Materials Chemistry Commons^™

Stimuli-Responsive Proton Transfer: Photoacid Design, Co2 Sorbent Regeneration, And Polymer Applications, Melyse Ava Laud

Theses and Dissertations

Control over proton transfer enables the regulation of many pH-dependent chemical and material processes. Stimuli-responsive functional materials provide a means of achieving this control. Functional materials such as Metastable-state photoacids (mPAHs) reversibly release large amounts of protons when stimulated by light from a weakly acidic site within their structure. However, the dark acidities of previously reported mPAHs limit their use under basic conditions. To address this limitation, a benzimidazole-type mPAH was developed with an improved ground-state pKa of 11.9 and a metastable-state pKa of 9.8, enabling reversible proton transfer under mildly basic conditions. Additional mPAHs were examined to determine how …

Electrolyte Development And Interfacial Reactions At Multivalent Metal Anode For Next Generation Energy Storage Systems, Leslie Gates

Graduate Masters Theses

The increasing demand for safe, sustainable, and high-performance energy storage systems has driven significant interest in multivalent-ion batteries, including aluminum, magnesium, and zinc-based systems. These technologies have attracted attention due to their high theoretical energy densities, natural abundance, low cost, and environmentally benign nature. However, their development remains hindered by a limited fundamental understanding of electrolyte development and interfacial processes at the electrode–electrolyte interface, where complex electrochemical interactions govern battery performance and stability.

This thesis investigates electrode–electrolyte interactions in both a novel aluminum electrolyte and divalent magnesium and zinc systems. Beginning with the development and characterization of a novel aluminum …

Synthesizing Viscoelasticity: Living Polymers, Micro-Macro Relations, And Paths For Resolution, Adam M. Hasler

Graduate Masters Theses

This thesis investigates the relationship between macroscopic rheological signals and underlying microscopic dynamics in complex fluids, specifically focusing on ”living polymers” within the cetyltrimethylammonium bromide (CTAB) and sodium salicylate (NaSal) surfactant system. The research addresses the inverse parameterization problem, demonstrating how bulk measurements like zero-shear viscosity can mask fundamentally different physical topologies, such as purely cylindrical, reptating micelles versus highly branched networks. Through the successful synthesis of viscoelastically ”degenerate” samples, the study utilizes an array of characterization techniques including frequency sweeps, Large Amplitude Oscillatory Shear (LAOS) to resolve these unique underlying states. Furthermore, the work explores further avenues of study …

Synthesis And Characterization Of Carbon Quantum Dots And Gold Nanoparticles For Norovirus Biosensing Applications In Water Systems, Breanne Evans

Master's Theses

Rapid, reliable detection of viral pathogens remains a significant challenge across water-treatment and environmental monitoring systems, including drinking-water, wastewater, water reuse, and environmental surveillance applications. Waterborne viral contamination can pose substantial public-health risks, making early detection essential for protecting water quality and responding quickly to treatment failures or contamination events. Direct potable reuse (DPR) is one particularly demanding example because it requires continuous verification of treatment performance and the broader need for rapid virus monitoring extends across many water-treatment and environmental surveillance applications. Norovirus is a priority target because of its widespread occurrence in wastewater, environmental persistence, and exceptionally low …

Imaging Oxygen Near Implanted Medical Devices Through Tissue With X-Ray And Ultrasound Modulated Luminescence Chemical Imaging, Vigjna Abbaraju

All Dissertations

Oxygen plays a crucial role in stem cell maintenance, tissue regeneration, disease progression, and treatment efficacy. For example, understanding oxygen dynamics within implanted medical devices, such as bone scaffolds, is essential for successful tissue regeneration and can serve as an early indicator of infection. The existing oxygen sensing and imaging techniques are often limited by narrow imaging depth, low spatial resolution in vivo resulting in poor understanding of oxygen dynamics in tissue microenvironments. This dissertation describes the development of implantable sensors using X-ray scintillators and thermochromic leuco dye paired with phosphorescent oxygen dye (PtTFPP) to image oxygen using X-ray luminescent …

