Inorganic Chemistry Commons^™

Accurate Quantitation Of Hexavalent Chromium For Reference Standard Certification And Quality Control Testing Using Speciated Isotope Dilution Mass Spectrometry, James E. Henderson

Electronic Theses and Dissertations

The ability to perform accurate, repeatable, and defensible elemental and molecular speciated analysis is immensely significant for measurements that support human health, environmental science, and industry. This is especially true since trivalent chromium [Cr(III)] is necessary for proper nutrition, while hexavalent chromium [Cr(VI)] is extremely toxic, genotoxic, and carcinogenic. The main challenges associated with speciated analysis are related to reactive species that are continuously transformed or converted to other species during sample processing. Accurate determination of Cr(III) and Cr(VI) species require a method that is capable of monitoring and correcting for interconversion, bias, and instrumental error. Traditional quantitative methods, such …

Nanomaterial Composites Based On Potassium Hexaniobate, Perovskites, And Iron Triazole Spin Crossover Complexes, Alexis A. Blanco

LSU New Orleans Theses and Dissertations

Development of novel materials with sought after properties has been the forefront in the field of nanomaterials. Hybrid nanomaterial architectures, or nanocomposites, is an important subgroup within the material chemistry umbrella. One such example of nanocomposite systems is peapod-like structures that are composed of 0D nanoparticles (“peas”) and 2D nanosheets (“pods”). Nanopeapods may display unique properties that were not attainable within individual components. BaTiO₃ nanoparticles can be produced using solvothermal methods (20 h) in the presence of Ba(NO₃)₂, titanium (IV) butoxide, and oleic acid as the surfactant. Synthesis parameters were modified to allow for both …

Fluorinated Phthalonitriles And Phthalocyanines: Synthesis And Spectroscopic Properties, Marius Pelmus

Seton Hall University Dissertations and Theses (ETDs)

Since their discovery at the beginning of the 20^th century, phthalocyanines (Pc) have come a long way; today they are replacing the porphyrins (natural products) in most of their applications. The functionalization of the organic macrocycle, the use of different metals, and the change of the axial ligands resulted in Pc applications in a wide range of fields, ranging from photochemistry, paints, catalysis, to fuel cells and cosmetic products.

In Dr. Gorun’s group was developed a series of electron-deficient Pcs that benefit from a Teflon-like chemical shield, meant also to break the π-π interactions, namely the F₆₄PcM …

A Library Of Low Molecular Weight Fluorescent Probes For The Detection Of Cu(Ii) And Fe(Iii) Ions, Ashley Johnson

Dissertations

This dissertation reports the synthesis and photophysical properties of a family of rhodamine dyes (compounds 3.9-3.13 and 4.6). The rhodamine dyes are prepared in two steps, and fully characterized by ESI-MS (Low and High resolution), X-Ray crystallography, NMR spectroscopy, and FT-IR spectroscopy. The coordination environment of the low molecular weight fluorescent probes (LMFPs) was systematically changed to investigate the thermodynamic behavior between the LMFPs and an array of metal ions (Cu²⁺, Fe²⁺, and Hg²⁺ ions) in protic and aprotic solvent systems. Upon coordinating to metal ions, the π-conjugation of the LMFPs changed, resulting in …

Design And Synthesis Of Novel No-Drug Hybrid Compound And Green Catalytic Activity Evaluation Of Synthesized Silver Nanoparticles-Halloysite Nanocomposite, Majed Abdullah Bajaber

LSU New Orleans Theses and Dissertations

Acetaminophen is a well-known analgesic that can manage pain and reduce fever. SCP-1 is a derivative of acetaminophen that showed significantly reduced hepatotoxicity and nephrotoxicity comparative to acetaminophen. Nitric oxides have been well known to play a key role in a wide variety of physiological and pathophysiological important processes. It was therefore of interest to synthesize a nitric oxide donor linked to SCP-1 that could have enhanced analgesic and antipyretic activity. A furoxan CAS 1609 as NO-donor was synthesized and linked to SCP-1 successfully. The furoxan CAS 1609 was initially synthesized from tetronic acid to give 1,2- dioxime in 86 …

