Festival of Science, Scholarship & Creativity 2022
At St. Lawrence’s Festival of Science, Scholarship, and Creativity on April 29, 2022, Chemistry majors and first-year students doing research in the Chemistry Department presented their results.
Aida Gueye, Faculty Amanda Oldacre, Chemistry
“Investigating electrocatalytic capabilities of functionalized petroleum coke for the electrosynthesis of ammonia”
Abstract: Ammonia is a compound that is used in many different products in our modern society, from fertilizers to refrigerants. In industries, ammonia is mainly produced through the Haber-Bosch process. Though it is an efficient process to meet our demands in ammonia, the Haber-Bosch method is energy intensive and involves ever - sophisticated instrumentation. This project focuses on providing an alternative to the Haber-Bosch process by tuning the electrocatalytic capabilities of petroleum coke, a cheap and abundant material, to catalyze ammonia synthesis electrochemically. Petroleum coke will be tuned through activation followed by acid functionalization. At this initial stage of the project, samples of petroleum coke activated with NaOH and with KOH at 60°C, a lower reaction temperature than previously reported, are compared. The methods used for the comparison are FT-IR spectroscopy and cyclic voltammetry. Cyclic voltammetry is used to determine the electroactive surface area when samples of activated petroleum coke are mixed with PTFE and used to coat a glassy carbon electrode surface. The end-goal is to determine the activation parameters that lead to the highest electroactive surface area in petroleum coke and draw correlation with the IR spectra. Those parameters will be used to study acid functionalization of activated petroleum coke and then nitrogen reduction by functionalized petroleum coke.
Joel Asare, Faculty Adam Hill and Mindy Pitre, Chemistry
“Microchemical Analysis of Metallic Compounds in Village of Heuvelton Gravesites”
Abstract: Unmarked graves have been found in the Village of Heuvelton, and we must carefully relocate the gravesites. The reality remains that in order to do so, we must respectfully record the artifacts found within. In the attempt to categorize and preserve coffins and burial sites via relocation process, often unknown inorganic materials such as metallic artifacts may be found. In the Heuvelton case, these artifacts were highly corroded which hinders the simple visual identification. Therefore, microchemical analysis was used to quantify and categorize the unknown metallic compounds within each artifact. Iron amounts were confirmed with a salicylate UV-vis titration and other metals were analyzed via flame atomic absorbance spectroscopy. Results were compared to published data which pertained composition details and identities of the possible artifacts.
Corryn Canell, Faculty Adam Hill, Chemistry
“Synthesis of ZrOCo Light Absorbers on Silica
Abstract: There have been many efforts to switch to renewable energy by the use of light-absorbing materials. For this to occur, air-free techniques need to be completed to allow binuclear units to attach to the surface of silica nanoparticles. Through these air-free techniques, we are able to attach Zr on silica, then proceed to add Co to make a final product of ZrOCo which will then be analyzed with infrared spectroscopy.
Blake Heston, Faculty Adam Hill, Chemistry
“Synthesis of Heterobinuclear Units for Artificial Photosynthesis
Abstract: The synthesis of heterobinuclear units is important for the study of artificial photosynthesis. My Research has focused on synthesizing different heterobinuclear units on a silica backing, such as Zirconium-Cobalt and Titanium-Cobalt. Specific air free techniques are used in this synthesis to create a metal to oxygen, to metal complex that is then bound to silica nanoparticles. Units can then be dosed with other molecules such as bipyridine. These particles are then pressed into optically transparent pellets that can then be used for spectroscopic measurements in instruments such as the Fourier Transform Infrared Spectrometer.
Stephanie Sauve, Faculty Matthew Skeels, Chemistry
“Investigation of the chemical and thermal stability of the coral cyan fluorescent protein from Anemonia majano
Abstract: Photodamage of symbiotic dinoflagellates exposed to thermal stress is involved in coral bleaching, a major cause of reef decline. When coral reefs die, the ecosystem the reef supports and the biodiverse species they protect die along with it. In addition to concerns surrounding biodiversity, economic goods and services provided by corals, valued at over US $20 trillion annually, would be lost if the reefs were to disappear. Photoprotection is therefore a vital aspect of coral stress physiology. Corals produce a variety of fluorescent proteins (FPs), some of which screen the symbiotic algae from excess sun light, and others enhance light availability for photosynthesis of the algal symbionts by converting longer wavelengths of light into a more usable form of light for the dinoflagellates. Cyan FPs have characteristically broad absorption/excitation spectra with peaks at 440–460 nm that overlap with the absorption spectrum of photosynthetic pigments of the symbiotic dinoflagellates, making these FPs photoprotective. The question arises about whether the thermodynamic stability of these cyan FPs are related to reef decline. To determine the thermodynamic stability of a cyan FPs, the CFP from Anemonia majano was cloned into an E. coli expression vector with an 6x His affinity tag. The 6xHis-CFP was overexpressed and purified from E. coli. Thermal and chemical denaturation curves of this protein were monitored using intrinsic tryptophan fluorescence. Additionally, we seek to understand which interactions within the protein are have the greatest impact on the protein’s stability. Mutagenesis studies were performed to determine which factors within the protein are most responsible for stability.
