The Supreme Court of Chemistry
by Lisa Greenhouse, NIST Historian
The annual Hillebrand Prize of the Chemical Society of Washington (CSW), awarded for original contributions to the science of chemistry by member(s) of CSW, is named for William F. Hillebrand (1853-1925), one of Washington's most distinguished chemists. Hillebrand achieved such stature during his career in Washington, first with the Geological Survey and then with the Bureau of Standards, that his colleagues referred to him as the "Supreme Court of Chemistry." more»
Michael P. Doyle
Michael P. (Mike) Doyle is distinguished for his contributions to asymmetric catalysis and metal carbene transformations, for providing basic understanding to nitrosyl chemistry that includes the biochemical reactions of nitrites and nitrogen oxides, and for his research in physical organic chemistry and synthetic method development. He began his research at Hope College in Michigan with nitrosyl chemistry, discovering the applications of nitrogen chemistry - from nitrosonium salts to nitrites – and providing the mechanistic details for modern understanding of the biological effects of nitrogen oxides and nitrosyls.
He is perhaps best known for his research in dirhodium-catalyzed reactions of diazo compounds and for his invention of the "Doyle catalysts" – dirhodium(II) tetracarboxamidates with chiral lactam ligands that are commercially available (Doyle dirhodium catalyst, Rh2(5S-MEPY)4 (Sigma-Aldrich). These catalysts have proven to provide the highest levels of stereocontrol in intramolecular cyclopropanation and carbon-hydrogen insertion reactions with diazoacetates of any catalyst ever developed for these chemical transformations. His research into metal carbene transformations of diazoacetates extended from addition reactions and insertion processes to ylide transformations and established the influence of ligands on reaction selectivities. In addition to having a catalyst named after him, chemical transformations also carry his name, the best known of which is the "Doyle-Kirmse Reaction". The vast majority of this research was performed with undergraduate students since from 1968 until 1997 he was a faculty member at undergraduate institutions, and only in 2000 did he begin to take graduate students.
Since coming to the University of Maryland in 2003 Doyle has developed chiral dirhodium carboxamidates as exceptional catalysts for highly enantioselective Lewis acid promoted reactions, developed highly enantioselective [3+3]-cycloaddition reactions as an alternative to hetero-Diels-Alder reactions for the construction of heterocyclic compounds, established new oxidation methods and oxidation catalysts, and discovered novel paddle wheeled dirhodium structures. His recent research on dirhodium caprolactamate catalyzed chemical oxidations with hydroperoxides has not only produced highly selective processes (allylic oxidation – the Umera-Doyle reaction - but he also clarified the mechanisms of these reactions from what had been a diverse array of interpretations.
Mike has been called the "guru of undergraduate research" (Rebecca Rawls, "An Undergraduate Champion", C&EN, Vol. 80, number 39, September 30, 2002, pg. 30-31) in recognition of his role in developing student careers in the chemical sciences through research and being an outspoken champion of research as an educational enterprise. More than 150 undergraduate students are coauthors of at least one publication with him, and there are several with five or more publications. The list of his undergraduate coauthors constitutes a virtual who’s who in organic and inorganic academic chemistry today. Postdoctoral associates who number fifty have been instrumental in his research endeavors with undergraduate students, and many of these associates are now faculty in academic institutions. He was one of the founders of the Council on Undergraduate Research (http://www.cur.org/), its first president (1978), and the Editor of its newsletter; and he was also the first Chairman (1987) for the Executive Committee of the National Conferences on Undergraduate Research (NCUR) that merged with CUR in 2011. Doyle is the recipient of the 1995 James Flack Norris Award for Outstanding Achievements in the Teaching of Chemistry sponsored by the Northeastern Section of the American Chemical Society and the 2002 George C. Pimentel Award in Chemical Education from the American Chemical Society.
