Physical and Surface Chemistry. The Utz group studies how molecules react on surfaces. Reactions at the gas-surface interface are highly dynamical events. Large-scale atomic and vibrational motions transform reactants into products on sub-ps and Å scales. The experiments probe ultrafast nuclear motion and energy flow dynamics that underlie heterogeneous catalysis and chemical vapor deposition. The goal is to to better model existing processes and direct the rational design of new catalytic materials and deposition techniques. The experiments use vibrational- and rotational-state selective laser excitation of molecules in a supersonic molecular beam to provide precise control over the energetics and orientation of the gas-phase reagent as it approaches the surface. Reaction probability and product identity is then quantified as a function of the reagent's energetic configuration. These experiments have shown that the vibrational state of the incident molecule can have a profound effect on reaction probability, and suggest that energy redisribution within the reaction complex is not complete prior to reaction and that the competing kinetics of energy redistribution and reaction might be manipulated to control the outcome of a reaction. This has been subsequently confirmed by exerting bond-elective control over a heterogeneously catalyzed reaction.
Organic Synthesis, Carbohydrate Chemistry, Synthetic Methodology, Bioorganic Chemistry. Complex carbohydrates play critical roles in a number of biological processes including, protein folding, cellular adhesion and signaling. Despite their importance, very little is understood about the molecular basis of their activity. This is largely due to the fact that the only source of pure oligosaccharides is tedious multi-step synthesis, which can take months or even years to compete. Our research is focused on developing methodologies, based on asymmetric catalysis, to streamline complex oligosaccharide synthesis. Ultimately such methods will aid in the rapid and routine preparation of oligosaccharides for biophysical studies and drug discovery.
Chemistry and STEM Education. In order to understand how and why successful teaching and learning of chemistry at the university level works, the Caspari research group focuses on analyzing students', teaching assistants' (TA), learning assistants' (LA), and instructors' reasoning, interactions, and culture. The group collects video data of classroom practices and conducts qualitative research interviews with instructors, TAs, LAs, and students to better understand how certain interactions and ways of reasoning lead to student sense making and learning. While zooming in and investigating how students connect aspects of chemistry, the group also zooms out and investigates classroom culture and how individual interactions and personal experiences integrate into larger systems of teaching and learning. The group uses this fundamental research as a theoretical basis for implementing teaching innovations and designing training opportunities in order to promote supportive learning environments for students that value and encourage their unique ways of being, knowing and doing.
I am interested in synthesis and characterization in inorganic and materials chemistry. I am especially interested in fundamental chemistry that has important societal implications.
My research laboratory currently works in several areas:
Earth-abundant molecular light absorbers and emitters.
Molecular light absorbers and emitters are used in photoredox catalysis, dye-sensitized solar cells, and organic light-emitting diodes (OLEDs). We are exploring high-spin complexes of iron and manganese to prepare new molecules that absorb and emit light.
Volatile molecules carrying metal-atom equivalents for superconducting wires.
Cryogenic superconducting wires enable quantum bits based on Josephson junctions. We are developing new molecules and methods to deposit the electropositive metals that make up these wires from chemical vapors.
Thin-film photovoltaics with earth-abundant, sulfide-based absorber layers.
Thin-film photovoltaics (solar cells) provide electricity from sunlight with just a few hundred nm of light-absorbing material. We are exploring binary and ternary sulfides as new sources of earth-abundant photovoltaics.
I am developing new research programs in several areas:
The synthesis of iron metal from iron ore contributes ca. 4% of global carbon dioxide emissions. I am interested in alternative thermochemical methods of making iron from iron oxides.
New superconducting materials.
Near-room-temperature superconductors have recently been realized in compressed hydrides. I am interested in new hydride compounds that are stable at ambient pressure and might serve as ambient-pressure, ambient-temperature superconductors.
Planetary Chemical Analysis & Astrobiology -
Over the past several decades it has become increasingly clear that there may be multiple worlds in our solar system besides Earth that either once had or may still have environments capable of supporting microbial life as we know it. Our current research is focused on two aspects of the search for life in our solar system:
(1) We are investigating how potential biomarker molecules on the surface of Mars would be altered or destroyed when exposed to solar ultraviolet radiation in the presence of various oxychlorines and their intermediate formation products. Knowing the potential products of biomarker alteration will help in identifying what type of compounds and where to look for them in the search for life on Mars.
(2) We are developing in-situ analytical instrumentation that is designed to unambiguously detect microbial life and determine the habitability of planetary environments that may be present at the surface or subsurface of Mars, and the oceans of icy-worlds such as Saturn's moon Enceladus or Jupiter's moon Europa.