Hannah Anderson, Faculty Samuel Tartakoff, Chemistry
“Synthesis of Opioid Derivatives through Wagner-Jauregg Cycloaddition”
Abstract: Since the end of the twentieth century, an opioid addiction epidemic has impacted millions of people across the United States. Despite attempts to regulate their distribution, misuse of prescription painkillers can lead to people losing their life as a result of their addiction. The aim of this research is the synthesis of molecules with the opioid substructure that have pain-relieving qualities without the side effects of addiction. The Wagner-Jauregg reaction is a type of Diels-Alder cycloaddition in which the diene is a styrene molecule or styrene derivatives. Due to the conjugated nature of the aromatic ring component, this reaction is high-energy and can only be accomplished by altering the functionality of the ring. I will be synthesizing various substituted dienes and examining what structural features improve the Wagner-Jauregg reaction over the previously published Wagner-Jauregg reactions.
Annie Knapp, Faculty Adam Hill and Catherine Jahncke, Chemistry
“Time-Resolved Photoluminescence Spectroscophy of Charge Transfer States in ZrOCo and TiOCo Heterobinuclear Units”
Abstract: Heterobinuclear unit light absorbers consisting of chemically dissimilar transition metals can serve as light absorbers for nanoscale artificial photosystems. TiOCo and ZrOCo units on silica nanoparticles were coupled with 2,2’-bipyridine (bipy) as a luminescent electron acceptor, with TiOCo observed as a negative control. The synthesis steps were confirmed using FT-IR and the geometries of the heterobinuclear unit-bipy diads were modeled using DFT. The particles were pressed into pellets and then placed into a home-built 3D printed gas cell. Time-correlated single photon counting (TCSPC) and time-resolved emission spectroscopy (TRES) data were collected under argon and oxygen atmospheres to measure the relaxation of the excited state. The quenching of emission in the presence of oxygen supports that the long-lived excited state of the ZrOCo-bipy system is due to a change in spin state.
Catie Leberman, Faculty Amanda Oldacre, Chemistry
“The Electrochemical Degradation of PET Plastic Monomers Using Fe(lll)-TCPP”
Abstract: Plastic pollution is a rising concern due to its negative environmental and health effects. There is no pathway for plastic to naturally degrade, it only breaks down into smaller pieces. Eventually the size of the plastic is small enough that it can easily be ingested, where it can potentially have carcinogenic effects. There are some microorganisms that have the ability to mineralize these complex polymers. By looking at the active site of the enzyme capable of performing mineralization reactions, it can be used as a reference for creating a bio-inspired catalyst with similar functions. Herein, we proposed metalated meso Tetra(4-carboxyphenyl) porphyrins (TCPP) as catalysts for the oxidation of polyethylene terephthalate (PET) plastic. The metalated Zn(II)TCPP will be used as a control, which is predicted to not show catalytic activity. We propose that Fe(III)TCPP will have catalytic activity towards the degradation of PET. UV-vis will be used to determine if porphyrins have been completely metalated. Electrochemical experiments, such as cyclic voltammetry, bulk electrolysis, and hydrodynamic voltammetry will determine if the proposed porphyrin structures act as electrocatalysts towards the degradation of plastics.
Jenna Mack, Faculty Adam Hill, Chemistry
“Coordination Thermodynamics of Thiocyanate to Heterobinuclear Units”
Abstract: Heterobinuclear light absorbers are pairs of metal atoms on silica surfaces. While these pairs can perform electron transfer, their ability to do so may depend on how they are coupled to electron acceptors. Thiocyanate was used as a model system to understand this binding. Silica nanoparticles containing zirconium and cobalt were dosed with various thiocyanate at concentrations and coordination to each metal was monitored by infrared spectroscopy to determine the coordination thermodynamics.