Structure And Dynamics Of Associative Polymers Under Quiescent State And Flow, Rosita Sivaraj

All Dissertations

Associative polymers, including ionizable polymers, are widely used in membranes, coatings, fuel cells, energy storage, and other advanced soft materials. Their properties are governed by ionic aggregation and associative interactions, which influence chain mobility, phase behavior, self-assembly, interdiffusion, and flow response. This dissertation employs large-scale molecular dynamics (MD) simulations to investigate the structure, dynamics, phase behavior, interdiffusion, and extensional flow response of ion-containing and associative polymer systems under quiescent and nonequilibrium conditions.

The influence of molecular architecture is first examined by comparing ring and linear associative polymers using the Kremer–Grest bead-spring model. In linear chains, their closed-loop architecture reduces interchain …

Exploring The Nature And Role Of Local Cation Ordering In Disordered Rock Salt Cathodes For Li- And Na-Ion Batteries, You Wang

Chemistry and Chemical Biology ETDs

Cation-disordered rock-salt (DRX) cathodes provide a highly tunable platform for next-generation Li- and Na-ion batteries, but their electrochemical behavior is strongly influenced by local structural features hidden in average crystal structures. This dissertation systematically investigates local cation ordering in Li- and Na-based DRX cathodes to understand its effects on Li+/Na+ transport, redox activity, structural evolution, and electrochemical performance. In Li-based systems, Raman spectroscopy and electrochemical analysis reveal that local layered cation ordering in Mn- and Fe-based DRX cathodes is closely correlated with electrochemical behavior. Over-stoichiometric Li-based DRX oxyfluorides further demonstrate that excess Li can regulate local cation ordering, improve Li+ …

Tuning Ion Mobility And Molecular Confinement In High-Performance Polymer Electrolytes For Energy Storage, Ezzeldien Yousef Muhammed Yousef

Theses and Dissertations

This research addresses the critical energy density limitations of aqueous supercapacitors, which are traditionally constrained by the narrow electrochemical stability window (ESW) of water 1.23 V. By employing two distinct molecular engineering strategies, this study developed high-performance electrolyte systems that significantly extend voltage stability and thermal resilience.

The first system, CsBr@PAM/HA, utilizes a polyacrylamide and hyaluronic acid hydrogel matrix. This system exploits the chaotropic nature of Cs⁺ ions to disrupt the aqueous hydrogen-bonding network, enhancing ionic conductivity to 104 mS cm^-1. Through systematic salt screening, CsBr was identified as the optimal electrolyte, enabling a stable 2.0 V …

Thermally Induced Color Changes In Iron Oxide Containing Coatings, Tabatha Whitfield

Master's Theses

Wildland-urban interface (WUI) fires and residential conflagrations present significant challenges for post-fire damage and fire propagation analysis. CAL FIRE observed reddening in architectural coatings during the 2025 Pacific Palisades fire with no determination of the cause. While heat-induced color change of infrastructure coatings has been studied, its potential use as a thermal exposure indicator in residential fire events remains largely unexplored. The objective of this study was to characterize the heat-induced color change of yellow iron oxide containing coatings subjected to thermal exposures, replicating residential fire conditions. The coatings were applied to commonly used building materials and exposed to direct …

Characterization Of The Thermally Driven Red Hue Effect In Coated And Uncoated Concrete Systems: Implications For Post-Fire Assessment In Wildland Urban Interface Communities, Juan C. Palominos Jr

Master's Theses

The increasing frequency and intensity of Wildland-Urban Interface (WUI) wildfires, such as the destructive 2025 Pacific Palisades Fire that destroyed over 6,000 structures, have underscored the urgent need for rapid post-fire safety assessment methodologies. This study sought to quantitatively characterize the Thermally Driven Red Hue Effect (TRHE), a unique, irreversible color shift observed in architectural coatings and concrete substrates, to determine its reliability as a permanent visual record of thermal exposure. Concrete substrates were formulated with three distinct coarse aggregates: gold granite (14.7% Fe), red cinder (22.4% Fe), and green rock (33.6% Fe) and coated with a 20 PVC waterborne …