Bioorganic, Biophysical, & Chemical Biology. Peptides and their mimetics can target protein surfaces in ways small molecules rarely do, making peptide libraries attractive for screening for nontraditional modes of action. The Kritzer research group takes advantage of peptide and peptidomimetic libraries to bypass many of the disadvantages of small molecule screening. They also explore how modifications such as substitution of peptide bonds with isosteres, amide N-methylation, and head-to-tail cyclization affect the activities, specificities, and bioavailabilities of functional peptides. By combining powerful techniques from organic synthesis, biophysical chemistry, molecular biology and genetics, they are developing new molecules and new strategies to attack cancer, inflammation, and autoimmune diseases.
Bioorganic Chemistry and Chemical Biology. Prof. Kumar and his group are involved in areas of research that lie at the interface of chemistry and biology. The main goal of the research is to use chemical and biological methods to create novel and functional molecules that allows us to understand the mechanism of, and/or control biological processes. His group uses the traditional techniques of organic chemistry, such as synthesis and spectroscopy, of biological chemistry, such as recombinant DNA technology, protein purification and enzyme kinetics, and of biophysics, including investigation of protein structure in membranes. Current projects in his laboratory focus on: De novo protein design and evolution; Combating bacterial resistance to antibiotics; Understanding the origin of the intron-exon gene structure of modern day enzymes; Catalysis by small molecules and peptides; and Design of membrane protein architectures for specialized functions.
Theoretical and Computational Biophysical Chemistry. The YSL Group aims to elucidate the structures and functions of biomolecules by integrating the power of advanced computations with the elegance of chemical theory. Our focus is to develop and apply computational methodology to significant biological problems that are difficult to address experimentally. Two major research projects in the YSL Group are (1) to understand and design cyclic peptides with desired conformations to modulate protein–protein interactions and (2) to elucidate the structural and functional roles of post-translational modifications and non-natural amino acids on protein folding.
Bioanalytical and Materials Chemistry. The Mace group applies a multidisciplinary approach—combining aspects of chemistry, materials science, biophysics, and engineering—to study the properties of interfaces, develop new materials, and solve outstanding problems in global health. Immiscible Systems. When mixed, many solutions of polymers, surfactants, and salts form immiscible phases. We are interested in characterizing the properties of the interfaces between immiscible liquid phases and applying immiscible systems to the study of complex mixtures. We are particularly interested in those immiscible systems that share water as a common solvent. Paper Diagnostics. Successful implementation of point-of-care diagnostics has the potential to affect the global management of diseases. Paper is an attractive platform with which to develop assays designed specifically for the developing world because the infrastructure required to develop them is minimal and the materials needed to manufacture them are inexpensive. We will develop new materials that can enable biochemical assays that are not currently possible using paper alone.
Professor Robbat's area of expertise is in separation science and mass spectrometry. His group develops data analysis software that automatically identifies and quantifies target compounds by mathematically deconvolving mass spectra for up to 20 coeluting compounds. Once identified the spectra of target compounds are subtracted from the total ion current chromatogram resulting in mass spectra of unknowns. Once these compounds are identified, they are added to the retention time and mass spectrum library to analyze a wide variety of samples. They routinely track plant-climate interactions for tea, coffee, citrus fruit, and berries of between 500 and 1500 volatile metabolites. The objective is to learn how changes in climate will affect the sensory and nutritional compounds in foods we consume. Toward this end, they employ GC/MS, GC-GC/MS, and GCxGC/MS all with olfactory detection to learn first-hand how changes in metabolite distribution and concentration are affected.
Professor Robbat's research interests include the development of innovative analytical instruments, methods, and data analysis software used to solve a wide range of environmental problems, including: a subsurface sampling and analysis probe that detects pollutants without bringing soil or groundwater to the surface for analysis. This technology is used to rapidly characterize hazardous waste sites and to provide monitoring data during cleanup.
Bioorganic Chemistry and Chemical Biology. A significant frontier in chemical biology lies in the ability to develop new, selective chemical transformations that transpire at mild temperatures amidst many other reactive species and in parallel with the countless transformations that occur inside of a living cell. Research in the Scheck laboratory focuses on the invention and application of encodable, bioorthogonal chemical strategies. These tools will be used to report on inducible changes in protein function in living cells. Current efforts in the lab fall into two broad categories: 1) The development of new chemical methods that are used to study complex posttranslational modification networks and 2) The study of native and unnatural posttranslational modifications to provide valuable chemical and synthetic biology tools.
Physical Chemistry and Surface Science. The Shultz group applies physics and chemistry to understand the inner workings of hydrogen bonding. Hydrogen bonding plays key roles in environmental, biological, and atmospheric chemistry. Our program has research thrusts in all three directions. We specialize both in devising environments that clearly reveal key interactions and in developing new instrumentation. The most recent focus is on icy surfaces and on clathrate formation. Probing the ice surface begins with a well-prepared single-crystal surface. We have unique capabilities for growing single-crystal ice from the melt and for and preparing any desired ice face. Our clean water efforts are aimed at developing new materials to fill the significant need for safe drinking water. According to the World Health Organization, over one billion people lack safe drinking water. Our program is based on using photo catalysts to capture readily available sunlight to turn pollutants into benign CO2 and water. We developed methods to grow ultra-nano (~2 nm) particles that have well-controlled surface structures and chemistry.
