Tuning Iron-Based Macrocyclic Catalysts for Efficient C–C Coupling

Type: Graduate
Author(s): Tahmina Afroz Chemistry & Biochemistry
Advisor(s): Kayla Green Chemistry & Biochemistry

Tuning Iron-Based Macrocyclic Catalysts for Efficient C–C Coupling
Our study investigated high-spin iron/tetra-aza macrocyclic complexes as sustainable catalysts for Suzuki–Miyaura C–C coupling, demonstrating ligand modifications as key regulators of catalytic activity. Initial findings showed that ligand modifications influenced yields but could not separate redox effects from geometry. Later studies on PyN3 confirmed that 4-substituted pyridine ligands provide direct electronic control, with EWGs boosting yields and EDGs reducing efficiency due to dimer formation. A comparative analysis revealed that FeIII(RPy2N2)³⁺ outperformed FeIII(RPyN3)³⁺ by at least 10%, highlighting scaffold design as a key determinant of activity. Substrate scope showed broad functional group tolerance (43–78% yields), and mechanistic studies identified an iron(III)-hydroperoxo species as the active oxidant, ruling out a Fenton-type radical pathway. These findings establish iron-based macrocyclic catalysts as a tunable and sustainable alternative to palladium for direct arylation of un-activated arenes.

Towards a Comprehensive Benchmark of Quantum Mechanical pKa Prediction: Conformational Sampling, Model Solvent, Basis Set, Density Functional, and Empirical Corrections for the SAMPL7 Dataset

Type: Graduate
Author(s): Donatus Agbaglo Chemistry & Biochemistry Minh Ho Biology
Advisor(s): Benjamin Janesko Chemistry & Biochemistry

The fight against Alzheimer’s: Synthesizing a multifunctional antioxidant molecule with increased blood-brain barrier permeability

Type: Undergraduate
Author(s): Saba Anjum Chemistry & Biochemistry Shrikant Nilewar Chemistry & Biochemistry
Advisor(s): Kayla Green Chemistry & Biochemistry

Oxidative stress is associated with the development and progression of neurodegenerative diseases, including Alzheimer’s, but there are no approved drug therapeutics that effectively target oxidative stress in Alzheimer’s. The Green Research Group has previously synthesized and reported a pyridine-containing tetra-aza macrocycle, L2, which acts as a multifunctional antioxidant agent by targeting oxidative stress directly through radical scavenging and metal ion chelation as well as catalytically through activation of the Nrf2 pathway. While multiple preliminary studies conducted on L2 have confirmed its potent antioxidant activity, its high hydrophilicity results in reduced blood-brain barrier permeability, which is a concern when designing drug therapeutics for neurodegenerative diseases. It is hypothesized that incorporating a self-immolative linker onto L2 will result in increased blood-brain barrier permeability while maintaining antioxidant activity under physiological conditions.

Shape-shifting Molecules: The Search for Low Cost, Ring-shaped Drugs

Type: Undergraduate
Author(s): Grace Bobo Chemistry & Biochemistry
Advisor(s): Eric Simanek Chemistry & Biochemistry

The shape of a drug will determine how it interacts in the body. For it to work, it must dissolve, be absorbed into the bloodstream, avoid breakdown, enter the cell and bind to its target. Each of these steps likely requires a different shape. The pharmaceutical industry has historically only focused on the shape required to bind the target. This research has identified molecules that can readily adopt multiple shapes. These ring-shaped molecules (called macrocycles) represent a new model for drug design. Usual drugs (ie ibuprofen) are small and interact with a specific target to stop a chemical reaction. Macrocycles can work by an additional mechanism. They are larger and can interfere with interactions between proteins but are still small enough to travel the body. The preparation of these macrocycles is inexpensive and quick, properties that are important for the pharmaceutical industry. This poster describes the design and synthesis of a macrocycle and an analysis of the shapes that it adopts.