Thermally Induced Color Changes In Iron Oxide Pigments Used In Architectural Coatings, Han Diep

Master's Theses

The 2025 Palisades Fire was one of the most destructive wildfires in the history of Los Angeles, destroying thousands of structures and severely impacting the communities after. This widespread destruction demonstrated an urgent need for more effective wildfire prevention strategies. Architectural coatings do not only provide aesthetics and protection against environmental conditions but can also function as a thermal indicator when a fire breaks out. This study examines the thermally induced color transformation of iron oxide pigments, commonly used in earthtone paint, to provide information relevant to CAL FIRE for improved analysis of wildland-urban interface (WUI) fire behavior and mitigation …

Synthesis, Characterisation, And Electrochemical Performance Of Efb-Derived Biochar-Metal Oxide Composite Electrodes For Hybrid Supercapacitors, Yogini Gunasekaran

Student Works (2020-2029)

Supercapacitors are essential for energy storage due to their high-power density and longevity, particularly in increasing demand for sustainable energy. However, their low energy density and specific capacitance hinder widespread use. Advancements in next-generation electrode materials that are high-performing, cost-effective, and scalable are necessary to address these issues. Herein, this work reports the development of novel electrode materials and explores the fundamental relationship between their structural properties and electrochemical performance in supercapacitors. In this study, biochar was derived from oil palm Empty Fruit Bunch (EFB) via a gasification process. Different samples of metal oxide/biochar composites were subsequently synthesized using a …

Mediating Energy And Charge Transfer Dynamics Of Lead Halide Perovskite Nanocrystals Via Surface Chemical Approaches, Aaron S. Malinoski

Dissertations, Theses, and Capstone Projects

Energy and charge transfer are the fundamental mechanisms by which semiconductor nanocrystals interact with their external environment and underpin all light-conversion related applications. Lead halide perovskite nanocrystals (PNCs) are a relatively new class of semiconductor nanocrystals that possess a unique and dynamic surface chemical environment. Investigations into the influence of these surface chemical conditions on the electronic coupling between surface-bound molecular acceptors and the perovskite nanocrystals, and how the surface chemistry can be manipulated, in turn controlling the charge and energy transfer mechanisms, is the focus of this dissertation. Through ligand-shell engineering using commercially available, inexpensive small molecules, the surface …

Computational-Experimental Synergy As A Predictive And Interpretive Tool Through Metal-Organic Framework Investigations, Cristian Sayers

Graduate Student Theses and Dissertations

In the search for tunable materials platforms capable of addressing both clean energy conversion and viable post-combustion carbon capture, metal-organic frameworks (MOFs) have emerged as a uniquely versatile class of porous solids offering high specific surface area, structural tunability, and chemically addressable metal nodes and organic linkers. Realizing their potential requires understanding behavior that spans atomic-scale electronic structure and bulk-scale property response, a regime in which neither computation nor experiment alone is sufficient. This work attempts to develop a tighter integration between density functional theory (DFT) and laboratory investigation, treating the two modalities as mutually informing probes of the same …

Nanoscale Structure And Spontaneous Self-Assembly Of Hydrothermal Organic Products, Glorianne P. Dorce

Chemistry and Chemical Biology ETDs

Carbon nanomaterials derived from citric acid and urea exhibit behaviors that challenge conventional structure–property models based on static bulk descriptions. This study examines how precursor pairing and reaction duration, post‑synthetic thermal history, and time‑dependent aging govern nanoscale organization and optical response. Through controlled synthesis and processing, distinct nanostructures with tunable structural and spectroscopic profiles are generated.