Dr. Charles W. Fotis A37, AG39 Assistant Professor
Quantum Simulations. The quantum-mechanical motion of atoms and electrons is at the heart of the quantum information and energy conversion technologies. The operation of quantum computers, the measurement of tiny, nanoscale objects, catalysis at surfaces, and harnessing of novel energy sources all require an in-depth understanding of the quantum dynamics that govern the flow of energy and information. We develop and apply new theoretical methods to simulate and understand quantum systems and processes at the forefront of the quantum and energy technologies. Our research focuses on the theoretical description of emergent platforms for quantum sensing and computing, such as color centers in insulators and semiconductors, and single-molecule magnets and their assemblies. We also explore how molecules interact with the surfaces of superconductors and novel materials with exotic electronic structure like topological insulators to drive new chemical reactions.
Physical Chemistry, Surface Science, and Nanoscience. The Sykes group utilizes state of the art scanning probes and surface science instrumentation to study technologically important systems. For example, scanning tunneling microscopy enables visualization of geometric and electronic properties of catalytically relevant metal alloy surfaces at the nanoscale. Using temperature programmed reaction studies of well defined model catalyst surfaces structure-property-activity relationships are drawn. Of particular interest is the addition of individual atoms of a reactive metal to a relatively inert host. In this way reactivity can be tuned, and provided the energetic landscapes are understood, novel bifunctional catalytic systems can be designed with unique properties that include low temperature activation and highly selective chemistry. Newly developed curved single crystal surface are also being used to open up previously inaccessible areas of structure sensitive surface chemistry and chiral surface geometries. In a different thrust, the group has developed various molecular motor systems that are enabling us to study many important fundamental aspects of molecular rotation and translation with unprecedented resolution.
Organic Materials Chemistry
Our group applies the philosophy of physical organic chemistry to organic materials, in the forms of polymers, crystals and surfaces. Specifically, we investigate new materials that show macroscopic changes in properties upon exposure to external stimuli. Our main focus has been new materials that respond to light, which has a unique combination of characteristics: i) easy control over where light goes and when it goes there (spatiotemporal control), ii) easy control over intensity and energy, and iii) the ability to pass through many solid materials that traditional chemical reagents cannot. Our research has focused in three separate areas.
1. Photochemical control of charge. As interactions between charges dictate much of molecular behavior, controlling charge can yield control over matter. We have developed a series of materials in which light switches the charge-based interactions between polymer chains from attractive. By combining this top-down fabrication approach of with the bottom-up fabrication method of layer-by-layer assembly, we have developed thin films in which photochemical lability is confined to individual nanoscale compartments, yielding photo-delaminated free-standing films and multi-height photolithography.
2. Using functional side chains to control conjugated materials. Conjugated materials hold great promise for applications including solar cells and displays. We have focused on expanding the role of the side-chains of these materials, which occupy up to half of their mass but are typically reserved only for solubility. Early work in our group focused on integrating photolabile side chains for negative conjugated photoresists. This has evolved to using the non-covalent interactions of aromatic side-chains for controlling interactions between molecules, and therefore their material properties, including the use of mechanical force to control luminescence—mechanofluorochromism.
3. Singlet-oxygen responsive materials. Singlet oxygen (1O2) is a critical reactive oxygen species in photodynamic therapy for cancer as well as in damage to plants upon overexposure to light. Its photochemical production is also chemically amplified through a photochemical reaction, which is the lynchpin of several commercial bioanalytical technologies. Through a combination of fundamental physical organic chemistry and materials chemistry, we have luminescent conjugated polymer nanoparticles as probes for 1O2 in water that shows improved limit of detection over the commercially available luminescent probe for 1O2.
Physical Inorganic and Materials Chemistry. Current work is largely in the area of solid-state electronic and ionic conducting materials, and attempts to achieve useful optical and electronic properties through an understanding of the fundamental contributing effects. An example is the attempt to obtain nearly-free-electron (metallic) behavior in metal oxide bronzes and other intercalation compounds, in both bulk and thin-film materials. Synthesis of new materials and the characterization of their electronic, structural, and transport properties is the major goal of the work. To this end, we use optical spectroscopic (UV-VIS, NIR, IR) and magnetic measurements to probe electronic ground state structures, single crystal and powder X-ray diffraction to investigate crystallography and conductivity, Hall-effect measurements to probe electronic transport, and electrochemical means to investigate thermodynamic properties and kinetics of ionic motion.