BOILED-eggs and the Blood-Brain Barrier: How BOILED-egg Modeling Can Predict Permeability of Pyridine Macrocyclic Molecules to Combat Alzheimer's Disease

Type: Undergraduate
Author(s): Luke Chouteau Chemistry & Biochemistry
Advisor(s): Kayla Green Chemistry & Biochemistry

Every 65 seconds, someone develops Alzheimer's disease, which is the seventh leading cause of death in the United States. A major barrier to potential therapeutics is the permeability of these molecules across the blood-brain barrier. We have developed small molecules with strong reactivity to combat the oxidative stress known to cause Alzheimer’s disease. However, the permeability is less than ideal. As a result, my goal is to produce a molecule that has enhanced permeability but retains the reactivity of the parent molecules. To achieve this, the BOILED-Egg model assessed different derivatives of our parent molecule, Py2N2. This model showed the differences in lipophilicity among different Py2N2 compounds and how they impact permeability into the blood-brain barrier and gastrointestinal tract. Background information on our parent molecule and its function regarding Alzheimer's development will be outlined to give a scope of what these compounds can target and how they function. Compounds with high lipophilicity reflected in the model will have schemes of synthetic synthesis for future directions.

Reimagined Route to Drug Discovery: Macrocyclization leads to 20 predicted and persistent products for chemical library development

Type: Graduate
Author(s): Liam Claton Chemistry & Biochemistry
Advisor(s): Eric Simanek Chemistry & Biochemistry

In the pursuit of new ways to develop libraries of compounds for pharmaceutical drug discovery, the utilization of a robust and tunable macrocycle synthetic scaffold has led to the discovery of persistent and structurally well-defined conformational isomers. Targeting these macrocycles that exist as an ensemble of preorganized conformations represents a compromise between the pursuit of flexible molecules of undefined structure and rigid molecules biased towards a single conformation. This system is based on the quantitative dimerization of a monomer to afford macrocycle. When a single monomer is used, six unique structures are obtained. When two monomers are used, twenty unique structures are obtained. These different structures (conformational isomers) are accessed via hindered bond rotation with a barrier of ~18 kcal/mol and are observable by ¬1H NMR. Current drug discovery methods heavily rely on screening large chemical libraries of small, ridged molecules against protein targets and typically sacrifice entropy in favor of stronger ligand-target binding. Using our system, synthesis of 50 monomers allows for the generation of a library of over 10,000 structurally unique macrocycles. The goal of this work is to provide new chemical libraries for drug discovery.

Spectrophotometric detection of PFAS in water using bovine serum albumin and tetrasodium tetraphenylporphyrintetrasulfonate

Type: Undergraduate
Author(s): Ngan Dinh Chemistry & Biochemistry
Advisor(s): Onofrio Annunziata Chemistry & Biochemistry

Perfluoroalkyl substances (PFAS), known as "forever chemicals", are ubiquitous environmental contaminants whose remarkable persistence poses significant risks to human health and ecosystems. Thus, it is important to develop analytical assays to determine PFAS concentrations based on widely accessible, readily available instrumentation, such as UV-VIS spectrophotometry. Tetrasodium tetraphenylporphyrintetrasulfonate (TPPS) is a water-soluble porphyrin known for its spectrophotometric property in water. It is also known that TPPS binds to the protein bovine serum albumin (BSA). We investigated the effect of BSA on the absorption spectrum of TPPS and how PFAS presence impacts BSA-TPPS interaction in water. Interestingly, we found that BSA induces TPPS precipitation. As BSA concentration increases, TPPS solubility first dramatically decreases, then increases, ultimately leading to the formation of homogeneous solutions at relatively high BSA concentration. Furthermore, addition of two different PFAS, sodium perfluorohexanoate and potassium perfluorobutanesulfonate salts, to homogeneous BSA-TPPS mixtures appreciably alter TPPS spectra. Our results show that these mixtures can be used to produce calibration curves relevant to the determination of PFAS concentrations in water.