The Utilization Of Metal-Ligand Cooperativity For Electrocatalytic Reduction And Catalytic Hydration., Steven Cronin

Electronic Theses and Dissertations

Small molecules are building blocks for developing larger materials. These small molecules could be extremely small, such as hydrogen, or larger such as a nitrile, but their impact on the global economy is massive. This dissertation describes a catalyst for three reactions involving small molecules; 1) the hydrogen evolution reaction, 2) the carbon dioxide reduction reaction, 3) nitrile hydration. The catalyst Zn(DMTH) (DMTH = diacetyl-2-(4-methyl-3-thiosemicarbazonate)-3-(2-pyridinehydrazonato)) use “metal-ligand cooperativity” between the Lewis acid Zn(II) metal ion and an uncoordinated Lewis base nitrogen in the ligand framework to activate substrates. The complex has been analyzed via NMR, UV/Vis, single crystal X-ray crystallography, …

Selective Electrocatalytic Reduction Of Co2 To Co With Iron Nheterocyclic Carbene Complexes And Near-Infrared Absorbance Of Ruthenium(Ii) Photosensitizers Containing A Merocyanine Π-Acceptor, Peter Andrew Catsoulis

Graduate Masters Theses

The catalytic proton-coupled reduction of carbon dioxide into C-1 or “common engine” liquid fuels is currently a highly desirable and green approach to removing anthropogenic CO2 from the atmosphere. The most common approach to this is through electrocatalytic homogeneous reductions utilizing inorganic complexes as catalysts. Current research has moved towards the use of first-row transition metals in catalysts due to their high natural abundances and cheap cost. Iron porphyrin complexes have been vastly studied due to their high product selectivity and turnover frequencies. However, these complexes exhibit short lived activity because of competing reactions in their catalytic cycles, rendering them …

Study On Cation Exchange Of A Lead Coordination Polymer Targeting Dynamic Mixed Cation Doped And Mixed-Valent Coordination Polymers, Hamisu Aliyu Mohammed

Student Works (2020-2029)

Solid solution in Metal-Organic Coordination Polymers (MOCPs) is an emerging synthetic pathway for modifying chemical compositions and has been expansively investigated. It has been demonstrated to be an important tool for engineering novel functional materials that otherwise have not been synthesized via the conventional technique. Although stable solid material with variable functionalities and intriguing structural motifs could be engineered by judicious selection of multivariate metal centers and multifunctional ligands. However, solid solution featuring mixed valence in MOCP is rare. Motivated by the ability of Pb2+ to adopt range of coordination numbers (CN) and chemical environments (CE), in addition to its …

Multifunctional Metal-Organic Frameworks (Mofs) For Applications In Sustainability, Gaurav Verma

USF Tampa Graduate Theses and Dissertations

Climate change, affordable and clean energy, and responsible consumption and production are some of the important goals to be achieved for sustainable development. The current technologies used to address these challenges are energy and resource intensive. Furthermore, there are various limitations related to cost, storage, scalability and safety.Adsorbent materials are seen as a promising alternative remediation system due to their low energy consumption and minimal chemical waste production. However, most of the traditional adsorbents, such as activated carbon and zeolites lack the structural tunability to have long-term effectiveness and their use is limited. As discussed in Chapter 1, metal organic-frameworks …

Covalent Organic Frameworks As An Organic Scaffold For Heterogeneous Catalysis Including C-H Activation, Harsh Vardhan

USF Tampa Graduate Theses and Dissertations

Linking small organic molecules into an extended solid usually afford disordered amorphous polymers. The instigation of order into such a material is of profound interest to induce inherent fine control of the overall structure. Covalent organic frameworks (COFs) are new class of porous crystalline material prepared by connecting organic building blocks via strong covalent bonds. The judicious choice of organic monomers can give rise to highly ordered and predictable frameworks with high crystallinity, surface area, and thermal/chemical stability. The role of connecting linkages such as B─O, C─C, C─N extends the principle of fundamental molecular covalent chemistry to the formation of …

