Inorganic Chemistry Commons^™

The Novel Chlorination Of Zirconium Metal And Its Application To A Recycling Protocol For Zircaloy Cladding From Spent Nuclear Fuel Rods, Breanna K. Vestal

Doctoral Dissertations

A novel protocol has been developed for the chemical removal of zirconium alloy (Zircaloy) cladding from spent nuclear fuel rods and subsequent isolation and purification of nuclear-grade zirconium chloride derived therefrom. This protocol is based on the chemistry developed from two new scientific findings.

First, two new oxidative chlorination reactions have been discovered for zirconium metal. In both solvents, zirconium can be quantitatively chlorinated at temperatures less than 150°C, with the operative equations seen below. In sulfur monochloride, the reaction is completed in 2 – 4 hours via surface etching, exhibiting 0^th order kinetic behavior. The elemental sulfur byproduct …

Synthesis, Characterization, And Cytotoxicity Studies Of A Copper(Ii) Complex With Vanillin 3-Ethyl-Thiosemcarbazone A Ligand, Novia Mann, Ifeoluwa Oyeyemi, Duaa R. Alajroush, Elizabeth A. Tonsel-White, Stephen J. Beebe, Alvin Holder

Undergraduate Research Symposium

Triple-negative breast cancer (TNBC) is one of the most aggressive and challenging breast cancer subtypes to treat, as these cancer cells lack three common receptors: estrogen, progesterone, and human epidermal growth factor receptor 2. The multiple oxidation states transition metals can occupy have made this narrowly explored group popular for anti-cancer research in recent decades. Furthermore, the success of cisplatin, which has platinum as a metal center, while being a cancer-fighting agent with serious side effects, has caused other metal centers to be investigated as possible alternatives as chemotherapeutic drugs. Copper, as a biologically essential metal, makes an attractive candidate …

Investigating The Structure Of Metal-Organic Frameworks And The Behaviors Of Adsorbed Guest Molecules In Mofs Via Solid-State Nmr Spectroscopy, Yihao Shen

Electronic Thesis and Dissertation Repository

Metal-organic frameworks (MOFs) are a class of hybrid organic-inorganic microporous materials with lots of significant applications including gas capture and storage, gas separation, batteries, catalysis, ion exchange and drug delivery. MOFs based on s-block metals are important due to their many practical applications. These MOFs are also very interesting because the s-block MOFs often exhibit unpredictable behavior of coordination. In this thesis, the structures of six s-block metal (Li, Na, Cs, Mg, Ca, Sr) based MOFs involving V-shaped link, 4, 4′- sulfonyldibenzoate (SDB) are characterized by various techniques including, powder X-ray diffraction, TGA and solid-state NMR spectroscopy. ¹³C CPMAS …

Optimized Peptide Nanomaterials As Delivery Vehicles For Hydrophobic Metal-Based Anticancer Agents, Yaron Marciano

Dissertations, Theses, and Capstone Projects

Enzyme-responsive materials have been well explored, particularly as therapeutic and diagnostic agents. In this thesis we demonstrate that anionic self-assembling peptides can be utilized as delivery vehicles for metal-based hydrophobic payloads. The tunability of the system is highlighted as well as the increase in cytotoxicity and selectivity in vitro. The rapid degradation of peptides in cell media may lead to the formation of new peptide-drug bioconjugates with increased activity and selectivity. The physiological stability of these peptide delivery vehicles has been optimized by capping the N-terminus with an acetyl group. This simple backbone modification was shown to not prevent self-assembly, …

Influence Of Synthesis Conditions On The Physicochemical And Electrocatalytic Properties Of Non-Stoichiometric Ba2sr2la2ti4o12 Perovskites, Ofeliya Kostadinova, Iliyan Popov, Simeon M. Stankov, Hristo Kolev, Tamara Petkov

Karbala International Journal of Modern Science

Present work studies the influence of the pretreatment milling media (deionized water (BLTOS-H) and isopropanol (BLTOS-i)) on the surface characteristics, structure, chemical composition and catalytic activity of non-stoichiometric Ba2Sr2La2Ti4O12 perovskites. The IR spectroscopy and XRD analyses shows a difference in the structure and phase composition of the two materials. X-ray photoelectron spectroscopy detects a Ba2+- and La3+-enriched and Sr2+-depleted surface. The BLTOS-i sample appears to exhibit higher specific surface area (SSA) and pore volume in comparison to BLTOS-H. The electrochemical tests showed that BLTOS-H sample have similar behavior to platinum at current densi-ties up to 10 mA cm-2, while BLTOS-i …