Mimicking Nature's Strategy for Making Drugs with Large, Predictable, Ring-shaped Molecules

Type: Undergraduate
Author(s): Annie Downum Chemistry & Biochemistry Liam Claton Chemistry & Biochemistry
Advisor(s): Eric Simanek Chemistry & Biochemistry

Some of the most effective drugs from Nature are large and ring-shaped, so-called macrocycles. Macrocycles are interesting because they can interfere with protein-protein interactions, a different strategy for therapy than that used by small molecules (like aspirin). The challenge with the design of macrocycle drugs is that they are difficult to make and behave unpredictably. Here, an efficient strategy to make macrocycles is described. These molecules behave consistently (with preserved shapes) and can be tailored to optimize binding (a hallmark of drug design). The two macrocycles described differ in the choice of one group with significant (and predictable) consequences. Both groups mimic amino acid sidechains that are implicated in protein-protein interactions. One amine, N-methylbenzylamine, yields a macrocycle that will adopt six conformations in solution (an advantage when looking for drugs). The second amine, isobutylamine, gives more than eight conformations. Structural analysis was accomplished by NMR spectroscopy.

Influence of the Quinoline Moiety on the Pharmacological Properties of Tetra-aza Pyridinophanes and Their Anticancer Activity

Type: Graduate
Author(s): Sarah Dunn Chemistry & Biochemistry
Advisor(s): Kayla Green Chemistry & Biochemistry

The development of novel anticancer agents with enhanced selectivity and reduced toxicity remains a critical challenge in medicinal chemistry. In this study, we investigate the influence of the quinoline moiety on the pharmacological properties of tetra-aza pyridinophanes, with a focus on their anticancer activity. A series of structurally diverse derivatives were synthesized, incorporating variations in the quinoline moiety position and R-group functionalization. The compounds were characterized using multiple spectroscopic and analytical techniques, and their biological activity was evaluated in cancer cell lines. Results indicate that the presence of the quinoline moiety significantly improves anticancer efficacy compared to its absence, suggesting enhanced interactions with cellular targets. Furthermore, permeability studies reveal that the methoxy (-OMe) substitution on the pyridine ring enhances cellular uptake relative to the hydroxyl (-OH) counterpart. These findings highlight the potential of quinoline-functionalized tetra-aza pyridinophanes as promising candidates for targeted cancer therapy. By improving the selectivity between normal and cancerous cells, this work advances the design of next-generation chemotherapeutics with reduced systemic toxicity.

Streamlined Synthesis of a Potent Inhibitor of Dehydroquinate Synthase

Type: Undergraduate
Author(s): Ella Fitterer Chemistry & Biochemistry
Advisor(s): Jean-Luc Montchamp Chemistry & Biochemistry

This project is to synthesize a known nanomolar inhibitor of dehydroquinate synthase for evaluation as an antimicrobial agent in collaboration with TCU's Biology Professor McGillivray. It is estimated that nearly 10 million individuals could die per year due to antimicrobial resistance by the year 2050 (1). The focus will be two-fold: first, the improved synthesis of alkenylphosphonate 1, and then its elaboration into various prodrugs to improve its activity in vivo. The in vitro activity of 1 on dehydroquinate synthase is Ki = 0.29 nM, while the enzyme's substrate has Km = 4 microM (2). Dehydroquinate synthase is an enzyme that is part of the aromatic amino acid biosynthetic pathway, which is essential to bacteria and plants but does not exist in mammals - which is why we must eat vegetables and fruits. Thus, the toxicity to humans of antibacterial compounds targeting this pathway should be minimized.

Compound 1 was synthesized previously (2), but improvements to its synthesis must be made since it will be the starting material for the preparation of prodrugs. Prodrugs are compounds that are precursors of 1 but where the charge is masked. Because inhibitor 1 is highly hydrophilic, this prodrug strategy should be necessary to achieve biological activity in vivo. Initial work will aim at the large-scale preparation of 1 and particularly eliminate as much as possible the need for purification by chromatography.

The Goldilocks Combination to Unprecedented Perovskites

Type: Graduate
Author(s): Maegyn Grubbs Chemistry & Biochemistry Sergei Dzyuba Chemistry & Biochemistry Zygmunt Gryczynski Physics & Astronomy Bong Lee Physics & Astronomy
Advisor(s): Jeff Coffer Chemistry & Biochemistry