Ru(Ii)-Diimine Complexes And Cytochrome P450 Working Hand-In-Hand, Celine Eidenschenk, Lionel Cheruzel

Faculty Publications, Chemistry

With a growing interest in utilizing visible light to drive biocatalytic processes, several light-harvesting units and approaches have been employed to harness the synthetic potential of heme monooxygenases and carry out selective oxyfunctionalization of a wide range of substrates. While the fields of cytochrome P450 and Ru(II) photochemistry have separately been prolific, it is not until the turn of the 21st century that they converged. Non-covalent and subsequently covalently attached Ru(II) complexes were used to promote rapid intramolecular electron transfer in bacterial P450 enzymes. Photocatalytic activity with Ru(II)-modified P450 enzymes was achieved under reductive conditions with a judicious choice of …

Pointing The Zinc Finger On Protein Folding: Energetic Investigation Into The Role Of The Metal-Ion In The Metal-Induced Protein Folding Of Zinc Finger Motifs, Inna Bakman-Sanchez

Dissertations, Theses, and Capstone Projects

Interactions between inorganic metal-ion cofactors and organic protein scaffolds are important for the proper structure and function of metalloproteins. Zinc finger proteins (ZFPs) are an example of proteins with such crucial metal-protein interactions. Incorporation of the Zn(II)-ion into ZFPs allows for their correct folding into structures that can carry out vital biological functions which include gene expression and tumor suppression. In addition, engineered ZFPs have shown to be promising genetic therapeutics in the clinic. And yet, there is still a gap in a quantitative understanding of the energetic contribution of the metal-protein interactions towards the structure and function of these …

Synthesis, Structure Elucidation And Selected Biological Activities Of Ag(I) And Au(I) Complexes Constructed From Thiosemicarbazone And Phosphine Ligands, Syahrina Nur ‘Ain Abdul Halim

Student Works (2020-2029)

New Ag(I) and Au(I) mixed ligand complexes were synthesised using thiosemicarbazone and phosphine in search of a new biologically active compounds. CHN elemental analysis, powder X-ray diffraction (PXRD), single crystal X-ray diffraction as well as several spectroscopic techniques such as FT-IR, Energy-dispersive X-ray (EDX), 1H, 13C, and 31P{1H} NMR were performed to elucidate the structure of these complexes. Elemental analysis suggested that the stoichiometry of the complexes formed by the reaction of Ag nitrate with thiosemicarbazone in the presence of phosphine was indeed 1:2:1 molar ratio, while for the Au to be in 1:1:1 molar ratio. The Ag and Au …

An Investigation Of Antenna, Ligand Side-Chain, And Metal Ion Effects On The Optical And Mri Properties Of Bimodal Lanthanide (Iii) Complexes, Marisa Poveda

Master's Theses

Magnetic Resonance Imaging (MRI) is a leading anatomical imaging modality for disease diagnosis. With the aid of Gd³⁺ based contrast agents, high resolution images of biological structures can be obtained. However, there is an increased need for contrast agents that are responsive to specific analytes and chemical environments. Paramagnetic Chemical Exchange Saturation Transfer (PARACEST) agents that utilize a paramagnetic lanthanide ion chelated with a ligand have shown great promise in this area. Lanthanide ions also possess luminescence properties that do not suffer from common limitations of conventional optical imaging agents such as autofluorescence and photobleaching. The projects described in …

Functionalized Pyridine In Pyclen-Based Iron(Iii) Complexes: Evaluation Of Fundamental Properties, Magy A. Mekhail, Kristof Pota, Timothy M. Schwartz, Kayla N. Green

