Inorganic Chemistry Commons^™

Computational Studies Of Triplet State Formation In Zinc Dipyrrin Complexes, Reuben Kwabla Adigbli

Electronic Theses and Dissertations

Zinc dipyrromethene complexes are promising earth-abundant photosensitizers due to their strong visible-light absorption and tunable excited states. To rationally design them for photocatalysis and photodynamic therapy, a molecular-level understanding of triplet-state formation is needed, but details of intersystem crossing remain unclear. To study the effect of π-extension, we synthesized an indole-substituted zinc dipyrrin complex: the dipyrromethane ligand was prepared from indole and mesitaldehyde, oxidized to the dipyrromethene, then coordinated with zinc. DFT and TD-DFT calculations determined ground and excited-state geometries and energies in different solvents, modeled absorption spectra, and visualized charge distributions. The results show how solvent polarity shifts energies …

Lignin Valorization To Phenolic Compounds Over Metal Oxide-Modified Hierarchical Zsm-5 Zeolites Derived From Indonesian Minerals, Arnia Putri Pratama, Iman Abdullah, Yuni Krisyuningsih Krisnandi

Makara Journal of Science

Lignin, a key component of lignocellulosic biomass, offers significant potential as a renewable raw material for the sustainable production of aromatic chemicals. To investigate its heterogeneous catalytic depolymerization, benzyl phenyl ether (BPE) was used as a model compound. Hierarchical ZSM-5 catalysts were synthesized and modified with metal oxides (NiO and CuO). Belitung kaolin and Bayat natural zeolite, natural minerals from Indonesia, were used as silica and alumina sources to synthesize hierarchical ZSM-5 zeolite (labeled as ZSM-5N), which was compared with hierarchical ZSM-5 synthesized using pro-analysis precursors (labeled as ZSM-5S). Comprehensive physicochemical characterization using FTIR, XRD, BET, XRF, SEM-EDX, and NH₃-TPD …

Amorphous Calcium Phosphate Maintains Casein Microarchitecture While Modulating Bacterial Growth Kinetics, Vuk Uskoković, Michael Ibba, Lorenzo Eugenio Leiva

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Casein, the primary source of protein in ruminant milk, represents a family of proteins that self-assemble into globules composed of finer spherical subunits and stabilized by calcium phosphate (CP) nanoparticles. These globules act as holdase-type chaperones for unfolded or partially folded proteins, preventing their aggregation. Simultaneously, by integrating CP nanoparticles, they enable the bioavailability of calcium and phosphate beyond their solubility limits, thereby enhancing the nutritional value of milk. Using a range of physicochemical and biological characterization techniques, including scanning and transmission electron microscopy, organic and inorganic elemental analyses, SDS-PAGE, and vibrational, UV/Vis and NMR spectroscopies, it is demonstrated that …

The Exploration Of One-Dimensional And Two-Dimensional Frustrated Magnetic Transition Metal Phosphates And Arsenates Via Hydrothermal Synthesis, Emily D. Williams

All Dissertations

Geometric magnetic frustration is a term that refers to magnetic spins that are “confused” or frustrated due to geometric arrangements of magnetic ions that prohibit the spins from magnetically ordering. This phenomenon has been subject to much research due to the ability to study exotic magnetic states and expand upon knowledge that would allow for materials to be implemented into quantum computing, memory storage and advanced sensor processing. One of the most exotic magnetic states, quantum spin liquids (QSL), has never been achieved but shows much promise. In the QSL state, magnetic spins do not order down to 0 K …

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+ …

Elucidation Of Spin-Hamiltonian Parameters Via Spectroscopy, Magnetization, And Computation, Joshua C. Mengell

Chemistry and Chemical Biology ETDs

Molecular Quantum Information Science (QIS) is fundamentally concerned with using spin-systems as quantum bits (qubits) or as sensors. Prerequisite to using molecular systems for QIS applications, it must be understood how one can design molecules with bespoke magnetic characteristics. Herein we study various paramagnetic molecular compounds, describing their complex magnetic characteristics using a spin-Hamiltonian formalism. We utilize various (sometimes novel) methods for determining these spin-Hamiltonian parameters. Many of these molecules possess magnetic characteristics, which make them attractive as qubits or for sensing applications. These characteristics include higher total spin-states (qudits—S_T>1/2), forbidden interstate electronic transitions, systems of spatially distant …

Photoluminescent Studies Of Metal-Organic Frameworks For Small Molecule Sensing, Julia T. Dematteo

USF Tampa Graduate Theses and Dissertations

Metal–organic frameworks (MOFs) are highly tunable nanoporous materials with broad applications in gas separation, drug delivery, light harvesting, and chemical sensing. The incorporation of photoactive components into MOFs enables the development of optical sensors capable of detecting a wide range of analytes. Porphyrins and metalloporphyrins are particularly attractive for such applications due to their high molar absorptivity, strong emission quantum yields, and versatile interactions with chemical species.