Metal-halide perovskites are crystalline semiconductive materials with a tunable direct bandgap, defect tolerance, and high charge carrier mobility. These useful properties have led to application perovskites such as LEDs, solar cells, and more recently lasers.
In this project, cetyl ionic liquid (IL) enhanced Methylammonium Lead Tribromide perovskites thin films were studied on substrates with varying refractive indices to determine how refractive index impacts photophysical properties. Methylammonium Lead Tribromide perovskites have a refractive index of 2.19. In comparison glass, a common substrate, has a refractive index of 1.51 while yttrium-stabilized zirconium oxide (YSZ) is 2.15.
Thin films of Methylammonium Lead Tribromide grown on yttrium-stabilized zirconium oxide (YSZ) in the presence of an ionic liquid are found to be strongly emissive in the green at a wavelength of 535 nm (with quantum efficiency values above 60%). The associated photoluminescence excitation (PLE) spectra show an unprecedented series of distinct peaks, one set with an average energy separation of ~200 milli-electron volts, the other set with a ~100 milli-electron volt separation indicating possible Giant Rashba Splitting. The preparation and structure of these films, along with origins of this splitting, are presented.

Don't spill the tea(or the chemicals): A safety intiative at TCU

Type: Undergraduate
Author(s): Tatum Harvey Chemistry & Biochemistry Ibukun Alausa Biology Grace Bobo Chemistry & Biochemistry Nick Boehly Biology Delaney Davis Biology Audrey Dolt Biology Annie Downum Chemistry & Biochemistry Isabelle Galvan Biology Jacquelyn Ha Biology Daisy Li Chemistry & Biochemistry Aidan Meek Biology Jonah Morgan Engineering Kadie Nguyen Chemistry & Biochemistry Mark Sayegh Chemistry & Biochemistry Samantha Shah Chemistry & Biochemistry William Stites Biology Sophia Tunks Chemistry & Biochemistry Lexi Winter Biology Amarige Yusufji Chemistry & Biochemistry Troy Zambak Biology
Advisor(s): Kayla Green Chemistry & Biochemistry Heidi Conrad Chemistry & Biochemistry Julie Fry Chemistry & Biochemistry

Lab safety across independent academic and research labs for undergraduate and graduate students is critical to creating a successful chemistry experience. Many students at Texas Christian University (TCU) are heading into the medical field where healthcare professionals work in sensitive and controlled environments every day. Others are moving to research and industrial labs where safety is a critical component of success. Safety concerns constantly arise within these environments. Understanding how to manage a hazard or safety concern is a critical skill that translates to a successful professional skillset and creates a positive professional environment. TCU is offering a groundbreaking safety course for undergraduates and graduate students starting Fall 2024. Students in the course will focus on learning objectives from American Chemical Society’s, “Guidelines for Chemical Laboratory Safety in Academic Institutions”. The TCU Chemistry Club is working to complement this new course with a campus awareness campaign and include local elementary schools that work with Chemistry Club. We will be discussing the various awareness strategies that the Chemistry Club has implemented to achieve awareness at various campuses.

Predicting pKas of flexible polybasic pyclen derivatives: A pKa challenge

Type: Undergraduate
Author(s): Tatum Harvey Chemistry & Biochemistry
Advisor(s): Benjamin Janesko Chemistry & Biochemistry

Predicting pKa and pH-dependent speciation is an important aspect of drug design. Often, pKa behaviors govern various properties including solubility, docking poses, and membrane permeability of drug molecules. Understanding these properties is critical for synthesizing an applicable drug molecule for a given ailment. Traditionally, fairly accurate computational pKa predictions are achievable for small rigid gas-phase molecules with a single acid/base site. However, the same level of accuracy has not been reached for larger, macrocyclic molecules that more closely resemble pharmaceuticals. To predict the pKa for their large, flexible, polybasic molecules in water, new workflows were developed to account for solvation and conformational dynamics incurred by these larger molecules in solution. We evaluated a series of flexible tetra-aza macrocyclic small molecules derived from pyclen using conformational analysis alongside continuum solvent models and DFT calculations to obtain pKa predictions. Utilizing a linear fit we can obtain an RMSD of 0.9 pKa units which is competitive with the best physics-based methods in the SAMPL6 benchmark for pKa predictions. This presentation will focus on the development of the workflow, benchmarking, and results.

