two departments that jointly administer this curriculum, we have followed the successful development of these labs with great interest, and have learned much from the experience. As a result, we are convinced that a modular approach to the advanced laboratory curriculum in chemistry offers significant advantages. Thus, we are proposing that all of our advanced laboratories be offered in modules starting with an introductory semester (two modules) of general training in synthetic organic/inorganic chemistry and in analytical techniques. Chemistry majors would be required to take at least four modules in addition to the introductory semester. However, we anticipate that many students will opt to take more than the required number. The specific modules that an individual student will take will be chosen with the approval of a departmental committee whose membership will embrace all of the major branches of chemistry. In discussing the requirements for the degree, the department placed a high priority on offering students a range of opportunities that reflect the growing diversity of career opportunities now available for chemistry graduates. These options should allow students to make choices consistent with their individual educational and career goals. The department feels that the proposed oversight committee represents the best mechanism for assuring that the elements of individual choice exist while maintaining balance and breadth in each student's experience. The bold new program that we envision entails considerable equipment needs.

The modular approach to laboratory teaching is very exciting because it represents a new way of organizing the traditional disciplines of inorganic, organic, physical and analytical chemistry in a way which should provide an integrated lab experience. In addition, laboratory modules which incorporate other disciplines such as materials science, electrical engineering, chemical engineering are in the planning stage. We also have plans to accept credit for some laboratories offered by other departments (e.g., advanced biochemistry labs) and to cross list some of our modules with other departments. What we hope to achieve is an experience that is closer to that encountered in modern research rather than insist on the arbitrary boundaries of the traditional disciplines. Thus, most of the modules that we are developing, including the one in lithographic chemistry which we intend to offer jointly with the Department of Electrical Engineering, are, as much as possible, interdisciplinary in nature combining as many of the elements of the traditional subject areas as feasible in one module. To support and augment these modules, we will have a few highly specialized modules, for example in nuclear magnetic resonance spectroscopy or in electron microscopy, which will meet the needs of students who wish to have some specialized training that involves serious hands-on skill-building. It is not intended, however, that the students' overall laboratory experience be dominated by such specialized modules.

One module of particular note that we wish to develop in the initial phase of the reorganization, focuses on the chemistry of the fullerenes. This is particularly relevant given that these very important compounds and materials were discovered in Nobel-Prize-recognized research carried out at this university. We very much wish our undergraduates to have exposure to this type of cutting-edge research as part of their undergraduate laboratory experience. As will be seen in the more detailed description provided below, this is a particularly appropriate module for an integrated lab as it utilizes a wide range of synthetic, analytical and physical techniques.

Besides the introductory modules which will be offered every year, we intend to offer six additional modules spread out over the two semesters of each year. Some of these will be offered regularly based upon demand (we expect the fullerene module to be one such offering), others may be available only in alternate years. This will allow for the continual development of new modules that will be introduced in response to new developments in chemistry and related disciplines.

Description of Proposed Modules

Introductory Semester: The introductory modules are designed to introduce students to methods in both inorganic and organic synthesis as well as routine analytical procedures. The experiments chosen for incorporation in these modules have been used very successfully in our honors freshman and organic synthesis laboratories.

Inorganic Synthesis and Characterization Module: The first half of the semester (or module) will deal with the synthesis of tetraphenylporphyrin and its metallated derivatives. These biologically important molecules represent a very broad field of coordination compounds. The molecules are synthesized in simple procedures involving refluxing solvents and distillation. Their purification is accomplished by column chromatography and/or fractional recrystallization. They are very conveniently characterized by infrared spectroscopy, UV-vis spectroscopy, magnetic susceptibility measurements, and 1H and 13C NMR (depending upon the magnetism of any metal ions present). Depending upon the metal chosen, the metallated version may also undergo interesting reversible electrochemical waves which can be studied via cyclic voltammetry.

Organic Synthesis and Characterization Module: The second module will introduce organic chemistry techniques with a 6-step macro scale synthesis of fluoxetine. The procedure is technically challenging, as enantioselective catalysts are prepared and used to create the chiral starting compound. Most of the steps must be run under argon. The department has successfully piloted this project with inexperienced undergraduate assistants. We are confident that most students will be successful in this project. The conventional spectroscopic methods introduced in the first part of the module will also be used to characterize the compound and the intermediates which lead to it. This will involve a great deal of NMR characterization as well as the introduction of the concepts of optical activity and optical rotation which will be measured using an existing polarimeter.

Equipment need: Three additional rotary evaporators are needed to supplement those that we already have. This will be necessary in order for the introductory module to accommodate the number of students which will be taking this class. The rotary evaporators chosen are Buchi/Brinkmann Rotary Evaporator Model #144A with a quoted price of $3,660 each.

