MIT Reports to the President 1999–2000


DEPARTMENT OF CHEMISTRY

In the 1999—2000 academic year, the Chemistry Department continued its strong program in research and undergraduate and graduate education. Associated with the department currently are 200 graduate students, 114 postdoctoral researchers, and 102 undergraduate chemistry majors.

As of July 1, 2000, the Chemistry Department Faculty comprises full-time faculty members including 6 Assistant, 2 Associate, and 21 Full Professors including one Institute Professor and four TBA slots, one of which will be filled by Joseph Sadighi who joins the Department as an Assistant Professor on July 1, 2001. Harald Schwalbe joined the Department as an Assistant Professor on October 20, 1999. Professor Satoru Masamune retired on December 31, 1999. Professor Robert J. Silbey was selected to be the Interim Dean of Science, effective February 1, 2000.

FACULTY AWARDS AND HONORS

Professor Robert W. Field was selected Haslam & Dewey Professor of Chemistry.

Professor Dan Kemp received the ACS Ralph F. Hirschmann Award in Peptide Chemistry.

Professor Alan Davison was elected as a Fellow to the Royal Society of Chemistry.

Professor Cathy Drennan received the Surdna Foundation Research Award and also

the Cecil and Ida Green Career Development Chair.

Professor John Essigmann was awarded the honorary Mutation Research Award for Scientific Excellence by the American Chemical Society.

Professor Greg Fu received the School of Science Undergraduate Teaching Prize and the Chan Memorial Award in Organic Chemistry.

Professor Frederick D. Greene was awarded the distinction of Fellow by the American Association for the Advancement of Science.

Professor Jeff Steinfeld received the 1999 Director’s Award for Advancing ACS Public Policy in Environment. Professor Steinfeld was also named as the Chair of the American Chemical Society's Committee on Environmental Improvement. The Committee's mission is to coordinate the American Chemical Society's agenda for sustainability and to act as the ACS's voice on environmental issues.

Professor Jianshu Cao was selected as one of the recipients of the Solomon Buchsbaum AT&T Research Fund and was also awarded the Young Researcher Award in Japan for his paper entitled "Quantum Coherence in Nonlinear Optical Professes: Theory and Possible Application to Control of Chemical Reaction and Quantum Computation."

Professors Kit Cummins and Peter Seeberger were chosen by Technology Review Magazine as two of the TR100 Young Innovators at a ceremony honoring 100 creative young people who will make significant contributions to information technology, biotechnology and materials science.

Professor Mario Molina was awarded the United Nations Environment Programme (UNEP) Sasakawa Environment Prize.

Professor Harald J. Schwalbe was awarded the Karl-Winnacker-Stipend, a five-year Hoechst AG sponsored award.

Professor Steve Buchwald received the ACS Award in Organometallic Chemistry.

and was also elected to the American Academy of Arts and Sciences.

Professor Tim Swager received the ACS Arthur C. Cope Scholar Award.

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 have brought us to our $4 million external funding goal. These campaign resources (including a challenge grant from Visiting Committee Chair Richard Simmons), combined with department and Institute commitments, have enabled $20 million of reconstruction in buildings 2, 4, and 6. A $44 million renovation of building 18, approved by the central administration, and construction has begun in the summer of 2000. We summarize below the progress made in the main group, buildings 2, 4 and 6.

Completed in prior years were renovations to space housing the Chemistry Education Office on the 2nd floor of building 2, Professor Nocera’s wet labs on the 2nd and 3rd floors of building 2, Laser labs for Professor Bawendi in the basement of building 18, the Department of Chemistry Instrumentation Facility (DCIF) in the sub-basement of building 18, the first half of Professor Ceyer’s labs on the 1st floor of building 6, the departmental X-ray laboratory on the 3rd floor of building 2 and the contraction and relocation of the departmental machine shop to make way for the renovations of the laser labs in the basement of building 6.