Simulating the redox potential of tetra-aza macrocycle copper complexes

Type: Undergraduate
Author(s): Minh Ho Chemistry & Biochemistry
Advisor(s): Benjamin Janesko Chemistry & Biochemistry

Superoxide dismutase (SOD) enzymes are a major defense against superoxide, which is a potent reactive oxygen species. SOD mimics have potential clinical relevance as treatments for neurodegenerative diseases. The Green group at TCU synthesized tetra-aza macrocycle copper complexes since they serve as promising SOD mimics. The redox potential of these complexes is a critical factor in their antioxidant activity, as it determines their ability to bind and transfer electrons. However, the vast number of possible tetra-aza macrocycles presents a challenge for experimental synthesis and testing. To address this, we perform computational simulations to predict the redox potential of un-synthesized tetra-aza macrocycles, helping to identify the most promising candidates for further study. This work, in combination with other predictive models for properties such as pKa, solubility, permeability, and metal binding, accurate redox potential simulations can help focus experimental efforts on the most viable SOD mimics, accelerating the development of effective treatments.

Liquid Phase Deposition of Nickel Oxide as a Hole Transport Layer for TEMPO-Mediated Oxidation

Type: Undergraduate
Author(s): Favor Igwilo Chemistry & Biochemistry Qamar Hayat Khan Chemistry & Biochemistry Daisy Li Chemistry & Biochemistry Ines Soto Chemistry & Biochemistry
Advisor(s): Benjamin Sherman Chemistry & Biochemistry

Liquid Phase Deposition of Nickel Oxide as a Hole Transport Layer for TEMPO-Mediated Oxidation

Favor Igwilo, Texas Christian University, Class of 2026
Laboratory of Dr. Benjamin Sherman, PhD;
Department of Chemistry and Biochemistry

Efficient positive charge (hole) transport is essential in photoelectrochemical systems for driving oxidation reactions. In our target process, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO), a stable free radical mediator, drives the redox reaction of benzyl alcohol to benzaldehyde, a reaction with significant applications in industrial processes and synthetic chemistry. TEMPO-mediated oxidation offers a sustainable alternative to conventional oxidation methods that generate hazardous waste, highlighting the need to enhance its viability in photoelectrochemical applications. Nickel oxide (NiO), a p-type semiconductor, is suited for this role due to its hole transport ability, abundance and cost-effectiveness compared to conventional alternatives such as TiO₂. To integrate NiO as a hole transport layer in TEMPO-mediated oxidation, we developed a liquid phase deposition (LPD) protocol for fabricating uniform NiO films on fluorine-doped tin oxide (FTO) glass. These films were incorporated into FTO|WO3-BiVO4 photoanodes to improve charge separation and hole extraction under light conditions.

Our experiments indicates that the uniformity and quality of NiO films are affected by deposition parameters, including the pH of the boric acid (H₃BO₃) solution, the type of base employed for pH adjustment (NH₄OH vs. NaOH)), and the temperature of nickel(II) fluoride tetrahydrate (NiF₂·4H₂O) to H₃BO₃ precursors. Characterization by profilometry reveals that maintaining a pH between 7.5 and 8 consistently produces uniform films with thicknesses in the range of 100–200 nm. UV–Vis spectroscopic analysis confirms the expected optical absorption of NiO in the near-ultraviolet region, while further electrochemical characterizations via cyclic voltammetry and chronoamperometry will further assess hole transport efficiency. This work establishes a scalable approach for NiO film fabrication that will enhance the performance of WO₃–BiVO₄ photoanodes in TEMPO-mediated oxidation processes, advancing sustainable, solar-driven alcohol oxidation with reduced environmental impact.

"Synthesis of Penicillin G Prodrugs and Assessment of Antibiotic Activity"

Type: Undergraduate
Author(s): Emma Kulla Chemistry & Biochemistry Emily Rathke Chemistry & Biochemistry
Advisor(s): Jean-Luc Montchamp Chemistry & Biochemistry

Emma Kulla, ¹Emily Rathke, ¹Braden Chadwick, Shauna M McGillivray, and Jean-Luc Montchamp*

¹Contributed equally

"Synthesis of Penicillin G Prodrugs and Assessment of Antibiotic Activity"