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

The use of tetra-aza pyridinophanes is of increasing interest in the fields of bioinorganic modeling, catalysis, and imaging. However, a full study of how modifications to the pyridyl moiety affect the characteristics of the daughter metal complexes, has not been explored. In this study, six tetra-aza macrocyclic ligands were metalated with Fe(iii) and were characterized for the first time. The pyridyl functional groups studied include: 4-hydroxyl (L1), 4-H (L2), 4-chloro (L3), 4-trifluoromethyl (L4), 4-nitrile (L5), and 4-nitro (L6) modified pyridyl on a pyclen base structure. The resulting iron …

Transition Metal Complexes Of Pyridyltriazole And Bipyridine Ligands, Sen Gao

LSU Doctoral Dissertations

Four Ni(II) complexes have been obtained with the pyridyltriazole ligand, bpt, or the bis(pyridyltriazole) ligand, m-xpt, in chapter 2. This work was carried out as a comparison with the previously established coordination chemistry of copper(II) with bpt and m-xpt. Initially, the reaction between Ni(II) and bpt only produced one mononuclear compound, [Ni(bpt)₂(H₂O)₂](NO₃)₂ (1). In order to study the formation of Ni-bpt and Ni-m-xpt complexes in solution, mixtures of Ni(NO₃)₂ and ligand (m-xpt or bpt) were prepared in different ratios and …

Synthesis And Assessment Of Radiotherapy-Enhancing Nanoparticles, Hayden Winter

Dissertations and Theses

Radiation Therapy (RT) is a common treatment for cancerous lesions that acts by ionizing matter in the affected tissue, causing cell death. The disadvantage of RT is that it is most often delivered via an external beam of radiation which must pass through healthy tissues to reach the target site, ionizing matter within healthy tissues as well. To address this drawback, techniques are being developed for increasing RT-induced cell death in a target tissue while minimizing cell death in surrounding tissues. This effect is known as radiation dose enhancement or RT enhancement.

The approach to RT enhancement studied in this …

Assessing The Robustness And Versatility Of Nanojars For Anion Binding, Mia Lily Ann Jawor

Masters Theses

Supramolecular chemistry is a field in chemistry that focuses on intermolecular bonds in a “host-guest complex” or supramolecular assemblies. Nanojars are supramolecular assemblies of the formula [anion⊂{Cu(μ-OH)(μ-pz)}_n] (n = 27‒33) which incarcerate kosmotropic anions, such as carbonate (CO₃^2‒), sulfate (SO₄^2‒) and hydrogen phosphate (HPO₄^2‒). Nanojars consist of three [Cu(μ-OH)(μ-pz)]_x (x = 6‒14, except 11) rings that are assembled similarly to Matryoshka dolls, where the top and bottom rings act as guests for the central ring. The larger central ring is bound to the two smaller rings by multiple …

Doping Effects On Transition-Metal Silicides: Crystal Structures And Physical Properties Of Aluminium Doped Rhenium Silicide, Victoria Decocq

Graduate Theses/Dissertations

Semiconductive transition-metal silicides (e.g., ReSi) express weak thermoelectric properties. These properties can improve through n-type or p-type doping (e.g., Al), resulting in altered crystal structures. Binary rhenium silicide (ReSi_1.75) exhibits promising thermoelectric properties and an intriguing crystal structure. Previous research has shown ReSi_1.75 changes from a commensurate supercell MoSi₂-type structure to an incommensurate superspace group structure, when doped with aluminium to ReAl_0.074Si_1.67. ReSi_1.75 expresses a figure of merit (ZT) of 0.70 at 800°C, which improves to a ZT of 0.95 at 150°C for ReAl_0.02Si_1.75. Because of …

Synthesis, Characterization, And Biological Studies Of Novel Organoantimony(V) Cyanoximates, Kevin Anthony Pinks

Graduate Theses/Dissertations

The requirement of new antimicrobial treatments has become an urgent field recently. Multi-drug resistant (MDR) bacteria are now resistant to common antibiotics. To antagonize such bacteria 8 novel organoantimony(V) cyanoximates were synthesized to be characterized and submitted for biological activity studies. Eight organoantimony(V) cyanoximates were characterized by elemental analysis, thermal analysis, IR-, ¹³C{¹H} NMR, some with UV-visible spectroscopy, and single crystal X-ray analysis. Antimicrobial Disk studies indicated Sb(Ph)₄(ACO) and Sb(Ph)₄(ECO) had significant antimicrobial effect against all three strains: two gram-negative a) Escherichia coli strain S17 and b) Pseudomonas aeruginosa strain PAO1, alongside a …