Renovations in the basement of building 2 and 6 creating Laser labs for the Field, Nocera, Nelson and Tokmakoff groups were completed in early 2000 and these groups have moved into these new labs from their temporary locations in the Francis Bitter Magnet Lab and the Steinfeld lab. Renovations of the Steinfeld lab in building 2 are underway and will completed this summer. The Steinfeld group, which has been temporarily housed with the Field group in their new labs, will move back to their new labs by the end of the summer. The completion of the Steinfeld labs will mark the completion of the renovations in the basement of building 2, 4 and 6.

Renovations for the Schrock and Cummins groups on the 3rd and 4th floors of building 6 are nearing completion and these groups will move back to their new labs by the end of this summer. The Schrock group will be moving back from swing space on the 1st floor of building 18, clearing the way for Phase One renovations in building 18. The Cummins group will be moving back from swing space in the former Seyferth labs on the 2nd and 3rd floors of building 2, making this space available for Professor Jamison use as swing space during the renovations of building 18 and for the initial, temporary, space for Professor Sadighi who will be joining the department in July of 2001.

Renovations for the second half of the Ceyer labs are tentatively scheduled to begin in the fall of 2001. The actual date will set once a new instrument and constructed and is operational in the new space, allowing an existing instrument in the un-renovated space to shut down.

The renovation program for building 18 is progressing and is currently on schedule. Preparation of construction documents (CDs) are underway and are expected to be issued for bidding in September of 2000 with Phase One renovations commencing soon there after. In Phase 0, taking place this past spring and over this summer Temporary Faculty Offices (TFOs) have been located adjacent to building 18 and have been occupied by Headquarters, six faculty and three support staff so that space in 18 can be made available for renovations and for swing space for the researchers remaining in the building. Also occurring over the remainder of the summer and early fall will be the compression of the research labs to empty approximately one-third of the building for renovations in Phase One. Phase Two is scheduled to begin in the summer of 2001 and Phase Three in spring of 2002.

Phase IV represents the final phase of renovations to Chemistry’s space. The laboratories previously assigned to Deitmar Seyferth on the 2nd and 3rd floors of building 2, unarguably the wet laboratories in the worst shape at the start of the renovations program, will be renovated to the general design and level of finish as those of Professors Schrock and Cummins’ laboratories currently under renovation in Phase III. Renovations to the Seyferth space was assigned to the last phase for two reasons. First, Seyferth preferred not to endure renovations in the final years before his retirement in July of 1999. Second, in anticipation of Seyferth’s retirement, we were able develop a plan to use these labs as swing space during the Phase III renovations, and later, during the building 18 renovations. In 2002—2003 when these labs are longer needed as swing space they will be renovated for Joseph Sadighi, an inorganic chemist joining the department in July of 2001.

The major lab design features of the Phase III/IV design are the separation of student desks from the laboratory and the elimination of unconditioned fumehood makeup air. The latter can be accomplished by the adoption of horizontal opening fumehoods, even while increasing the total liner feet of hood space. In Phase III the change to horizontal opening sash fumehoods has allowed the elimination of the unconditioned auxiliary hood make up air system and a downsizing of the building HVAC system by roughly 50%. This approach will result in reduced building operation costs.

In addition to the completion of the laboratory renovations, the other major objective of the Phase IV renovation is the correction of the non-compliant rooftop fumehood exhaust system for building 2. During the course of renovations to Professor Nocera’s labs in Phase I it was discovered that fumes from all of the hoods in building 2 were not being properly dispersed at the rooftop. A smoke test conducted by the Industrial Hygiene Office revealed that fumes pool on the roof could create an unsafe condition for Department of Facilities maintenance personnel and contractors, and can spill over the edge of the roof. The latter creates the opportunity for chemical fumes to be pulled into the building fresh air intake duct located in the courtyard formed by building 2,4,6, and 8, and generally enter the buildings through windows. The conventional means of correcting this condition is with exhaust stacks that are at least 10 feet above the highest structure on the roof. However, on the building 2 roof this is not possible owing to the high roof parapet, roof top structures and adjoining buildings. Exhaust stacks some thirty plus feet tall would be required. Numerous stacks of this height would be very difficult to secure and would be unacceptably visible from Killian Court. The architects and engineers developed a design to correct this problem, however its implementation had to be deferred to the phase IV. Briefly, the solution incorporates the manifolding the exhaust stacks from all of the fumehoods in building 2 at the roof top and exhausting at a very high rate to ensure proper dispersal of the fumes. Implementation of this design will require a upgrade of all of the fumehoods and fumehood controls in building 2. This activity represents a substantial portion of the estimated cost of Phase IV.