ABSTRACT
The goal of our project is to synthesize and evaluate prodrugs for phosphorus-containing antibiotics. To begin, we evaluated common prodrug moieties. This is because the preparation of phosphorus prodrugs is significantly more complex than that of carboxylic acids. In an attempt at determining the best prodrug moieties or at least establish if there are significant differences among the various bacterial strains, a series of compounds was synthesized. Penicillin G (potassium salt) was chosen as the model compound since it is a well-established antibiotic, and since there is only a carboxylate group needing derivatization. The potassium salt of penicillin G (PenCOOK) was esterified directly to PenCOOR by alkylation in DMF. The following R groups have been prepared: CH₂OC(O)t-Bu, CH₂C₆H₄(4-OAc), CH₂C₆H₄(4-NO₂), and CH₂C₆H₅. The former two compounds should be triggered by bacterial esterases, whereas the nitrobenzyl ester should be triggered by bacterial nitrogenases. The benzyl ester provides a control for the para-substituted benzyl derivatives. These compounds were then tested against the gram-positive pathogen, Bacillus anthracis Sterne. We find that the minimum inhibitor concentration (MIC) of the control (non-derivatized) penicillin-G was 120 μM (approximately 40 μg/ml), which is consistent with our previous studies. The addition of the prodrug moieties substantially increased the effectiveness of penicillin for all 4 pro-drugs. This result was most striking with EK31 (R = CH₂OC(O)t-Bu), which lowered the MIC to 3.75 μM (1.25 μg/ml). These results may be confounded by the lack of solubility of these prodrugs in aqueous media as EK31 also had the best solubility of the prodrugs tested. Future experiments will be needed to address this challenge and optimize the prodrugs, but our results indicate this is an effective approach.

Synthesis of Pyclen-KLVFF for Alzheimer's Disease Treatment

Type: Undergraduate
Author(s): Spencer Lanyon Chemistry & Biochemistry Sarah Dunn Chemistry & Biochemistry Hannah Pyle Chemistry & Biochemistry
Advisor(s): Kayla Green Chemistry & Biochemistry

Oxidative stress through the production of reactive oxygen species (ROS) has been shown to damage molecules in the brain and lead to the neuronal damage characteristic of AD. Additionally, metal ions like iron, copper, and zinc have been shown to not only bind to amyloid beta proteins and induce their aggregation, one hallmark of AD, but these metals also stimulate the production of ROS. To effectively fight AD, therapeutics should not only be able to chelate these metals and reduce oxidative stress but also prevent the aggregation of amyloid beta proteins. The Green Lab has produced ligands that both effectively chelate metals and reduce oxidative stress through interacting with ROS, but these ligands simply prevent the progression of the disease without affecting amyloid-beta protein aggregation directly. In this presentation, a synthetic scheme is proposed for the creation of a Green Lab ligand with the KLVFF peptide attached. The KLVFF peptide in the past has been shown to prevent amyloid-beta plaques from aggregating in vitro. Additionally, research has also been done showing that KLVFF, when attached to nanoparticles, can pass through RAGE receptors that are produced in the brains of AD patients. Through the addition of this peptide to the ligand, a small molecule that can chelate transition metals, reduce the effects of ROS, and prevent amyloid-beta aggregation will have been synthesized, providing a potential new therapeutic solution for Alzheimer's Disease treatment.

Salt-Induced Diffusiophoresis of a Cationic Micelle in Water

Type: Undergraduate
Author(s): Minh Le Chemistry & Biochemistry Onofrio Annunziata Chemistry & Biochemistry Josie Nguyen Chemistry & Biochemistry Nick Reuter Chemistry & Biochemistry
Advisor(s): Onofrio Annunziata Chemistry & Biochemistry

Salt-induced diffusiophoresis is the migration of a charged nanoparticle in water, induced by an imposed directional gradient of salt concentration. This transport phenomenon has emerged as a valuable tool for particle manipulation inside porous materials and microfluidics. Micelles represent a common example of nanoparticles with the crucial ability of hosting small guest molecules. Thus, micelle diffusiophoresis is important in the manipulation of small molecules. Micelle diffusiophoresis depends on micelle Brownian mobility or diffusion coefficient. This transport parameter describes the intrinsic ability of a micelle to randomly move (diffuse) in water. The poster reports diffusion-coefficient measurements carried out on aqueous solutions of the surfactant, hexadecylpyridinium chloride (CPC), in the presence of aqueous NaCl by dynamic light scattering. The effect of surfactant and salt concentrations on the diffusion coefficient of CPC micelles is discussed. These data are used to characterize salt-induced diffusiophoresis of charged micelles.

