The Demoranville group investigates the chemical components of bourbon using chromatographic methods. Currently we are developing methods to accomplish that goal and long term hope to study the impact of different production processes using those methods.
Dr. Jeff Fieberg’s current research interests are in technical art historical investigations of modernist paintings and analysis of artists’ materials. In 2011-2012, he participated as the first Sabbatical Leave Research Fellow in Technical Art History at the Indianapolis Museum of Art (IMA). Working in the Conservation Science Laboratory directed by Dr. Greg Smith ’95, technical analyses of paintings from the IMA’s European collection were performed using x-ray fluorescence spectroscopy, Raman microspectroscopy, and infrared microspectroscopy. Artwork analyzed included Mysterious Departure by Giorgio de Chirico and the Cincinnati Art Museum’s Undergrowth with Two Figures by Vincent van Gogh. In Van Gogh’s Undergrowth with Two Figures, a pink geranium lake pigment had photochemically faded to white. Analysis of 387 white flowers in the painting revealed that 37.7 % of the white flowers were originally pink. A digital reconstruction of the painting was made to suggest the painting’s original appearance with regard to the faded flowers. This study on Undergrowth with Two Figures was published in 2017 in Applied Spectroscopy and may be downloaded here. Fieberg is currently on sabbatical (spring 2019) at the IMA (Newfields) where he will continue to analyze artwork—primarily paintings from their Modern European Collection.
Fieberg transforms the technical art analyses of paintings into pedagogical materials used in his Molecular Modernism course. For example, Fieberg designed a dry laboratory in which students investigate whether de Chirico’s painting, Mysterious Departure, is authentic, a forgery, or a verifalsi (painted by the artist but backdated). This student activity was presented as a poster at the International Council of Museums-Committee on Conservation Triennial Meeting in Copenhagen, Denmark, in 2017 (you can view the poster here). Fieberg has taught Molecular Modernism as a three-week travel course in Paris and Provence (France), a semester-long course in Strasbourg (France) and London (England), and a first-year studies course on campus with field trips to Indianapolis, Chicago, and/or Washington D.C.
On campus, Fieberg and his students have collaborated with religion professors, Dr. Beth Glazier and Dr. Tom McCollough, to work with ancient lead amulets to date, electrolytically reduce, and unroll them. Current projects include a forgery investigation of an early 20th century painting and collaboration with a student to refabricate ancient glass colors.
In our group we are interested in exploring the species which exist in solutions using a combination of infrared spectroscopy and computations. Solutions are held together by networks of intermolecular forces. Though these are often thought of as transient interactions, solutions with strong interactions have a tendency to order into pseudo-stable structures. With infrared spectroscopy we can probe these structures and their environments using the vibrational motions of involved functional groups. We also perform structural computations to investigate how various ordered species will impact the vibrational motion being used as a probe. Combining these two data sets gives us the ability to elucidate what these ordered species might be. Currently, our group is exploring non-lithium ion battery electrolytes, which contain magnesium or zinc ions in organic solvents. The species likely to exist in these electrolytes include solvated ions, ion pairs, or ion aggregates. Magnesium and zinc ions are particularly interesting because they can provide insight into what properties have the most influence on solvation structures. Since these two ions have identical charge and ionic radii, the differences which arise must be from their electronic configurations. We are also currently investigating the effects of salinity on hydrogen-bond interactions between water and small organic molecules. The effect of salinity on aqueous biochemical solutions is commonly called the Hoffmeister effect. However, most molecular scale studies of what happens to cause the observed trends in protein folding and unfolding have either looked from the perspective of water or that of large polymers and proteins. We are attempting to approach this puzzle from the perspective of something in between by looking at effects on intermolecular forces as probed by the vibrational motions of small organic solutes.
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Research in the Scott lab lies in the interface between chemistry, biology/biochemistry, and nanotechnology in an effort to develop improved diagnostic and therapeutic systems with implications across medicine and pharmaceutical sciences. There are several different projects students can be involved in with the major theme of generating new ways to treat and monitor cancer or other diseases.
Bacteria are used to produce new anti-cancer molecules, which will be further modified to enhance not only the potency, but also the specificity of the drugs toward cancer. These new molecules will be investigated with regard to their ability to selectively kill cancerous tissue (cytotoxicity). We are currently exploring the drugs ability to kill lung cancer cells grown in the lab. Once generated, the new anticancer agents will also have the opportunity to be incorporated into a nanoparticle drug delivery system. The delivery systems will be used to further optimize the delivery to drug to the tumor and reduce non-specific side effects.