Fullerene Module - Synthesis, Chemistry and Physics of C60: C60 will be synthesized following a standard literature procedure and extracted from the soot using a continuous extraction apparatus. Final purification will be achieved by column chromatography over alumina. C70 will also be isolated during this step. The C60 will be reduced to C60H2 by diimide and isolated by preparative HPLC using a commercially available Buckyclutcher column. An organometallic derivative such as C60Pt(PPh3)2 will also be prepared. These compounds will be characterized by infrared and UV-vis spectroscopy. Cyclic voltammetry of C60 will demonstrate the use of electrochemistry in determining multiple reversible reduction waves.

Pulses from a Nd:YAG laser system already dedicated to the advanced laboratory program will be used to excite deoxygenated solutions of C60 and C60H2. The resulting triplet state population will be monitored through absorption of a simple red diode laser beam that is detected by a silicon photodiode and a digitizing oscilloscope. Students will measure decay kinetics of the C60 triplet states for a range of conditions and then analyze their data to find rate constants for triplet-triplet annihilation, quenching by ground state species, and intrinsic triplet decay.

Equipment need: A fullerene generator ($4,000, fabricated in house) will be needed to produce the raw fullerene samples. A state of the art electrochemical analyzer (BioAnalytical Systems CV50-W electrochemical analyzer with PC controller, software and accessories package (electrodes, polishing kit, electrochemical cell, etc.); $13,650) will also be required. The triplet lifetime measurements will be made using an existing Nd:YAG laser from New Wave Research but ancillary equipment will be needed. This includes a 670 nm diode laser for probing (Power Technology, Inc.; $500), sealable sample cells (fabricated in house; $200), silicon photodiode detectors (EG&G; $200), optics and mounts ($2000), a digitizing oscilloscope (Tektronix TDS-430-A; $4,700) and an apparatus control computer with interface (Dell, National Instruments; $2,500) for a total cost of $10,100.

Catalysis Module: Most organic chemicals produced in bulk quantities are derived from natural gas or petroleum, usually by their conversion into alkenes. The use of soluble transition metal complexes as homogeneous catalysts for the conversion of these unsaturated substances into polymers, alcohols, ketones, carboxylic acids, etc., is of great interest. The compound most responsible for changing modern homogeneous catalysis, RhCl(PPh3)3 - commonly called "Wilkinson's catalyst", is readily prepared and is active for the hydrogenation of olefins at 25 oC and 1 atm H2. It is especially appropriate for study in an undergraduate laboratory because it is involved in a well-defined sequence of reactions which can be monitored spectroscopically. It is intended that this basic laboratory unit in transition metal chemistry and catalysis will involve the following steps: synthesis and characterization of RhCl(PPh3)3, the determination of the relative rates of hydrogenation of terminal versus internal alkenes and the effect of different phosphines and their concentrations. Techniques and concepts that will be developed include: 1H and 31P NMR, GC, handling flammable gases, phosphine cone angle, catalyst cycles, kinetics, and reactions of transition metals.

Equipment need: This module can be conducted using existing equipment.

Computer Modeling: With the advent of powerful molecular modelling software and graphical interfaces for quantum chemistry programs such as Gaussian, computational chemistry has become an invaluable and necessary tool for physical and synthetic chemists alike. This module will introduce students to a number of modelling programs used in industrial and academic laboratories. A laboratory format is an ideal way in which to illustrate the applications of these programs, and students will be given various problems to solve using computational chemistry. Projects will be drawn from diverse areas and could include the use of molecular simulations to visualize large biomolecules and the computation of vibrational spectra of simple inorganic complexes.

Equipment need: 3 computer workstations with 64 Mb of memory and 2 Gb hard disk at $7,495 list price with 30% university discount for a final price of $5,246 each or $15,740 total.

Lithographic Chemistry: Molding the Shape of Silicon: This module, which is designed to run as a semester class, will be jointly taught by members of the chemistry and electrical engineering department. Its purpose will be to introduce advanced chemistry majors and interested electrical engineers to basic methods of lithography. The first project will revolve around the synthesis and characterization of molecules which when illuminated with light create acids. This synthesis is relatively straightforward and produces photoacid generators active in the ultraviolet region of the spectrum at high yield. Next, students will blend these molecules with monomers making a photoresist and use vibrational spectroscopy to evaluate the kinetics of the photoinduced reactions. Finally, students will actually do lithography on silicon using both their own and a variety of commercial photoresists. The final characterization will involve both scanning tunneling microscopy as well as scanning electron microscopy.

Equipment need: Atomic Force Microscopy (AFM) Attachment Upgrade (Burleigh Metris-2000) for the existing Burleigh Metris-1000 Scanning Tunneling Microscope at $14,500.