A multiscale framework integrating nano‑FTIR, atomic force microscopy, and thermal analysis reveals chemical heterogeneity and continuous structural reorganization across length scales. By correlating local chemical environments with optical behavior, we show that fluorescence efficiency and photostability depend on specific nanoscale architectures rather than average …

Adsorption Of Pfas On Bridged Functionalized Organosilica Materials, Elisha Lawerh Kabutey

Electronic Theses and Dissertations

PFAS are hazardous contaminants that have a devastating impact on human health and the environment. Their hazardous nature has led to the development of various adsorption methods for removing these contaminants from water sources. In this study, functionalized organosilica materials were synthesized from bis[3-(trimethoxysilyl)propyl] amine using the sol-gel method. The surface amino groups of the organosilica were converted into amine hydrochloride groups. Their adsorption properties were evaluated using salts of perfluorooctanoic acid, perfluorooctanesulfonic acid, and perfluorobutanesulfonic acid. Results showed excellent adsorption capacity of the materials. Adsorption of PFAS leads to particle agglomeration and flotation of the spent material. A column …

Engineering Silicone Magnetic Fluids For Localized Radiation Attenuation During Ocular Melanoma Brachytherapy, Zachary L. Caprow

All Dissertations

Ocular melanoma is commonly treated using plaque brachytherapy; however, radiation-induced damage to healthy ocular tissues frequently results in partial or complete vision loss. This work investigates the development of an injectable, magnetically responsive silicone magnetic fluid designed to localize adjacent to the tumor and attenuate low-energy gamma radiation during treatment.

The material system consists of iron oxide nanoparticles surface-functionalized with a siloxane polymer, in which the nanoparticles provide magnetic responsiveness and radiation attenuation, while the polymer coating ensures colloidal stability, injectability, and biocompatibility. A one-pot synthetic approach was developed wherein a functionalized siloxane polymer containing iron-affinitive groups was reacted with …

Exploring The Effects Of Polymer-Graphene Interactions On Bulk Composite Properties Using Finite Element Analysis, Bryant Grove

Dissertations

As a filler in high performance materials, graphene significantly enhances the mechanical properties of polymer composites. Experimental characterization of graphene composite enhancements is limited by labor-intensive processes in both synthesizing composites for different purposes and in characterizing the interactions between graphene and polymer composites that lead to these enhancements. Computational approaches such as finite element analysis (FEA) are suitable alternatives that go beyond experimental analysis. This dissertation demonstrates the utility of FEA in analyzing polymer graphene composites with an emphasis on modeling the interaction between graphene fillers and the matrix within the interphase formed between them. The accessible design framework …

Comparative Development Of Mof‑Based And Mof‑Free Agnp Functionalized Zno Nanorod–Cotton Fabric Composites For Photocatalytic Applications, Md Al Mamun

Master's Theses

Photocatalysis offers a cost‑effective and environmentally friendly strategy for degrading organic pollutants and addressing energy and environmental challenges. This study initially explored MOF‑based cotton‑fabric‑supported ZnO nanorod composites but found that the MOF component primarily acted as an adsorbent rather than an effective photocatalyst. Consequently, MOF‑free composites were developed by directly growing ZnO nanorods on cotton fabric and functionalizing them with silver nanoparticles. Photocatalytic testing revealed that AgNP‑modified ZnO nanorods, particularly at 10 mM AgNP, exhibited superior dye degradation efficiency, thereby demonstrating a scalable and effective photocatalytic platform.