The involvements of Mike Doyle in the American Chemical Society and other professional organizations have been extensive. As Chair of the Department of Chemistry and Biochemistry at the University of Maryland, he led the department to national recognition for efforts in increasing diversity (see Lauren K. Wolf, "Blueprint for increasing Diversity", C&EN, Volume 89, issue 51, pg. 41-42, 2011). Mike was General Chair for the 2011 Middle Atlantic Regional Meeting of the ACS during the same year that he was President of the Chemical Society of Washington; and he and his colleague, Andrei Vedernikov, chaired the Scientific Committee and organized the host site for the 2012 International Chemistry Olympiad.
Dirhodium, Dinitrogen, and Determined Influences from Talented Associates
The elements of a career in the chemical sciences are not only those whose combinations construct chemical compounds but also colleagues and students who shape the progress of what is yet to come. This presentation will briefly trace the origin of current research through those who created the opportunity and focus on the development of asymmetric catalysis applied to the synthesis of many classes of organic compounds through metal carbene formation with dirhodium compounds. The FDA increased the flow of research by their publication in 1992 of "The Development of New Stereoisomeric Drugs", and the NIH took up the challenge by focusing some of their resources on asymmetric synthesis with the beneficiaries being pharmaceutical companies and the general public who benefited from resulting advances.
Professor Akos Vertes
The George Washington University, Washington, DC
Dr. Vertes (right) receives the 2012 Hillebrand Award from CSW President Raber
Dr. Akos Vertes is a Professor of Chemistry and a Professor of Biochemistry and Molecular Biology at The George Washington University in Washington, D.C. He is a co-founder and co-director of the W. M. Keck Institute for Proteomics Technology and Applications, a center of strategic excellence at the university. Professor Vertes received his Ph.D. in 1979 at the Eötvös Loránd University in Budapest, Hungary, followed by postdoctoral work at the University of Notre Dame in Notre Dame, IN. He arrived to The George Washington University in 1991, where by 2000 he rose through the ranks to Full Professor. In addition to his position there, he served as a Guest Researcher at the Naval Research Laboratory in Washington, D.C, and as an Adjunct Scientist at the National Institutes of Health in Bethesda, MD. He also served as a Visiting Professor at the Swiss Federal Institute of Technology Zurich (ETH Zurich) in Zurich, Switzerland, and as a Visiting Faculty at the Lawrence Berkeley National Laboratory in Berkeley, CA. His research interests span from fundamental studies in analytical and physical chemistry to the development of new technologies for biomedical analysis. Based on these new tools, his laboratory develops new methods for the molecular imaging of biological tissues and the analysis of single cells and subcellular compartments to answer fundamental questions in biology. His interdisciplinary research has been disseminated in over 140 peer-reviewed publications, and in two books. More than 10 of his papers are featured on the covers of high impact journals. His inventions are documented in 5 issued US patents and 13 pending patent applications. Much of this intellectual property has been licensed by the biotech industry. His honors and awards include Hillebrand Prize, the Velmer A. Fassel Lecture in Analytical Chemistry, the Oscar and Shoshana Trachtenberg Prize for Scholarship, the Elsevier/Spectrochimica Acta Award, the Fellow of the Royal Flemish Academy for Science and the Arts in Brussels, Belgium, and the Doctor of the Hungarian Academy of Sciences in Budapest, Hungary. His inventions garnered a "Top 10 Innovations of 2011" award from the magazine The Scientist, in the UK, a "2012 R&D 100 Award" from the R&D Magazine, the Editors’ Bronze Award at the 2012 International Pittsburgh Conference on Analytical Chemistry and Applied Spectroscopy (PITTCON) and the Frost & Sullivan 2012 New Product Innovation Award in Bioanalytics. He serves as an Academic Editor for the journal PLoS ONE.