Palladium (Ii)-Catalyzed Selective Reduction Of 4’-(Phenylethynl)Acetophenone In The Presence Of A Formic Acid-Triethylamine Mixture, Suzanne Chayya, Akram Hijazi, Anis Daou, Ali Alaaeddine, Mohamad Sakr, Ghassan Younes, Mohammad El-Dakdouki

BAU Journal - Science and Technology

An efficient and straightforward palladium acetylacetonate-catalyzed hydrogen transfer of 4'- (phenylethynyl)acetophenone was developed in this study. Formic Acid was found to be the best hydrogen source in this catalytic system in the presence of triethylamine. Excellent conversions and selectivity were obtained in reducing the starting internal aromatic alkyne to either (E)-1-(4- styrylphenyl)ethanone or an interesting cyclic product, 1-(phenanthrene-3-yl)ethenone, over the ketone functional group present. Over-reduction was rarely seen. The reaction conditions were optimized in terms of the choice of the palladium catalyst, temperature, solvent, and the H-donor/base combination. Using this catalytic system, a one-step synthetic pathway of the …

Gold (I) Tetrathiomolybdate Clusters: Synthesis, Characterization, Computational Studies, And Reactivity With Thiophenol And Selenophenol, Dhirgam Humaidy

Electronic Theses and Dissertations

This thesis describes the synthesis and reactivity of heterometallic complexes containing medicinally active Au(I) and tetrathiomolybdate, [MoS₄]^2-. The research is motivated by the idea of multifunctional drugs, which are designed to treat diseases through two or more mechanisms of action. Five clusters of the general form, [MoS₄(AuL)₂] were prepared: C-1 (L=IPr), C-2 (L=IBzMe), C-3 (L=IMes), C-4 (L=PPh₃), and C-5 (L=PEt₃). The clusters with NHC ligands, C-1, C-2, and C-3 were prepared for the first time and thoroughly characterized by ¹H NMR,¹³C{¹H} …

Designing And Synthesizing A Warhead-Fragment Inhibitory Ligand For Ivyp1 Through Fragment-Based Drug Discovery, Samuel Moore

Symposium of Student Scholars

Fragment-based drug discovery (FBDD) is a powerful tool for developing anticancer and antimicrobial agents. Within this, magnetic resonance spectroscopy (NMR) provides a comprehensive qualitative and quantitative approach to screening and validating weak and robust binders with targeted proteins, making NMR among the most attractive strategies in FBDD. Inhibitor of vertebrate lysozyme (Ivyp1) of P. aeruginosa serves as an excellent target because of its active cellular location and implications in clinical prognosis for cystic fibrosis and immunocompromised patients. This study uses current NMR and biophysical techniques to develop a covalent, fragment-linked warhead inhibitor for Ivyp1 through synthetic methods, warhead linking, and …

Transition Metal Computational Catalysis: Mechanistic Approaches And Development Of Novel Performance Metrics, Brett Anthony Smith

Doctoral Dissertations

Computational catalysis is an ever-growing field, thanks in part to the incredible progression of computational power and the efficiency offered by our current methodologies. Additionally, the accuracy of computation and the emergence of new methods that can decompose energetics and sterics into quantitative descriptors has allowed for researchers to begin to identify important structure-function relationships that predict the properties of unexplored subspaces within the overall chemical space. Catalytic descriptors have been used frequently in data driven high-throughput computational screenings. With the use of machine learning, a large portion of the chemical space an be predicted in matter of minutes or …

Synthesis And Characterization Of 2,6-Diisopropylphenoxy Tetrapyrazinoporphyrazines As Potential Molecular Qubits, Benjamin Marx