Preparation and Characterization of WO₃ Films on FTO Glass for Optimizing Photoelectrochemical Cell Performance

Type: Undergraduate
Author(s): Daisy Li Chemistry & Biochemistry
Advisor(s): Benjamin Sherman Chemistry & Biochemistry

In this work, a single-layer tungsten oxide (WO₃) film on fluorine-doped tin oxide (FTO) coated glass was successfully prepared by the dip-coating method, followed by thermal treatment at 450°C. The structure and electrochemical properties of the WO₃ film were then determined via UV-Vis spectroscopy, IR absorption, surface profilometry, and XRD analysis. The result suggests that the films have consistent thickness and uniformity, with future investigations needed to explore how they interact with the addition of a nickel oxide layer and bismuth vanadate layer determined by electrochemical measurements such as cyclic voltammetry, chronoamperometry under light and dark conditions. WO₃ electrode can be used as the base layer to make FTO-WO₃-Bismuth Van(BiVO₄)-Nickel Oxide (NiO) electrode ,which has the potential to improve the photochemical performance in photoelectrochemical cells.

Cancelling Cancer through Copper capture

Type: Graduate
Author(s): David Mingle Chemistry & Biochemistry
Advisor(s): Kayla Green Chemistry & Biochemistry

Copper plays particularly important roles in tumor growth and metastasis, making it a new target for anti-cancer therapies. The goal of this project is to exploit the pathways that cancer uses for proliferation as a target to inhibit cancer cell growth. To achieve this, tetra-aza macrocyclic small molecules will be used to sequester copper from the copper metabolizing pathways, recently we have discovered these molecules have high affinity for copper, water solubility, low toxicity, available in gram-quantities, and well-characterized. Our lead compound will be evaluated for anticancer activity on normal and breast cancer cells. This project also seeks to examine the pharmacological properties of the lead compound and explore of our compound on cooper pathways that leads to oxidative stress and inflammation.

Improving Density Functional Theory Simulations: M11plus Implementation and Reparameterization in the open PySCF package

Type: Undergraduate
Author(s): Jonah Morgan Chemistry & Biochemistry
Advisor(s): Benjamin Janesko Chemistry & Biochemistry

Density Functional Theory (DFT) is a method for simulating molecules by approximating their electron densities, with various functionals available to model these systems. M11plus is one such functional, a range-separated hybrid meta functional that combines long-range non-local Hartree–Fock exchange with the non-local Rung 3.5 correlation, which has demonstrated effectiveness across a broad range of chemical databases. This work implements the M11plus functional into the PySCF open-source Python library and reparametrizes necessary fitting constants.

Green Synthetic Routes to Porous Silicon for Drug Delivery Applications

Type: Undergraduate
Author(s): Iris Nguyen Chemistry & Biochemistry
Advisor(s): Jeffery Coffer Chemistry & Biochemistry

Silicon is a fundamental material in modern technology, with common applications including solar panels and numerous electronic devices. While high-purity silicon is necessary for these industries to ensure optimal electrical properties, biomedical applications such as drug delivery can tolerate alternative synthetic methods that prioritize sustainability and cost-effectiveness. This research focuses on developing an environmentally friendly approach to producing high-surface-area porous silicon using self-propagating high-temperature synthesis (SHS). This method utilizes silicon dioxide (SiO₂) as the silicon source, magnesium (Mg) as a reducing agent, and sodium chloride (NaCl) as a reaction moderator. The exothermic reaction between SiO₂ and Mg rapidly generates the heat necessary to facilitate silicon production, while NaCl helps regulate temperature, maintain porosity, and control grain growth. Unlike traditional silicon production processes that require high thermal energy input and costly purification steps, this SHS-based approach is designed to be scalable and accessible, particularly in resource-limited settings.
In a typical reaction, the Mg and SiO₂ reactants are exposed to a finite voltage (~12V) for a fixed amount of time (minutes) to initiate the reaction. After synthesis, the crude silicon product undergoes purification by dissolving the magnesium oxide (MgO) byproduct in hydrochloric acid, leaving behind high-purity silicon. This study aims to optimize reaction parameters (magnitude of voltage and duration) to maximize silicon yield and structural integrity while minimizing environmental impact. X-ray powder diffraction (XRD) is employed as the primary characterization technique to evaluate crystallinity and purity. The combination of a low-energy, cost-effective synthesis process and naturally derived raw materials positions this method as a promising green alternative for producing porous silicon. Its potential for drug delivery applications, particularly in developing regions with limited access to advanced manufacturing infrastructure, further underscores its significance in the field of biomaterials and sustainable materials science.