Tunable Physical Color In Nanostructured Materials: Exploring Reversible Mechanisms For Active Optical Control, Matt Hughes

Chemistry & Biochemistry Undergraduate Honors Theses

Vanadium Dioxide (VO₂) thin films have been grown on silicon wafers using atomic layer deposition of TDMAV (tetrakis(dimethylamino)vanadium(IV)) and H₂O as precursors. A quartz crystal microbalance (QCM) measurement was used during deposition to confirm growth and resulted in a growth rate of approximately 0.6 Angstroms/cycle. X-Ray Reflectivity (XRR) was performed to confirm growth thickness and reported an approximately 30 nm thin film after 500 cycles of TDMAV precursor deposition. X-Ray photoelectron spectroscopy was utilized to determine the phase of the vanadium samples and confirmed the presence of vanadium dioxide as prepared and after annealing under nitrogen …

Hollow Nickel-Iron Nanoshells As Electrocatalysts For The Oxygen Evolution Reaction, Jonathan Batey

Chemistry & Biochemistry Undergraduate Honors Theses

The development of highly active and affordable catalysts for the oxygen evolution reaction is crucial to achieve a future where hydrogen is generated cleanly using renewable methods. Ni-Fe nanocatalysts show great promise in this area, as they are affordable and highly active. However, to overcome the industrial dominance of steam methane reforming, their activity needs improvement. This work aims to increase the activity of Ni-Fe nanocatalysts by making hollow nanostructures. Hollow Ni-Fe nanostructures were synthesized by coating a Cu template with Ni and Fe, followed by the etching of the Cu template. This left hollow Ni-Fe nanoshells, which were used …

Taking A Deeper Look: Attributing Tonal Values Of Photolumens To Their Emulsions Using Scanning Electron Microscopy, Anna M. Moore

All Theses

This thesis examines whether tonal variation in photolumens made with historic silver gelatin photographic papers can be linked to differences in elemental composition. Photolumens are cameraless photographic images created by placing objects directly on light-sensitive paper and exposing them to ultraviolet light. Because expired and historic darkroom papers often produce unpredictable colors and tones, this study asks whether visually defined tonal groups also show measurable chemical differences.

Twenty historic paper samples were exposed, documented, and sorted into five tonal groups based on visible image characteristics. Each sample was then analyzed using scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) …

Synthesis And Performance Evaluation Of Zeolite-Based Ni–Cao For Integrated Co2 Capture And Conversion, Zhang Xinggang

Student Works (2020-2029)

Carbon capture and utilization (CCU) is increasingly being adopted as a strategy to minimize carbon dioxide (CO₂) emissions. Integrated CO₂ capture and utilization (ICCU) is more attractive as it reduces overall cost and energy consumption by eliminating the need for gas compression and transportation. Advances in ICCU and the development of dual functional materials (DFMs) capable of adsorbing and in situ converting CO₂ have attracted increasing attention in both academia and industry, driven by the need for efficient CO₂ utilization pathways. After a detailed analysis of the literature, zeolites have emerged as prominent materials for use as adsorbents and catalyst …

Evidence Of Metal-Microcystin Complexation And Its Potential Role In Environmental Fate, Ashley Marie Womer

Theses and Dissertations

Microcystins that enter freshwater systems pose a threat to human health therefore their fate and transport throughout the water column have been intensively studied. While sediment has been regarded as an environmental fate for microcystin (MC), less is known about the molecular mechanisms by which microcystin interacts with the sediment and/or the thermodynamic stability of these interactions. While microcystin has a half-life in lake water on the order of weeks, microcystin adsorbed to sediment can be detected hundreds of years later1-2. Microcystin has been desorbed from these sediments with various EDTA solutions, therefore, work is presented to support the hypothesis …

The Use Of Machine-Learning Interatomic Potentials To Study Bulk Properties Of Aqueous Zn Ion Batteries, Ria Vasdev

Theses and Dissertations

Aqueous Zn-ion batteries (AZIBs) have emerged as a promising energy storage tech- nology owing to their high Coulombic efciency and low environmental impact. However, their practical development is impeded by limited cycling stability, pri- marily caused by parasitic side reactions occurring at the anode surface. These side reactions are strongly infuenced by the bulk solvation structure of Zn-based elec- trolytes, which remains challenging to characterize using conventional experimental techniques. Machine-learning interatomic potentials (MLIPs) provide a powerful computational approach to investigate these systems and can be employed to eluci- date the bulk structural properties of Zn electrolytes.