Masters Theses

This thesis reports the synthesis of metal-free and metal-containing phthalocyanine derivatives using methods typical for that class of functional dyes. A mixture of the target compounds prepared here, one paramagnetic and one diamagnetic tetrapyrazinoporphyrazine, will be tested for their potential use in spintronics – the application of spin-active species in molecular electronics. Phthalocyanines and their derivatives are well-known for their ease of preparation and tunability; they have been utilized as sensitizers for photodynamic therapy of cancer and solar cells, as well as in catalysis and chemical sensing. Tetrapyrazinoporphyrazine complexes are compared with the parent phthalocyanine as their chemistry is similar …

Computational And Experimental Investigations Of Alkali Cation Interactions At The Rutile – Water Interface, Isaac Johnston

All Dissertations

Overall, the objective of this dissertation was to investigate the degree of sorption for the alkali cations on rutile to ascertain the impact of different cation properties, such as ion size and charge density, on sorption mechanics as well as probe how the ion may alter the surface – aqueous interface. Initial molecular dynamic simulations and batch experiments showed minimal surface sorption for any alkali cation at relatively low concentrations while simultaneously suggesting the enthalpy of deprotonation shifts slightly in the presence of the alkali cations at different ionic strengths. The cations are likely causing small reorientations of the near-surface …

The Synthesis, Lewis Acidity And Catalytic Activity Of Bis(Catecholato)Germanes, Andrew T. Henry

Electronic Thesis and Dissertation Repository

Main group Lewis acids have been shown to be viable alternatives to state-of-theart transition metal catalysts. While extensive research into a variety of p-block Lewis acids have been reported, the field of germanium Lewis acid chemistry has been described as “almost non-existent”. A variety of bis(catecholato)germane derivatives have been synthesized. The Lewis acidity of these compounds was analyzed by the Gutmann-Beckett and fluoride ion affinity methods demonstrating the high Lewis acidity of these complexes. The bis(catecholato)germanes were utilized as Lewis acid catalysts for the hydrosilylation of aldehydes, the hydroboration of alkynes, Friedel-Crafts alkylation of alkenes, and the oligomerization of styrene …

The Coordination Chemistry And Reactivity Of Pd Phosphine 1-Azaallyl Complexes, Kyle M. Jackman

Electronic Thesis and Dissertation Repository

Structurally responsive ligands (SRLs) are a class of ligands that change their coordination mode with a metal centre, which permits reactions that are difficult with non-SRLs, allow access to unique mechanisms, and allow isolation of unusual coordination complexes. The 1-azaallyl (1-AzA) family of SRLs are capable of isomerizing between η³-NCC and κ¹-N modes that occupy two and one coordination sites, respectively. This thesis investigates a new class of phosphine 1^AzA (P^AzA) ligands and the reactivity of their coordination complexes with palladium.

The first-generation P^AzA ligand contains a phenyl linkage between the two heteroatoms and affords a …

Bismuth Binding In Human Metallothionein, Emily M. Toswell

Undergraduate Student Research Internships Conference

Bismuth metal is one of the least toxic heavy metals for humans. It is used in a wide variety of applications including organic synthesis, cosmetics and pharmaceutical applications. In biomedicine, bismuth is a therapeutic metal used in metallodrugs such as Pepto Bismol for its antimicrobial and antibacterial properties. Metallothionein (MT) is a cysteine rich protein found in the liver, kidneys, brain and central nervous system. MT can bind a variety of metals including essential metals such as zinc and copper. This research investigates the binding pathway of Bi[EDTA]- with fully metallated Zn₇MT by using mass-spectrometry and UV-vis absorption.

Hierarchically Structured Photoelectrodes Via Atomic Layer Deposition, Justin Rowan Reed Demoulpied

Graduate Theses and Dissertations

In the search for a sustainable method to meet increasing energy needs, solar energy emerges as an underutilized, plentiful resource. Solar intermittency and requirements for transportation necessitate storing solar energy in the form of chemical bonds via artificial photosynthesis. Photoelectrochemical (PEC) water splitting generates hydrogen fuel from solar energy and water. A semiconducting material that successfully meets the complex requirements for building an industrially scalable PEC device has yet to emerge. This is leading to a reevaluation of materials previously overlooked within PEC research, mainly materials with limitations such as minimal charge carrier mobility and propensity to corrosion under illumination …