Water Cluster Motifs In Structurally Similar N-(2-Aminoethyl)-1-Methylimidazole-2-Carboxamide Metal Complexes: Synthesis, Characterization, Thermal And Electrical Properties., Nina Saraei

Electronic Theses and Dissertations

Water is a remarkable molecule and in all of its forms exhibits an amazing collection of properties and functions. Besides its crucial role in life and many technological processes, water displays some unusual and anomalous properties at various interfaces and under different conditions. Although the role of hydrogen-bonding interactions and their fluctuations are well known to determine the properties of water, the main obstacle exists in the complexity of correctly describing the interactions between water molecules. The key to understanding the behavior of water is to collect precise structural data of various H-bonded water networks in diverse environments. In this …

Computational Elucidation Of The "Coloring Problem" In Rhenium Aluminum Silicon Compounds, Alec George Neeson

Graduate Theses/Dissertations

Re₁Si₁Al₁ and its related compounds are potential thermoelectric materials. Previously, it was reported to adopt a MoSi₂-type structure with Si and Al atoms statistically sharing the same crystallographic sites. This recent study indicates otherwise – Si and Al are segregated and occupy different sites when mixed with a 1:1:1 stoichiometry. To confirm and rationalize the segregation between Si and Al, this research studied this compound with first-principle calculations. Several model structures have been constructed for Re₁Si₁Al₁ including a number of different super-cell models. Energy analysis confirmed that the …

How Oxygen-Binding Affects Structural Evolution Of Even-Sized Gold Anion Clusters (Size Range 20 To 34), David Brunken-Deibert

Department of Chemistry: Dissertations, Theses, and Student Research

We report a joint anion photoelectron spectroscopy (PES) and theoretical study to investigate the effect of O₂-binding on the mid-sized even-numbered gold clusters, Au_n− (n = 20−34), a special size region of bare gold clusters that entail rich forms of structural evolution and transformation. Specifically, within this size range, bare Au₂₀₋ is a highly-symmetric pyramidal cluster, bare Au_21-25− are flat-planar or hollow-tubular clusters, bare Au₂₆₋ is the smallest core-shell gold cluster, while bare Au₃₄₋ is a magic-number/fluxional core-shell cluster with the high-symmetry tetrahedral Au₄ core. In light of the strong …

Visualization Without Vision – How Blind And Visually Impaired Students And Researchers Engage With Molecular Structures, Croix J. Laconsay, Henry B. Wedler, Dean J. Tantillo

Journal of Science Education for Students with Disabilities

This article examines the tools and techniques currently available that enable blind and visually impaired (BVI) individuals to visualize three-dimensional objects used in learning chemistry concepts. How BVI individuals engage with and visualize molecular structure is discussed and recent tactile (or haptic) and auditory methods for visualization of various chemistry concepts are summarized. Remaining challenges for chemistry education researchers are described with the aim of highlighting the potential value of educational research in further enabling BVI students to pursue careers in science, technology, engineering, and mathematics (STEM) fields.

Small Molecule Analog Studies Of Paramagnetic Dmso Reductase Enzyme Family Intermediates, Khadanand Kc

Chemistry and Chemical Biology ETDs

Pyranopterin molybdenum and tungsten enzymes are expressed in numerous organisms from all domains of life. These enzymes catalyze a variety of atom, hydride, and electron transfer reactions. The enzymes are of great importance in the biogeochemical cycles of nitrogen, carbon, and sulfur. In recent years, chemists have investigated applications for some of these enzymes as industrial biocatalysts. The dimethylsulfoxide reductase (DMSOr) enzyme family is the broadest family of pyranopterin Mo enzymes. The first coordination sphere of the Mo or W-containing active site for each member of this family is made up of 4 sulfur donors from the two pyranopterin dithiolenes …