Salt-Induced Diffusiophoresis of a Cationic Micelle in Water. Determination of Cross-Diffusion Coefficients

Type: Graduate
Author(s): Khanh Nguyen Chemistry & Biochemistry Minh Le Chemistry & Biochemistry
Advisor(s): Onofrio Annunziata Chemistry & Biochemistry

Salt-induced diffusiophoresis is the movement of a charged nanoparticle in water, driven by an imposed directional gradient of salt concentration. This transport phenomenon has become a valuable tool for manipulating charged nanoparticles within porous materials and microfluidic systems. Micelles are a typical example of nanoparticles with the important ability to host small guest molecules. Therefore, micelle diffusiophoresis is also crucial for manipulating small molecules. This poster reports measurements of diffusiophoresis coefficients carried out on aqueous mixtures of the surfactant, hexadecylpyridinium chloride (CPC) in the presence of NaCl by Rayleigh interferometry. Measurements of NaCl osmotic diffusion from high to low micelle concentration are also reported. We observe that diffusiophoresis of CPC cationic micelles occurs from high to low salt concentration. A model describing the behavior of micelle diffusiophoresis as a function of NaCl concentration is reported. Our diffusiophoresis results are explained in terms of micelle electrical charge, salt osmotic diffusion coefficients and zeta potential. This work offers new insights into diffusiophoresis of charged nanoparticles with potential applications for enhanced-oil recovery from porous rocks, soil remediation and diffusion-based mixing inside microfluidics.

Europium-doped Cerium Oxide Nanotubes as a potential probe for bioimaging and optical sensors

Type: Graduate
Author(s): Leonardo Ojeda Hernandez Chemistry & Biochemistry Kayla Brownell Chemistry & Biochemistry Joseph Chouinard Physics & Astronomy
Advisor(s): Jeffery Coffer Chemistry & Biochemistry

The development of cerium oxide (CeO2) nanomaterials is rapidly advancing, driven by their wide range of applications in catalytic converters, solid oxide fuel cells, and biological sensors. Considering this, doping CeO2 with rare earth elements such as Europium (Eu3+) not only enhances its catalytic properties but also adds visible fluorescence to the list. To explore the variability of this effect, Eu3+ doped CeO2 nanotubes were synthesized and carefully analyzed by varying the Eu3+ concentration to investigate their optical properties, crystallinity, and morphology. Current research is focused on evaluating the potential of these doped CeO2 nanotubes as probes for bioimaging and optical sensors.

Copper Macrocycles as Mimics of SOD-1

Type: Undergraduate
Author(s): Mark Sayegh Chemistry & Biochemistry Dr. Katherine Smith Chemistry & Biochemistry
Advisor(s): Kayla Green Chemistry & Biochemistry

Reactive oxygen species (ROS) are byproducts of normal cellular metabolism. While essential in cell signaling and immune responses, unregulated or chronic levels of elevated ROS can cause oxidative stress. If this occurs in the brain, oxidative stress can lead to irreversible damage of macromolecular structures, including neuronal cell damage. Excessive ROS species are a hallmark of Alzheimer’s Disease (AD) and other neurodegenerative disorders. Superoxide dismutase (SOD) enzymes serve as a critical defense mechanism against ROS but have been found in lower concentrations in individuals with neurodegenerative disease. As a result, water-soluble small molecules that can mimic the SOD1 activity are of great interest to controlling diseases derived from oxidative stress. Herein, we present the SOD mimic activity for a library of copper tetra-aza macrocyclic small molecules and compare it to the most active congeners reported to date.