Dissolution And Electrochemical Recovery Of Uo2, Uo3, And U3o8 In Ionic Liquids, Katherine Iolani Thornock Luebke

UNLV Theses, Dissertations, Professional Papers, and Capstones

This research explores a novel method of increasing the solubility of uranium oxides and other actinide oxides in room temperature ionic liquids (IL) using direct dissolution. The goal is to further expand our knowledge of actinide dissolution and possible nuclear fuel cycle material applications using ionic liquids. The novelty of the methods is focused on the use of oxidizing gas generated using air passed through an ozone generator. While examples of dissolution exist in IL using acidic functionalized ionic liquids, the solubility of all possible oxide species was not demonstrated. Also, the addition of aqueous acid to IL containing actinide …

Synthesis And Evaluation Of Water-Dispersed Aryl-Gold Nanoparticles And Applications In Catalysis, Ahmad Al Ahmad

Electronic Theses and Dissertations

Gold nanoparticles have been used in environmental remediation as catalysts through biological and chemical redox reactions of many types of industrial waste including nitroarenes, organic dyes, carbon monoxide, and others. These reactions occur in harsh environmental conditions (e.g. changing temperature, presence of salts, extreme pH solutions) which require robust nanoparticles that can keep their activity and resist aggregation. This thesis describes the synthesis, characterization, and investigation of the catalytic activity of gold-aryl nanoparticles. Gold–aryl nanoparticles (AuNPs-COOH) fabricated using a mild reduction process of a molecular aryldiazonium gold(III) salt [HOOC-4-C6H4N≡N]AuCl4 showed high stability in the presence of high ionic strength salt, …

Synthesis, Characterization, And Reactivity Studies Of Highly Reduced Early-Metal Complexes Supported By Imidazolin-2-Iminato Ligands, Maria Alejandra Gomez Torres

Open Access Theses & Dissertations

Our group has shown that reduction of titanium complexes supported by the sterically encumbering N-donor ligands 1,3â??bis(Dipp)imidazolinâ??2â??iminato (ImDippNâ??) and ketimine guanidinate (ketGuan = [(tBuC=N)C(NDipp)2]-) gives access to electron rich platforms featuring a metal coordinated, reduced, dearomatized arene substituent, which act as an electronic reservoir capable of facilitating multi-electron transfer chemistry driven by the rearomatization driving force. For instance, the arene-masked Ti(II) synthon (DippketGuan)(η6-ImDippN)Ti (Dipp = 2,6-iPr2C6H3) (TiDipp) is a versatile and potent one- and two-electron reductant capable of distinctive late-metal type reactivity such as transfer hydrogenation and catalytic olefin hydrogenation. Interestingly, TiDipp can mediate the reversible cleavage of thiophene and, …

Alkylthiocarbamate Metal Complexes With Antiproliferation Activity., Kritika Bajaj

Electronic Theses and Dissertations

Bis(thiosemicarbazones) (BTSCs) and their metal complexes have been extensively studied for various applications including catalysis for hydrogen evolution reactions, treatment of neurodegenerative diseases, hypoxia imaging, and a wide range of pharmacological purposes including antitumor, antiviral, antibacterial, and antifungal agents. The paramount property that makes BTSC metal complexes interesting for their use in these applications is the reduction potential of the coordinated metal, which can be selectively tuned by varying the substituents present on the ligand framework. Although the BTSCs have shown a great deal of success as potential cancer therapeutic agents, they lack selectivity towards cancer cells. For this matter, …

Extracting Lithium Using The Steric Bulk Of An Aminimide Functional Group, Jacob Parker, Martin Chin Ph.D.

Summer Undergraduate Research Program (SURP) Symposium

An aminimide is a zwitterionic group containing a cationic nitrogen bonded to an anionic nitrogen. The goal of this project was to use the steric bulk and electronic properties of the aminimide to block other species in a brine solution such as potassium, and selectively pick up lithium. To test this, polymethacrylate beads which contain carboxyl groups were modified to the desired aminimide. Three different aminimide groups were tested, a trimethylaminimide, aminopyridiniumaminimide, and a triethylaminimide. The modified beads would be introduced to a solution containing lithium and the lithium concentration was measured before and after exposure to the beads using …