Nanotechnology is being utilized to create a tunable drug delivery platform. Unwanted side effects are a major hurdle with current chemotherapy options. A system capable of selectively delivering a drug payload, only when the nanoparticle has accumulated in a tumor, will greatly improve the perspective for new and old anticancer drugs alike. To that end, biomolecules will be combined with inorganic and polymeric materials to create a tunable “theranostic” nanoparticle that will not only deliver multiple drugs at specified intervals but also be used to monitor disease state and therapeutic response. Theranostic is a hybrid word, describing a particle that can combine therapy and diagnostic capabilities in a single entity.
Sensors are also being developed using gold and iron oxide nanoparticles. The sensors will be capable of monitoring different targets, such as DNA, proteins, or small molecules. Of particular interest is the development of a device that would capable of real-time feedback, with applications in analysis situations such as third world countries, operating rooms, and athletic sidelines.
Students will have the option to gain experience with a range of chemical and biochemical techniques including cell and tissue culture, natural product production and isolation, in vitro cytotoxicity assays, molecular biology, sensor development, and nanoparticle synthesis, optimization, and characterization. Students will be prepared for life after Centre whether that includes professional school (medical, pharmacy, etc.), graduate school, or the workforce.
Ruthenium polypyridyl complexes have many different properties that can be exploited. The ligands that bind to the ruthenium can be easily modified, the complexes absorb visible light, can be luminescent, and can bind DNA in different ways. I am specifically interested in studying the spectroscopic properties of ruthenium polypyridyl complexes as the environment around them changes, specifically when in the presence of DNA.
The synthesis of multimetallic complexes with unusual geometry, electronic and magnetic properties
My collaborative research with students focuses on synthesizing novel multimetallic complexes of polyanionic chelating ligands. These ligands stabilize transition metals in high oxidation states and unusual geometries. For instance, the cobalt ions below are in an uncommon square planar 3+ oxidation state. The Co(III) ions are also paramagnetic. The oxidation/reduction behavior of these compounds is fascinating. I have shown in previous research that these metal complexes can themselves act as ligands for other transition metals. This research introduces the possibility of using them to construct new materials with interesting electronic and magnetic properties. My student collaborators and I are in the process of synthesizing and characterizing a wide range of multimetallic complexes of different polyanionic chelating ligands.
Stable Isotope Geochemistry of Volcanic Supereruptions
I also have a collaborative research project with geologists at the University of Oregon studying the climate effects of ancient volcanic supereruptions. We study eruption products in the John Day Fossil Beds in eastern Oregon by oxygen isotope geochemistry. Very large silicic eruptions, called supereruptions, can inject massive quantities of sulfur dioxide, SO2, into the atmosphere. The SO2 is then oxidized by either hydrogen peroxide or ozone to produce sulfur trioxide, SO3. The sulfur trioxide will combine with water to form sulfuric acid, H2SO4, which will form very small droplets called an aerosol. The aerosol will block solar radiation and lead to local or global cooling. Over time, the sulfuric acid falls back to earth as acid rain. It is impossible to directly measure SO2emissions for ancient eruptions, but the sulfuric acid content can be measured in the rock record. We use a laser fluorination line to separate oxygen from the sulfur and then a mass spectrometer to measure the 17O:16O ratio. If the SO2 was injected into the stratosphere, the major oxidant would have been ozone and the 17O:16O ratio would be higher than normal. If the SO2was injected into the troposphere, the major oxidant would have been hydrogen peroxide and the 17O:16O ratio would be normal.
Lignin is a biological polymer that gives wood its rigid structure and fuel value. Lignin also contributes to the brown color of unbleached Kraft paper, the flavor of bourbon, and the vanilla smell of old books. However, from a chemist’s perspective, lignin is a vastly underutilized source of carbon atoms, which could use used to make biofuels, commodity chemicals, or pharmaceuticals. The reasons for the underuse of lignin are twofold: first, lignin has a complex, irregular structure that resists the chemist’s attempt to order it into smaller units and second, the chemical bonds in lignin are strong and stable and thus difficult to rearrange into more valuable products.
In nature, white-rot fungi selectively degrade lignin but not cellulose by producing enzymes that use metals such as iron and manganese to activate hydrogen peroxide as a relatively benign oxidizing agent. Inspired by the ingenuity of the white-rot fungi, my students and I are studying a family of iron, manganese, and cobalt complexes as catalysts for lignin oxidation. These complexes speed up the reaction between lignin-like molecules and oxidizing agents such as Oxone or hydrogen peroxide.
We use instruments like high performance–liquid chromatography (HPLC), gas chromatography–mass spectrometry (GC-MS), and nuclear magnetic resonance spectroscopy (NMR) to probe the secrets of these catalysts in order to understand how they work and how to improve them. Students who join my group gain may experience in instrumental analysis, kinetics, and chemical synthesis. While the Young Group is happy to consider students at all levels, students are usually more productive after they have taken CHE 241: Organic Chemistry I.