MIT Reports to the President 1998-99

DEPARTMENT OF CHEMISTRY

In the 1998—1999 academic year, the Chemistry Department continued its strong program in research and undergraduate and graduate education. Four new faculty were recruited and will arrive during the summer of 1999, reflecting new strength in both the organic and biological chemistry sections of the department. In the latest rankings, our department placed second nationally and first in inorganic chemistry. Associated with the department currently are 213 graduate students, 105 postdoctoral researchers, and 118 undergraduate chemistry majors. Growth in all three categories is expected in the next few years owing to the increase in faculty, restoring us to near the strength we enjoyed prior to MIT's early retirement program.

As of July 1, 1999 the Chemistry Department Faculty comprises 29 full-time faculty members including 5 Assistant, 2 Associate and 21 Full Professors. New faculty appointments during this year include Cathy Drennan and Timothy Jamison on July 1 (as both Assistant Professors) and Barbara Imperiali also July 1 as full Professor. Harald Schwalbe has just accepted our offer and will join us in the late summer as an Assistant Professor, raising our number to 30 FTE's. Professor Gregory C. Fu was promoted from Associate Professor without tenure to Professor with tenure and Professor Dietmar Seyferth retired effective June 30, 1999. He will remain as a 49 percent Professor without tenure for a three year period.

INFRASTRUCTURE DEVELOPMENTS

The MIT Chemistry 2000 campaign, helping to finance the renovation of 90,000 square feet of laboratory space, is now complete more than a year ahead of schedule. Generous gifts and pledges from department alumni/ae this year have brought us to our $4M external funding goal. These campaign resources (including a challenge grant from Visiting Committee Chair Richard Simmons), combined with department and Institute commitments, have enabled $21 million of reconstruction in buildings 2, 4, and 6. A $42M renovation of building 18, approved by the central administration, is far along in the planning process and construction will begin in the next academic year. We summarize below the progress made in the main buildings.

Relocation of the departmental X-ray laboratory was completed in February and Dr. Bill Davis moved the equipment to Bldg. 2, room 325, formerly occupied by the Chemistry Education Office. The new facility contains separate rooms for the diffractometer, computers, and Bill's office.

Renovations in the basement of building 2 to create Laser labs for the Nocera, Nelson and Tokmakoff groups are well underway. The current completion date for these labs is scheduled for fall of 1999. At that time, these groups will move back to the basement from their temporary location in the Francis Bitter Magnet Lab. Following shortly after these labs are finished, the renovations of the Field lab will finished, currently projected to the first half of October. When this lab is completed, the Field and Steinfeld group will share these new labs so the last phase of the laser lab renovation project, the Steinfeld lab, can begin. Completion of the Steinfeld lab is projected for the end of the year.

The Schrock group has already moved into swing space in the 1st floor of building 18. The Cummins group will be moving into swing space in the Seyferth labs in building 2 during construction. These renovations are projected to be complete around the end of this year. Although the original schedule projected completion in the early fall, extensive redesign of the roof top fume hood exhaust system delayed the final design, and thus the completion date has been pushed back.

The design development (DD) phase of the building 18 renovations is currently in progress. Iterative meetings between the architects, Goody, Clancey Associates, and the research groups of the building are in progress. The objective of these first series of meetings is to document and understand how the researchers use their space, the instruments that must be housed within the respective labs, and the initial layout designs. This phase, anticipated to continue through late summer, will be followed by the final design and the development of construction documents (CDs). The CDs are the documents upon which contractors will bid.

A major design goal of the building 18 renovations is a significant increase of the linear feet of fume hood per researcher. In order to reach this goal while staying within the air handling system capacity, it will be necessary to use a new fume hood design. Fume hoods from two manufacturers are currently under consideration.

FACULTY AWARDS AND HONORS

Professor Rick Danheiser was awarded the 1998 School of Science Prize for Excellence in Undergraduate Teaching

Professor Keith Nelson's start-up company Active Impulse Systems was sold to Royal Philips of the Netherlands, the company developed an optical metrology instrument used for measurement of metal film thicknesses in microelectronics fabrication.

Professor Peter H. Seeberger was selected as the Firmenich Career Development Professor of Chemistry

Professor Bruce Tidor was named an Alfred P. Sloan Research Fellow

Professor Andrei Tokmakoff was selected as the recipient of the Paul M. Cook Career Development Professorship.

RESEARCH HIGHLIGHTS

Steve Buchwald: During the last year the Buchwald group have developed a family of ligands that greatly enhance palladium-catalyzed cross coupling processes which are of tremendous importance in the pharmaceutical industry. These findings will be of great significance to those in both drug discovery (combinatorial chemistry, lead development) and manufacture. In addition, the same chemistry has broad application in a number of other areas of chemistry including electronic materials, polymer chemistry and pigments.