From Fundamentals to New Tools and Back to Fundamentals
Abstract: In the past three decades, new insights into two physical phenomena, laser-solid interactions and electrosprays, reshaped the landscape of bioanalytical chemistry. Specific interactions of lasers with condensed matter are used throughout chemistry to synthesize, modify and probe materials of interest. Important examples include, matrix-assisted laser desorption ionization (MALDI) for biomolecular analysis, photonic ion production from nanostructures, and phase explosion for laser ablation sampling of biological specimens. Electrification of liquid menisci finds similarly diverse applications in macromolecular ion production, nanoencapsulation and electrospinning. Our efforts to understand the volatilization, ionization and fragmentation of biomolecules in these processes resulted in the description of limited energy transfer between matrix and analyte, and the introduction of a fluid dynamic model for MALDI. Analyte internal energy measurements in MALDI, electrospray ionization (ESI) and photonic ionization revealed fragmentation patterns in these highly complex processes. Columnar nanostructures, for example, silicon nanopost arrays (NAPA), were shown to exhibit photonic ion production, including the polarization dependence of ion yields. The formation and disintegration regimes of electrified liquid droplets were followed from bulk solution to nanoscopic droplets to explain ion production in ESI.
Armed with extensive knowledge about laser ablation sampling and various forms of ion production, we set out to design a new bioanalytical modality. This technique capitalized on mid-IR laser sampling of microvolumes followed by ESI of the ablation plume for mass spectrometric analysis. The resulting method, termed laser ablation electrospray ionization (LAESI), enabled the direct local analysis of biological tissues and cells, and their mass spectrometric imaging at atmospheric pressure in two and three dimensions. In situ LAESI measurements on numerous biomedical systems included plant tissues and cells, virally infected lymphocytes, energy harvesting microorganisms, rodent brain tissue sections and the central nervous system of molluscs. Optimized nanofabrication of NAPA resulted in an ultrasensitive ionization platform that enabled the metabolic analysis of a single yeast cell.These novel tools enabled us to ask some fundamental questions that promised fresh insight in cell biology. Through the combination of cell dissection and LAESI mass spectrometry, we demonstrated the existence of significant metabolite gradients between the cytoplasm and the nucleus within a cell. Our ability to analyze individual cells on NAPA allowed the exploration of cellular heterogeneity and its changes under oxidative stress. In these endeavors we benefitted from an interdisciplinary approach that started with exploring the basic physics
Debra Rolison heads the Advanced Electrochemical Materials section at the NRL (also known as the U.S. Navy’s nanoarchitectural firm), where her research focuses on multifunctional nanoarchitectures for rate-critical applications, such as catalysis, energy storage and conversion, and sensors. She received a Ph.D. in Chemistry (UNC–CH, 1980) and is a Fellow of the American Association for the Advancement of Science, the Association for Women in Science, the Materials Research Society (inaugural class), and the American Chemical Society. Rolison received the 2011 ACS Award in the Chemistry of Materials and the 2012 C.N. Reilley Award of the Society for Electroanalytical Chemistry. She is also an Adjunct Professor of Chemistry at the University of Utah (2000–present). When not otherwise bringing the importance of nothing and disorder to materials chemistry, Rolison writes and lectures widely on issues affecting women in science, including proposing Title IX assessments of science and engineering departments. She is the author of over 200 articles and holds 24 patents.
Rewiring electrochemical power from start to finish via architectural design on the nanoscale
Abstract: Designing high-performance energy-storage devices that combine nanometric feature size with well-wired transport paths and that bridge to the macroscale requires an architectural perspective. We use aerogel-like carbon nanofoam papers as our architectural test-bed because they provide a low cost and scalable nanocomposite that offers an optimal balance of critical architectural features: (1) open, 3D interconnected macropores sized at 20-to-250 nm co-continuous with (2) ~20-nm pore walls of a size that reduces dead weight and volume yet retains mechanical strength and flexibility without compromising electronic conductivity. Charge-storage or catalytic functionality can then be imparted to internal carbon walls simply by transporting reactants within the 3D “plumbing” of the macroporous foam. Self-limiting modification strategies allow us to incorporate conformal, nanoscopic functional “paints” of metal(Mn, Ti, Ru, Fe)oxides or polymer (redox-active or electron insulating) or specifically adsorb metal nanoparticles (Pt, Au, Pd, Ag) throughout the macroscopic thickness (0.07 to 0.3 millimeter) of carbon nanofoam papers. For instance, painting the carbon walls with 10-nm MnOx increases the mass-, geometric-, and volume-normalized capacitance (2- to 10-fold) relative to the native carbon nanofoam without significantly altering its high-rate character. The oxide-modified paper is now a multifunctional electrode structure that can be used in an aqueous asymmetric electrochemical capacitor or as an air cathode in a Zn/air cell to electrocatalyze oxygen reduction and provide pulse power. Our redesign of electrode structures using modified carbon nanofoam papers has catalyzed breakthroughs in our work within a broad range of multifunctional energy storage and conversion, including asymmetric electrochemical capacitors, air cathodes for metal–air batteries, 3-D batteries, and semifuel cells.