Synthesis Of Cds/Zns Core/Shell Semiconductor Nanoparticles, Austin Skyler Antle

Masters Theses & Specialist Projects

Core/shell semiconductor nanoparticles are of great interest as photocatalysts due to their large surface area per volume and tunable band gaps. The synthesis of core/shell semiconductor nanoparticles has traditionally involved the use of binding ligands to ensure the particles do not aggregate. These binding ligands lower the surface area of the nanoparticles though, reducing their overall efficiency. Ionic liquids have been found to be capable of acting as both solvents and stabilizing agents for synthesis of catalysts with highly active surfaces. Our experiments focus on the synthesis of CdS/ZnS core/shell nanoparticles with the ionic liquid 1-butyl-3-methylimidazolium methyl sulfate, [BMIM][MeSO4], acting …

Solvent-Free Synthesis Of Metal Coordination Compounds Using Ball Mills, Jenna Cantway

Masters Theses & Specialist Projects

Mechanochemistry utilizes mechanical energy to promote chemical reactions to completion. Samples ground with a ball mill are placed under consistent pressure and temperature, which allows for increased surface area, shorter reaction times and overall better control of reaction conditions compared to the use of a mortar and pestle. Many synthetic techniques to prepare metal coordination compounds use a solvent. The solvent promotes the reactions by providing a route for reagents to interact. While solvents facilitate reactions, there is interest in reducing or eliminating solvents altogether during the synthesis process due to potential instability of a solvent under certain experimental conditions …

The Influence Of Carbon Nanotubes And Mn Dopant Onto Zinc Oxide For Degradation Of Organic Pollutant Model Under Visible Light Irradiation, Ab Wahab Norfarhanah

Student Works (2020-2029)

Globally untreated industrial wastewaters are contaminating soil, surface water, groundwater, and consequently, the environment. Therefore, there is a huge interest in developing efficient and effective removal methods, such as photocatalytic advanced oxidation processes (AOP) under visible light (~47% of solar irradiation). In this work, the effectiveness of Mn-doped ZnO composite decorated onto multiwall carbon nanotubes (MWCNTs) on photodegrading organic pollutants was studied. This composite was simultaneously synthesized by sol gel method. XRD was used to confirm the formation of ZnO/Mn nanocomposite and the crystalline phase changes as ZnO content decreases when other elements were added to form the nanocomposite. The …

Understanding The Interfacial Reactions Initiating On Lithium Metal Surfaces In Next-Generation Battery Technologies, Joshua A. Lochala

Graduate Theses and Dissertations

Li-ion batteries have started to reach the theoretical maximum energy. Next-generation batteries represent the future of portable energy sources for vehicle electrification and grid energy storage. Li metal battery is one of the most promising next-generation battery technologies that could potentially double the cell-level energy of conventional Li-ion batteries. However, Li metal has multiple drawbacks that require addressing before realization. These drawbacks include dendrite formation leading to internal short and increasing internal resistance due to the breakdown of electrolyte, leading to rapid cell death. These problems stem from the interfacial reactions occurring during the plating and stripping of Li metal. …

Ensemble And Single Particle Studies Of Cation Exchange In Cuins2/Zns Qds And Their Application In Super-Resolution Imaging, Anh Tue Nguyen

Graduate Theses and Dissertations

Colloidal quantum dots (QDs) have great potential in many applications such as bioimaging, light emitting diodes, solar cells and lasers. However, a great number of studies have been focused on Cd based (II-VI) and Pb (IV-VI) based materials which are not suitable for mass production. Therefore, alternative types of QD containing less toxic materials have been introduced, including CuInS2 QDs. This I-III-VI semiconductor nanocrystals also attract lots of attention due to their large Stock shift, long fluorescence lifetime and high defect tolerance, making them attractive emitters for applications in bioimaging, photovoltaics and light emitting diodes.

In the first project, we …