Jianshu Cao: Marcus explained the basic principle of electron transfer using simple marcus curves, for which he was awarded the nobel prize. However, the validity of marcus theory is limited to small electronic coupling constants (a few tens of wave number) and to static solvent environments. Cao extended classical electron transfer theory to large electronic coupling constants and dynamic solvents. in doing so, he has clarified several concepts implied in the Marcus model and developed a unified approach to the calculation of electron transfer rate constants. based on the progress he made during the year, he submitted three single author papers to Phys. Rev. Lett. J. Phys., Chem, and Chem. Phys. Lett. Preliminary results were presented at two quantum dynamics work-shops and has been well received by the experts in the field. recently, he was invited to present this work at ACTA. American Conference of Theoretical Chemistry is held once every three years. Only 20-30 leading theorists are invited to give a talk, and few junior faculty members have ever been invited. Prof. Cao is off to a great start.

Rick Danheiser: In 1998, Danheiser reported the first example of a "[4+2] heteroenyne cycloaddition," extending his work on the invention of new types of ring-forming reactions based on highly unsaturated conjugated molecules. The new transformation involves a remarkable rearrangement reaction and provides a very efficient synthetic route to an important class of oxygen ring compounds.

John Essigmann: This group discovered the potent mutagenic activity of oxidized forms of cytosine. These oxidized bases may be responsible for GC to AT mutations, which are the predominant spontaneous mutations in aerobic organisms.

Robert Field: The spectroscopic signature of bond-breaking unimolecular isomerization has been observed in two molecules, HCP and HCCH. Not only are the energy level and intensity patterns associated with isomerization now well specified, but these are accompanied by qualitative changes in the nodal structure of the wave functions and bifurcations in the form of the classical mechanical periodic orbits. This is a seminal result in vibrational spectroscopy and dynamics. It has become a focus for experiment and theory collaborations with many research groups.

Professors Field and Steinfeld, in collaboration with Drs. Alexander Kachanov and Sergey Panov have studied Cavity RingDown (CRD) and IntraCavity Laser Absorption Spectroscopy (ICLAS), two ultrasensitive absorption techniques. They have developed new variants of both techniques that provide quantum limited sensitivity. The new schemes are ideal for UV and IR applications, where high reflectance mirrors are often not available, and especially for double resonance studies, where the cavity decay time and the ~1 Ás lifetime of the labeled level should be comparable.

Stephen Lippard: In collaboration with the Pabo laboratory, Lippard's group determined the first X-ray crystal structure of an 80-amino acid protein fragment known as the HMG domain complexed to DNA containing the major adduct of the anticancer drug cisplatin. In related work, a fluorescent assay was developed to screen new platinum anticancer drug candidates prepared by combinatorial synthesis. These two studies formed the basis for a News of the Week story in C&EN in June.

Peter Seeberger: This laboratory has developed glycosyl phosphates as powerful new glycosylating agents for the synthesis of complex oligosaccharides in solution and on the solid support. Together with new linker technologies invented in the laboratory these methods are applied to the solid-phase synthesis of oligosaccharides which may ultimately lead to an automated oligosaccharide synthesizer. The synthetic chemistry community has long awaited such a development.

Tim Swager: This group made significant progress toward solving the problem of detecting buried land mines. It is estimated (C&EN, March 10, 1997) that there are 120,000,000 unexploded land mines worldwide which claim a new victim every 20 min. The predominately plastic composition of land mines complicates their detection by traditional methods such as metal detectors. Presently the most effective technology to find these buried land mines is a trained dog. it has been established that dogs locate the mines by smelling TNT and DNT (trinitrotoluene and dinitrotoluene), the principal components of the vast majority of menacing land mines. Swager's research group has developed a new approach to the detection of TNT and DNT by using electronic polymers (molecular wires) as amplifies in fluorescence. The detection limits of these battery operated hand-held devices are extremely small (10-15 g or less) and have resulted in successful field tests on actual (deactivated) buried land mines. The technology has been licensed from MIT and a new company focused on Swager's molecular wire amplification technology will be launched by fall of this year.