EDUCATION

In the Fall of 1999, 54 students entered the graduate program of the Chemisty Department and from September 1998 through June 1999 the department awarded 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 63 students will enter the program in the fall of 2000.

Enrollment in undergraduate chemistry courses has leveled off after increasing ca. 67% over the period 1987—1995. Three courses; 5.11, 5.12 and 5.60 are each taken by approximately 40% of the MIT undergraduate student body and most of our graduate 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. Recent initiatives include a "capstone experience" course 5.21 ("Design and Synthesis") which received national attention in an article in Chemical & Engineering News (June 7, 1999). This January, two IAP chemistry laboratory courses, 5.302 ("Introduction to Experimental Chemistry") and 5.301 ("Chemistry Laboratory Techniques"), were offered and attracted considerable interest among freshmen. 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 went into effect this academic year. 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.

A peer mentoring program has been introduced to facilitate the training of Teaching Assistants. Graduate students who excelled as TA’s in recent years were trained in providing feedback and support to novice TA’s throughout the term. In addition, all current TA’s now collect mid-term formative feedback from their students in an effort to promote and enhance effective teaching.

At the Senior Recognition Dinner in May, the recipients of the 2000 Undergraduate Chemistry Awards were announced:

The Alpha Chi Sigma Award (for achievement in research, scholarship and service to the department) - Connie Lu and Rachel Stanley

American Institute of Chemists Foundation Award (in recognition of outstanding achievement, ability, leadership and character) — Cynthia Liang

The Merck Index Award (for outstanding scholarship) — Eric Ferriera, Mark Stoykovich and Alice Wang

Research Award (for outstanding research in the field of chemistry) — Qinghao Chen, Daniel Crawford, Andrew Greytak and Krzystof Rybak

Hypercube Scholar (for outstanding achievement in the area of computational chemistry) — Thomas Baker

The Frederick D. Greene Teaching Award (for outstanding contributions in the area of teaching) — Victoria Gomez and Alice Wang

Service Award (for significant contributions in the area of service to the department) — Isabelle Halphen and Clifton Leigh

RESEARCH HIGHLIGHTS

Jianshu Cao used a modulated N-conformational-channel reactive system to model the recent single-molecule enzymatic experiment. This theoretical work helps establish the differences between single molecule and molecular ensemble chemistry.

Christopher Cummins showed that heterodinuclear Nb/Mo systems can effect the reductive cleavage of dinitrogen. Significant in this case is the first example of dinitrogen splitting by a heterodinuclear system.

Catherine Drennan determined the first structure of a nickel-dependent carbon monoxide dehydrogenase. This structure provides a much-awaited picture of the nickel-iron-sulfur cluster used in the biological oxidation of carbon monoxide.

John Essigmann devised the first system by which the mutagenic activity of a DNA adduct could be determined in all possible sequence contexts. Results showed that DNA repair proteins selectively repair adducts in some contexts in vivo.

Robert Field discovered that, at high excitation, the bending vibrations of acetylene become increasingly regular and localized rather than chaotic and coupled over the entire molecule. Moreover, the most stable motion is directly along the minimum energy pathway between acetylene and vinylidene, an unstable isomer of C2H2 (lifetime shorter than 1 picosecond) which is a postulated intermediate in many organic and inorganic reaction mechanisms.

Gregory Fu developed mild methods for effecting a variety of powerful palladium-catalyzed carbon-carbon bond-forming processes, including the Suzuki, Heck, Stille, and Negishi reactions. These processes will find application in both academia and industry. In addition efficient new catalytic asymmetric processes were devised.