Extension Of The Local Vibrational Mode Theory To Periodic Systems, Filippo Bodo

Chemistry Theses and Dissertations

Over the years, vibrational spectroscopy was used to gain a deeper understanding of the electronic structure and the chemical bond in both molecular and periodic systems. In this framework, the Local Vibrational Mode Theory (LVMT), as first introduced by Konkoli and Cremer in 1998, provides a unique tool to quantify the strength of a chemical bond, and better interpret the molecular vibrational spectra, thanks to the adiabatic force constants ($k^a$) and the composition of normal modes (CNM). While LVMT was originally developed for molecular systems, its application to periodic solids has remained limited. This thesis presents a complete and systematic …

Monosaccharide Binding To Synthetic Carbohydrate Receptor Microarrays, Milan A. Shlain

Dissertations, Theses, and Capstone Projects

Chapter 1: A glycan detection platform comprised of synthetic carbohydrate receptors (SCRs) immobilized onto polymer brushes was prepared. SCR043, an alkene-containing SCR, was incorporated into grafted-from polymer brushes using hypersurface photolithography, resulting in microarrays of SCR043-functionalized polymer brushes, where brush height (h) and SCR grafting density (Γ) is controlled precisely at each feature in the array. The influence of h and Γ on the binding to five fluorescently labelled monosaccharides – α-glucose (α-Gluc-FL), α-galactose (α-Gal-FL), α-mannose (α-Man-FL), β-glucose (β-Gluc-FL), and β-galactose (β-Gal-FL) – in aqueous buffer …

A Computational Study Of The Chemomechanics Of Paracetamol Polymorphs: Towards Improving Drug Tabletability, Karim Nader Samra

Theses and Dissertations

The mechanical properties of pharmaceutical crystals are of great importance in tablet manufacturing. Also, knowing the mechanical properties of different polymorphs of the same crystal can reduce the overall production cost. In this study, computational work was done via performing density functional theory calculations on 3 paracetamol crystal polymorphs Form I, II, and III. Understanding the chemical bonding helps in predicting the key elastic properties for different crystallographic directions. In Form II, lattice vector C is dominated with the intermolecular hydrogen bond OH…O giving it the stiffest Young Modulus and the least Poisson’s ratio. Then comes the A-Axis which contains …

Synthesis And Characterization Of Polymethylhydrosiloxane-Based Materials: Environmental Remediation, Unusual Oxidative Behavior, And Kinetic Analysis, Hannah M. Hayes

Chemistry & Biochemistry Dissertations

Porous materials have a wide range of applications. One of which is environmental remediation as a sorbent. Synthetic materials are beneficial as they have more selectivity compared to natural sorbents however, they are more costly. Recently, a publication produced an ambiently dried gel using a copolymer of polymethylhydrosiloxane (PMHS) and polydimethylsiloxane (PDMS) after modification with vinylmethyldimethoxysilane (VMDMS). PMHS is a byproduct of the silicone industry which makes the synthesis cheaper and more environmentally friendly. The precursor ratio must be tailored to account for the change in polymer used. In this study, various ratios of PMHS and VMDMS as well as …

Utilizing Coal For Mesophase Pitch-Based Carbon Fiber Production: Precursors, Processes, And Progress, Christina M. Thompson

Theses and Dissertations--Chemistry

Graphitic materials possess unique properties due to the unique combination of layered crystalline structure and carbon’s low atomic weight. High performance carbon fiber is one such example, displaying exceptional strength-to-weight ratios, stiffness, and thermal and chemical resistance. These properties render high performance carbon fiber a critical structural reinforcement material in the manufacture of composites across various industries, such as for automotive and aerospace applications. However, balancing fiber performance with precursor and processing costs remains a challenge. As alternative carbonaceous feedstocks are explored, coal has gained interest for utilization in graphitic products as a relatively abundant and low-cost source of aromatic …