Jeffrey Steinfeld: Professors Field and Steinfeld have been developing IntraCavity Laser Absorption Spectroscopy (ICLAS) as a tool for high-sensitivity spectroscopic investigations. By careful measurement of line intensitites and self-broadening coefficients in the oxygen A-band, ICLAS has been shown to be a reliable method for obtaining these parameters for weakly absorbing transitions. Using a recently developed double-timed-correlated ICLAS technique, the researchers have succeeded in detecting photolysis products resulting from the flash-decompostion of acrylonitrile. Further development of this technique should make ICLAS a useful technique for carrying out time-resolved spectroscopy of weakly absorbing species.

Andrei Tokmakoff: During the past year, the research work in the Tokmakoff group has been primarily dedicated to the development and construction of laser spectrometers, and preliminary experimental work on structural dynamics in liquids with one laser source. They demonstrated how to generate and compress 80 femtosecond pulses of mid-infrared light that they will be using in two-dimensional vibrational spectroscopy of peptides. In work on liquid dynamics, they demonstrated how one can measure the isotropic relaxation of liquids and thereby density fluctuations–an important quantity for comparison to theory. In addition, theoretical work has been ongoing to describe planned experiments in the field of femtosecond multidimensional vibrational spectroscopy. They have shown that molecular structural information can be extracted from the amplitude of cross-peaks in a two-dimensional Raman spectrum in a manner that is analogous to the equivalent NMR technique.

EDUCATION

In the fall of 1998, 40 students entered the graduate program of the Chemistry Department and from September 1998 through June 1999 the Department awarded 1 M.S. and 42 Ph.D. degrees. The number of graduate students in our program is expected to increase significantly as we rebuild the faculty to its previous level and in fact 54 students will enter the program in the fall of 1999.

Enrollment in undergraduate chemistry courses has leveled off after increasing ca. 67 percent over the period 1987—1995. Three courses, 5.11, 5.12, and 5.60, are each taken by approximately 40 percent of the MIT undergraduate student body, and most of our graduate student teaching assistants are assigned to these service courses. The Committee on the Chemistry Curriculum continues to review the undergraduate educational program and spearhead the introduction of new courses. This spring, our new "capstone experience" course 5.21 ("Design and Synthesis") was presented for the second time by Professors Danheiser, Stubbe, and Tidor, and the class received national attention in an article in Chemical & Engineering News (June 7, 1999). A second IAP chemistry laboratory course, 5.302 ("Introduction to Experimental Chemistry"), was introduced in January, joining the highly successful intensive practical training course 5.301 ("Chemistry Laboratory Techniques") which was introduced in 1998.

Construction of the Chemistry Department Computer Classroom (2-125) was completed last year in time for opening at the beginning of the fall semester. The creation of this facility was supported by a grant from the Dreyfus Foundation, supplemented with Department funds, and with matching equipment from the MIT Athena Program. The Computational Chemistry Classroom currently has six Athena SGI workstations (for individual and group work) located along two walls, and a central conference table for seminar-style instruction and discussion. A number of Chemistry Department subjects are making extensive use of this facility under the leadership of Professors Tidor, Cummins, Stern, and Stubbe. In addition, last year Professor Tidor introduced a new IAP 2-unit course (5.67) on "Computer Modeling of Protein Structure and Function" which meets in the Computer Classroom.

In the area of graduate chemistry education, the Chemistry Faculty approved a number of changes in the system for advising and supervising graduate students which will go into effect in September 1999. The aims of these changes include improving communication between students and faculty, reducing stress, and ensuring that every student develops substantive relationships with faculty members besides their research supervisor.

At the annual Chemistry Majors Dinner in May, the recipients of the 1999 Undergraduate Chemistry Awards were announced:

The Alpha Chi Sigma Award, given in recognition of outstanding achievement in research, scholarship and service to the department was given to Joshua Bittker, a senior from Katowah, NY and Jason Wong, a senior from Clifton, VA.

The Undergraduate Research Award, given in recognition of outstanding research in the field of chemistry by an undergraduate, was given to Iat Chio Chan, a senior from New York, NY, Susan Lang, a senior from Fairfield, CT, and J. Christopher Thomas, a senior from Hugo, MN.

The Frederick D. Greene Teaching Award, given in recognition of outstanding teaching in the field of chemistry by an undergraduate, was given to Matthew Bowman from Wray, CO.

Three seniors received the Merck Index Award for outstanding scholarship: Shirley Mihardja of Daly City, CA, Nathan Scott of Guilford, CT, and Alina Vrabioiu of Bucharest, Romania.

Songpon Deechongkit, a senior from Washington, DC, was the recipient of the American Institute of Chemists Foundation Award, for outstanding achievement, ability, leadership and character.

More information about the Deparment of Chemistry can be found on the World Wide Web at http://web.mit.edu/chemistry/www/

Stephen J. Lippard

MIT Reports to the President 1998-99