Barbara Imperiali, in research targeted at the design and synthesis of new mini-protein motifs with defined structure and function, recently completed the iterative design of a new miniprotein with predominantly b -structure. This miniprotein includes 32 amino acid residues and a single disulfide bridge. The new motif demonstrates a distinct molecular architecture for future design efforts targeted at the assembly of functional constructs.

Timothy Jamison developed three novel catalytic organic reactions that assemble useful molecules in a single operation from simple and convenient starting materials. The catalytic reductive coupling of an alkyne and an aldehyde provides a high-yielding, one-step method of synthesizing allylic alcohols.

Stephen Lippard discovered from fundamental research that treatment of human breast and ovarian cancer cells with steroid hormones caused expression of HMG-1 proteins that sensitized the cells to platinum anticancer drugs. A clinical pilot study was just approved at the Dana Farber Cancer Institute and Mass General Hospital to treat ovarian cancer patients by a similar strategy. Novel fluorescent sensors for zinc and nitric oxide were reported that eventually will facilitate their detection in neurochemical signaling pathways.

Jun Liu’s most important contribution this year is the discovery of a novel mechanism of regulation of gene transcription by calcium signaling.

Keith Nelson used Femtosecond to launch lattice vibrational waves that travel through their host crystals at light-like speeds, and additional femtosecond pulses were generated, arriving at later times and different locations, to manipulate the lattice waves as they move. This approach has fundamental applications in nonlinear lattice dynamics and practical applications in ultrahigh-bandwidth signal processing.

Daniel Nocera achieved, for the first time, "photosynthesis in a beaker." The overall strategy is conceptually no different than photosynthesis, distinguished only by the nature of the energy-rich products. In the leaf, sugar and oxygen are produced as fuels. In Nocera's beaker, the fuels are hydrogen and halogen gas, produced from the photocatalytic splitting of HX by a rhodium compound developed in the Nocera group.

Richard Schrock synthesized complexes that catalyze a variety of asymmetric olefin metathesis reactions. In a large number of cases these reactions proceed to give products with an enantiomeric excesses of 95% or better, in some cases essentially 100%. These are the only reported catalysts that will carry out such reactions and are expected to have a significant impact in the synthesis of drugs and pharmaceuticals. The group also discovered how to prepare a wide variety of sterically crowded cationic complexes of zirconium that will polymerize ordinary olefins such as ethylene in a living manner. They are the only olefin polymerization catalysts in over 40 years of research that produce relatively high molecular weight polyolefins in a wholly living manner.

Harald Schwalbe devised a model to predict the conformational averaging around the angles f ,y and c 1 in a random coil peptide tested from NMR measurements of chemical shifts, coupling constants and cross-correlated relaxation rates.

Peter Seeberger developed the first Automated Oligosaccharide Synthesizer, providing the non-specialists access to pure carbohydrates for biochemical and biophysical studies. A second major achievement is the synthesis of diverse libraries of heparin-like glycosaminoglycans. These defined oligosaccharide structures are used as molecular tools to identify heparin sequences responsible for interactions with a variety of proteins involved in signal transduction events.

Lawrence Stern discovered a new pathway for antigen presentation and molecular characterization of the T cell activation mechanism. In most cells, protein degradation and MHC peptide loading occur in intracellular digestion compartments. It was recently discovered that dendritic cells carry empty MHC proteins on their surface, and can directly load peptides from the extracellular medium. Dendritic cells are the "sentinel" cells of the immune system, with unique capabilities in activation and control of T cells. This work could lead to anti-tumor vaccines.

Jeffrey Steinfeld and collaborating investigators experimentally demonstrated Ring-Down Spectroscopy in the mid-infrared region. This technique is being developed as the basis of an ultra-high-sensitivity detection method for explosives and other contraband materials, and can also be used for measurement of trace species present in the atmosphere.

Bruce Tidor developed a novel and important theory for quantifying and analyzing the specificity of molecular interactions. The work shows that a natural tight-binding protein complex uses optimized electrostatic interactions as a prime mechanism for achieving stability. A new and general mechanism for enhancing the stability of proteins has been discovered through theoretical work and verified experimentally.

More information about the Department 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 1999–2000