In this work, two porphyrinic MOFs, PCN-222 and MOF1(Cd), are investigated. Both frameworks utilize tetrakis(4-carboxyphenyl)porphyrin (TCPP) as the organic linker, imparting optical functionality to the materials. Integration of TCPP into the framework induces …

Antioxidant Potential Of A Non-Heme Iron Complex: Mitigating H2O2-Induced Cellular Damage, Magy A. Mekhail, David M. Freire, Cameron Bowers, Grant Elam, Nora Del Bosque, Hannah K. Pyle, Sarah K. Dunn, Spencer Lanyon, Timothy J. Hubin, Giridhar Akkaraju, Kayla N. Green

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Iron complexes with antioxidant activity have garnered significant interest for both general and medical applications, yet few studies have yielded functional nonheme iron-based mimics for H₂O₂ mitigation in aqueous environments. Here, we investigate water-soluble nonheme iron complexes derived from 12-membered pyridinophanes (^CF₃PyN₃, PyN₃, ^NMe₂PyN₃, and Py₂N₂) to evaluate the impact of ligand scaffolds on H₂O₂ decomposition activity both in vitro and in a cellular model. Speciation and kinetic analyses reveal that both electronic and geometric modulation of the macrocyclic …

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 …

The Extraction And Chemical Characterization Of The Avian Pigments Turacin And Turacoverdin, Sarah R. Bekkali

Honors Scholar Theses

Bird coloration is a trait that extends beyond mere aesthetics as it has an extensive range of biological significance. Plumage patterns and hues can influence camouflage, mate choice, social dominance, and physiological performance. Bird fitness, their ability to survive and reproduce, is greatly dependent on color. Melanins, carotenoids, and pterins are well-studied pigment systems that are commonly found across many avian species’. Alternatively, porphyrin-based pigments are rare and less-studied as they only found in turacos a sub-Saharan African bird belonging to the family Musophagidae. This thesis focuses on two pigments of interest: turacin, the deep crimson-red pigment found in …

Virtualizing Practical Science Education: A Sociological Analysis Of Undergraduate Teaching And Learning, Sina J. Fakoyede, Femi E. Babalola, Oluwatoyin T. Obateru, Oluwayemisi D. Akomolafe, Deborah O. Alabi, Stella K. Ekundayo

Higher Learning Research Communications

Objectives: The study aims to investigate the perspectives of university teachers and students on integrating practical science teaching with virtual learning in a multicultural and diverse society, specifically within the context of southwestern Nigeria.

Methods: A mixed-methods approach was employed, involving data collection from 100 university lecturers and 400 undergraduate students across 10 universities. Qualitative data were gathered through semi-structured interviews with lecturers and focus group discussions with students. Quantitative data were obtained via structured questionnaires, allowing for triangulation and comprehensive analysis.

Results: Findings revealed that certain lecturers showed preferential support influenced by students’ cultural backgrounds or academic behavior during …

Increasing Photocatalytic Activity Of Tio₂ Nanocrystals With Cobalt Dopants And Nio Heterojunctions, Lara A. Haack

Honors Thesis

Carbon emissions and fossil fuel usage has increased dramatically in recent decades, and the need for renewable energy has grown with it. Photocatalytic processes on titanium dioxide (TiO₂) nanocrystals may be used for solar energy driven production of fuel/oxidizer pairs. Many different methods have been developed to increase the effectiveness of TiO₂ in photocatalysis, including dye sensitization, quantum dot sensitization, doping with metals and non-metals, and the surface attachment of cocatalyst materials. Impurity dopants are not susceptible to photo-bleaching or degradation and judicious selection of cocatalyst materials can lead to robust all-inorganic heteronanocrystal photocatalysts: whereas, the use of molecular dye …

Tissue-Specific Heavy Metal Accumulation And Sediment–Mangrove Dynamics In Port Everglades, Florida, Dimitrios Giarikos, Amy Hirons, Jason Gershman, Sophie Welch

SECLER Data

Coastal wetlands near industrialized waterways face increasing heavy metal contamination, yet the role of mangroves as biogeochemical buffers remains poorly understood. This study quantified 16 heavy metals in sediments and red mangrove (Rhizophora mangle) tissues (roots, branches, and leaves) across four sites near Port Everglades, Florida, examining tissue-specific partitioning, contamination patterns, and sediment-to-plant transfer. The South Turning Basin (STB) was the principal contamination hotspot, with geometric mean (GM) concentrations of arsenic (As; 27.8 µg/g) and zinc (Zn; 203 µg/g) exceeding threshold effect levels, while Cu exceeded its probable effect level (PEL; 193 µg/g). Mercury (Hg) exceeded its PEL …

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 …

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.

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 …

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 …

Targeting Chemical Pollutants Through Assimilation Of Hydrophobic Deep Eutectic Solvents With Metal-Organic Frameworks, Carbon Nanotubes, And Activated Carbon, Tanner William Baughman

ONU Student Research Colloquium

Water contamination by heavy metals has a harmful human threat to the environment and to human health. This is derived from their bioaccumulation and toxicity characteristics. The study directly looks at the assimilated of lignin-derived hydrophobic deep eutectic solvents (HDES) with 3 different class of materials: Metal-Organic Frameworks (MOFs), Carbon Nanotubes (CNTs), and Activated Carbon (AC). Four different HDES mixtures were assimilated into these porous materials through impregnation. Composites were evaluated by characteristic peaks through Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). The morphology of the samples was assessed as well through scanning electron microscopy (SEM). The colloidal stability …

Click Reactions With Surface-Bound Phosphonate Films Toward An Electrocatalytic System For Carbon Dioxide Reduction, Iaroslavna Kovalenko, Emma J. Goehner, K. Nicole Crowder

Research and Creativity Symposium

One way to electrochemically reduce CO₂ is to use modified electrode surfaces with bound transition-metal electrocatalysts. Optimal conditions for modifying copper surfaces with a 1.0 mM solution of (2-azidoethyl) phosphonic acid in acetone have been identified, forming a self-assembled monolayer (SAM) via the tethering by aggregation and growth (T-BAG) method. The SAM protects the copper electrodes from oxidation or side reactions on the copper surface. The copper-catalyzed azide-alkyne cycloaddition (CuAAC) click reaction between the terminal azide group on the phosphonate and the terpyridine ligand has been successfully carried out on the copper surface. This terpyridyl ligand was then used …