Photo: Hillebrand Prize winner, Debra Rolison and President Elect Doug Raber at the March Dinner Meeting
Born June 6, 1955 in London, England; Naturalized US citizen, Baltimore (1996). Education: BSc. in Biochemistry (1st Class Honors), University College London (1976); MD, University College Hospital Medical School, London (1979); PhD in Physical Biochemistry, MRC National Institute for Medical Research, London (1982). Positions held: House Physician, University College Hospital, London, U.K. (1979); House Surgeon, St. Charles Hospital (St. Mary's Hospital Group), London, U.K. (1980); Member of the Scientific Staff of the MRC at the National Institute for Medical Research, London, U.K. (1980-1984); Head of the Biological NMR Group, Max-Planck Institute for Biochemistry, Martinsried, Germany (1984-1988); Senior Investigator, Laboratory of Chemical Physics, NIDDK, NIH, Bethesda (1988-present); Chief, Protein NMR Section (1991-present). Honors: Francis Walsche Neurology prize, University College Hospital Medical School, London (1977); Lister Institute Research Fellow (1982); Elected Fellow of the Royal Society of Chemistry (1990); Scientific Achievement Award (Biological Sciences) of the Washington Academy of Sciences (1990); Distinguished Young Scientist Award of the Maryland Academy of Sciences (1990); Elected Fellow of the Washington Academy of Sciences (1991); National Institutes of Health Director's Award (1992); National Institutes of Health Lecture (1993); Dupont-Merck Young Investigator Award of the Protein Society (1993); The Harrington Lecture, National Institute for Medical Research (1996); Elected Fellow of the American Association for the Advancement of Science (1999); Original member, Institute for Scientific Information (ISI) Highly Cited Researchers Database, Biology and Biochemistry Section and Chemistry Section (2001); Elected Member, Lister Institute for Preventive Medicine (2003); Elected a Fellow of the Biophysical Society for "Pioneering contributions in the development of NMR spectroscopy for structural characterization of biological macromolecules" (2009); NIDDK Nancy Nossal Scientific Mentorship Award (2009); Elected a Fellow of the American Academy of Arts and Sciences (2010); Hillebrand Award of the Washington Chemical Society (2010).
Exploring Sparsely-Populated States of Macromolecules by Diamagnetic and Paramagnetic NMR Relaxation
Abstract: Sparsely-populated states of macromolecules, characterized by short lifetimes and high free-energies relative to the predominant ground state, often play a key role in many biological, chemical and biophysical processes. We will summarize various new developments in paramagnetic NMR spectroscopy that permit these heretofore invisible, sparsely-populated states to be detected, characterized and visualized. In the fast exchange regime (time scale less than ~250-500 μs) the footprint of sparsely-populated states can be observed on paramagnetic relaxation enhancement profiles measured on the resonances of the major species, thereby yielding structural information that is directly related to paramagnetic center-nuclei distances, from which it is possible, under suitable circumstances, to compute a structure or ensemble of structures for the minor species. This will be illustrated with regard to (a) the search process whereby transcription factors locate their specific DNA target site among a sea of non-specific sites, (b) the characterization of encounter complexes in protein-protein interactions; and (c) the visualization of large scale interdomain motions.
Dr. James E. Butler
Gas/Surface Dynamics Section, Chemistry Division
Naval Research Laboratory, Washington, DC
The Chemical Society of Washington will present the 2009 Hillebrand Prize to Dr. James E. Butler, Head of the Gas/Surface Dynamics Section at the Naval Research Laboratory, at its dinner meeting on March 11, 2010. Dr. Butler will address the meeting with a seminar entitled "Alchemy."