Solid State Chemistry: In this module students will learn techniques of solid state synthesis. One experiment will synthesize high Tc superconducting phases such as YBa2Cu3O8-x using conventional solid state methods. Students will also prepare soluble precursors (some of which are air sensistive) and prepare the material using the sol-gel methodology which has become a very important industrial technique in solid state synthesis. The samples prepared by different means will be compared. Analyses will be carried out by measuring the x-ray powder diffraction pattern, magnetic properties on the department's existing Quantum Design SQUID magnetometer. The Meissner effect will also be examined. Students will be sent to the literature to find other high Tc superconducting copper oxide materials and will be allowed to design their own synthesis of a new material and test its physical properties using the same techniques as above.

Equipment need: Fisher Isotemp Muffle furnace for carrying out the solid state syntheses. List price is $3176 with university discount giving a final price of $2224.

The Chemistry of Fermentation: The beer-making process provides the ideal focus for a module which integrates both biochemical as well as analytical chemistry lab techniques. Students will culture different strains of brewer's yeast and analyze the organisms for the presence of particular enzymes which provide the yeast with the ability to impart specific sugars and esters to beer. By using these same organisms to ferment their own beer, they can then analyze their products for the presence of certain complex sugars and simple esters. This analysis process involves basic methods of separation and extraction as well as derivatization. A number of modern analytical tools, including NMR, mass-spectroscopy and HPLC, will be used to identify the important sugars and esters responsible for the flavors in different types of beer. Commercial samples will be analyzed for comparison to the lab synthesized materials.

Equipment need: This module can be implemented using existing equipment.

The Demographics of Rice University and Its Department of Chemistry

Rice University is an institution dedicated to providing a high quality undergraduate education in a wide range of disciplines including natural sciences, engineering, social sciences and humanities. Highly recognized centers, many of which have been developed in the past two decades, include the Shepherd School of Music, the Baker Institute for Public Policy, the Rice Quantum Institute (of which Professors Smalley and Curl are members), the Keck Institute for Computational Biology, the Cox Laboratory for Biomedical Engineering and the Center for Research on Parallel Computation.

The student body is composed of approximately 2600 highly-accomplished undergraduate students. This year, the middle 50th percentile of entering freshman have SAT scores between 1350 and 1500 with 131 of the 704 entering freshman ranked number one in their high school class and 60% were ranked in the top 5% of their graduating classes. These figures are probably low since 25% of the students came from schools that did not report a class standing. While the numbers of National Merit scholars is not yet available for the current freshman class, the past three classes have had between 230 and 240 such scholars (approximately 35% of each entering class).

Enrollments in the freshman chemistry program average in the range of 350 students total for the General Chemistry and Honors Chemistry Classes. The introductory organic chemistry class typically has an enrollment of ca. 250 while on the order of 70 students take the junior level physical chemistry class. Over the past five years, the number of chemistry majors has varied between 18 and 26. Of those who have graduated, approximately 60% went on to graduate school in chemistry while about 30% chose further study in other professional programs (law and medicine) and the remaining 10% went directly into the chemical or related industries.

Besides the stellar undergraduate program, Rice University the graduate research program in chemistry which is nationally and internationally recognized. There are currently 19 faculty and 69 graduate students in the department with research programs in a variety of disciplines including synthetic organic chemistry, bioorganic chemistry, organometallic chemistry, inorganic chemistry and bioinorganic chemistry, physical chemistry and chemical physics. Many of the faculty are working in interdisciplinary areas such as materials science and nanoscience and a number of collaborative programs with professors in these departments have been established. In total the research programs in the Department of Chemistry received ca. $5.2 million dollars in external research funding in fiscal year 1997. The recent awarding of the Nobel Prize to Professors Smalley and Curl is a high point in the history of our department. The research accomplishments of many of our faculty have been recognized in numerous ways including the prestigious fellowships including Alfred P. Sloan Fellowships (6), Dreyfus Fellowship (1), DuPont Young Faculty Fellowship (2), Humboldt Research Fellowship (1) and Senior Scientist Award (3). Four of our faculty have attained the honor of being members of the National Academy of Sciences.

All of the proposed changes will be implemented during the two year period of the academic years 1998-1999 and 1999-2000. In the first year, we plan to implement the introductory modules as well as three advanced modules. The three modules to be implemented in the first year are: the fullerene module, the lithographic chemistry module, and the computer modelling module.

The Department of Chemistry feels very strongly that this program will be of general interest to the educational community and has committed to publishing the design and implementation of this modular program in a suitable journal such as the Journal of Chemical Education as well as presenting this development at suitable conferences and workshops in chemical education. A website will be developed and maintained by the department where these results will be accessible to the general public. As part of the development of the laboratory program, a laboratory manual will be prepared, published and distributed to those interested in developing a modular advanced laboratory program.

We thank you very much for your consideration of this proposal.