Dr. Butler joined the Naval Research Laboratory in 1975 where he applied laser spectroscopy to the study of elementary reaction dynamics, photochemistry, and gas phase chemical kinetics relevant to atmospheric and combustion chemistries. Following a sabbatical year at the Institute of Molecular Science in Japan (1982-3), he used high resolution IR laser diode spectroscopy to the study of reactive transient molecules relevant to plasma processing and chemical vapor deposition (CVD). His work on the use of in situ laser diagnostics to the gaseous and surface processes in CVD initiated the field for reactive chemical modeling of CVD processes (1983-86). Beginning in 1987, Dr. Butler focused on the understanding of the growth chemistry and mechanisms of the newly reported CVD of diamond. In 1988, he formed the Gas/Surface Dynamics Section in the Surface Chemistry Branch of NRL to focus on the basic gaseous and surface chemical processes occurring in the CVD and plasma processing of materials relevant to modern advanced technologies. His current research interests lie primarily with understanding and exploiting the growth, characterization, properties, and applications of chemical vapor deposited (CVD) diamond materials.
Dr. Butler has been a visiting scientist at the National Research Council of Canada (1982), the Institute of Molecular Science in Japan (1982-3), the University of Witswatersrand in South Africa (1996), a Distinguished Lecturer in the Department on Mechanical Engineering at the University of Minnesota (1996), the Benjamin Meaker Visiting Professor of Physics and Chemistry at the University of Bristol in England (1997), the University of Melbourne in Australia (2006), and the University of Warwick in England (2007, 2009). Dr. Butler has published over 245 refereed journal papers (H factor of 45 as of January 2010), and given numerous plenary and invited technical presentations at professional society meetings, international conferences, and universities.
In addition to serving as technical advisor to ONR, SDIO, NSF, and DARPA on various diamond research initiatives, he has participated as an technical expert in a White House inquiry on controlling trade of ‘conflict' diamonds, served a consultant to various companies in the industrial diamond industry, chaired a Gordon Research Conference on Diamond, participated in the organization of numerous international conferences, and serves on the advisory board for the journal Gems and Gemology. He was presented with the Sigma Xi NRL Edison Chapter Applied Science Award in 2001 and the NRL Technology Transfer Award in 2009.
Abstract: Alchemy is perceived by many as the art of turning "lead into gold", or more generally, something base (not valuable) into something valuable. In the last century, the science of chemistry has done exactly the same, converting base things such as sand into silicon wafers and ultimately the complex 'chips' that have enabled much of our modern technology. Thus 'Al Chemy', or 'the chemistry' is a way of describing the critical role of chemistry to modern society, just as ancient chemists and materials scientists may have used their knowledge to bring value to the market places of their times.
In this talk I will focus on a process, Chemical Vapor Deposition (CVD), which has become critical to the fabrication of many modern electronic materials and devices. The ‘Alchemy' I will describe is the growth of Diamond by CVD from as base a material as ‘sewer gas'. To understand the complexity of Diamond CVD requires knowledge of many processes: the decomposition of gaseous reactants, the fluid dynamics and transport of reactive species to the growing surface, the surface chemistry which in the case of diamond CVD, deposits diamond as opposed to graphitic or amorphous carbons, and the role of defects and impurities in the growth and quality of the diamond material. Thus Diamond CVD serves as an example of all the complex chemical and physical processes which occur during the CVD of materials, and provides an excellent platform for the development and testing of theoretical/computational tools since carbon has relatively few electrons and one can draw on the extensive knowledge base of organic and combustion chemistries. Diamond CVD has now enabled new technologies which exploit the extreme thermal, optical, mechanical, electronic, and chemical properties of diamond. CVD Diamonds provide the reproducible quality and morphology for technological applications, and a purity which can exceed that of the best natural diamonds.
Dr. Kurylo received a B.S. degree in chemistry from Boston College in 1966 and a Ph.D. in physical chemistry from the Catholic University of America in 1969. Following a National Research Council Postdoctoral Associateship at the National Bureau of Standards (now NIST), he was a Research Chemist at NBS and NIST from 1971 – 2003. During the last half of this period, he continued his NIST research in laboratory atmospheric kinetics and photochemistry while serving on a detailed assignment to the National Aeronautics and Space Administration as manager of NASA’s Congressionally-mandated Upper Atmosphere Research Program. In 2004 he transferred to NASA as a Program Scientist in Atmospheric Composition, and retired from the federal government in 2008.
Dr. Kurylo’s laboratory research has focused on gas phase free radical photochemistry and kinetics with an emphasis on atmospheric processes related to stratospheric ozone depletion and climate change. An author or co-author of 140 scientific articles, he has given more than 190 technical presentations nationally and internationally. As a NASA program scientist he was largely responsible for organizing and implementing several airborne scientific investigations that linked the depletion of stratospheric ozone to manmade chemicals containing chlorine and bromine. He has provided similar leadership for other field investigations utilizing measurements from satellites, aircraft, balloons, and the ground for examining the connections between changes in atmospheric composition and in climate. Since 1987, he has served at the interface between scientific research and international environmental policy through extensive participation in each of the Scientific Assessments of Ozone Depletion conducted by the United Nations Environment Programme and the World Meteorological Organization. These assessments are required by the Parties to the Montreal Protocol on Substances that Deplete the Ozone Layer and the Vienna Convention for the Protection of the Ozone Layer. He has been elected Chair of several past meetings of international Ozone Research Managers of the Parties to the Vienna Convention and has presented the consensus recommendations at subsequent meetings of the Parties (most recently in Doha, Qatar this past November). Dr. Kurylo also holds leadership positions on several international organizations in atmospheric chemistry.As an internationally acclaimed atmospheric research scientist and program manager, Dr. Kurylo has received numerous awards. These include the Department of Commerce Bronze and Silver Medals, two NASA Exceptional Service Medals, the NASA Cooperative External Achievement Award, more than a dozen NASA Group Achievement Awards, the Catholic University of America Alumni Achievement Award in the Field of Science, the National Oceanic and Atmospheric Administration Environmental Hero Award, and the US Environmental Protection Agency Stratospheric Ozone Protection Award. His efforts leading to the success of the Montreal Protocol have recently been acknowledged by his being named to the Montreal Protocol Who’s Who listing. Dr. Kurylo is a member of the ACS, the American Physical Society, the American Geophysical Union, and Sigma Xi.
At the CSW dinner meeting seminar, Dr. Kurylo will describe developments in laboratory measurement techniques for gas phase kinetics and photochemistry that have enabled atmospheric scientists to isolate and investigate specific chemical reactions. These studies have provided the data required for modeling calculations of the transformations of important atmospheric trace species. The role of measurement campaigns for studying the atmosphere itself as a complex photochemical reactor will also be described.
Dr. Kurylo will also provide an historical perspective of the development of past and present national and international research programs for investigating changes in atmospheric composition. Scientific achievement under these programs have led to the success of the Montreal Protocol on Substances that Deplete the Ozone Layer.
Abstract: Depletion of the Earth’s stratospheric ozone layer was the first manifestation of global environmental change attributable to human activity. Ranging from moderate losses at mid-latitudes to large-scale seasonal losses in the Polar Regions, its detection and attribution have required integrated efforts across the full spectrum of atmospheric science. Sophisticated atmospheric observations from the ground, balloons, aircraft, and satellites together with the results from laboratory investigations have provided the scientific bases for sound environmental policy at the national and international levels. Dr. Kurylo will describe the developments in laboratory measurement techniques for gas phase kinetics and photochemistry that have enabled atmospheric scientists to isolate and investigate specific chemical reactions. The role of measurement campaigns for studying the atmosphere itself as a complex photochemical reactor will also be described. The subsequent interpretation of the field measurement observations through the use of laboratory data has been a key element in the formulation of international assessments that underlie environmental treaties.