Inorganic Chemistry Commons^™

Remediation Of Ammonium Perrhenate Via Tris(2,2’-Bipyridine)Ruthenium(Ii) Chloride, Kaylin L. Thomas, Sandra A. Abdellah, Alvin A. Holder

Knowledge and Creativity Expo

Pertechnetate (TcO₄⁻) is a persistent radioactive byproduct resulting from the decay of uranium-235 or plutonium-239 in the nuclear fuel cycle. Its high environmental mobility, long half-life, and significant beta radiation make TcO₄⁻ a critical contaminant. Structurally tetrahedral and water-soluble, TcO₄⁻ behaves similarly to the sulfate anion, facilitating its rapid introduction into ecosystems.

It bioaccumulates in lower-level organisms, propagating radioactive and toxic effects through food chains. In mammals, technetium-99 accumulates in the thyroid and may also impact fetal development. Its small charge, chemical stability, and solubility present significant challenges for effective remediation.

Current remediation methods often suffer from poor selectivity, dependence …

Amphiphilic Tripodal Metalloligands: Synthesis, Coordination Chemistry And Preliminary Catalysis, Austin W. Medley, Paul D. Miller, Craig A. Bayse, Robert D. Pike, Trandon A. Bender

Chemistry & Biochemistry Faculty Publications

Triscatecholate binding has been widely studied in the context of biological systems, supramolecular chemistry, and weak aggregate interactions. However, the utilization of the triscatecholate binding motif for the preparation of metalloligands remains unexplored. Herein, we report the synthesis, structural characterization, and functional studies of a triscatecholate ligand with an appended pyridyl residue as a candidate for such applications. Our findings reveal that the selective formation of cis-triscatecholate-based metalloligands is influenced by electronic effects on the catecholate anions, enabling the targeted synthesis of Al(III), Ga(III), and In(III) triscatecholate metalloligands capable of binding Zn(II) and Ru(II) at the appended pyridyl moiety for …

Unraveling Visible Spectra Of S-Type Stars: The F3Δ–A3Δ (Α System) And E3Π–A3Δ (Β System) Band Systems Of Zro, Manish Bhusal, Peter Bernath, Jacques Liévin

Chemistry & Biochemistry Faculty Publications

ZrO has many low-lying states, and its spectra are essential for the characterization of S-type stars. A high-resolution emission spectrum recorded with a Fourier transform spectrometer at the National Solar Observatory is used for the analysis. The 0–0 and 1–0 bands of the f³Δ-a³Δ system (α system) and the 0–0 band of the e³Π-a³Δ system (β system) have been rotationally analyzed using the modern spectral fitting program PGOPHER. New ab initio calculations of transition dipole moments have been performed to determine the band strengths. These band strengths are used to produce line lists that are suitable for the …

Synthesis And Characterization Of Cobalt(Iii) Complexes And A Vanadium(Iv) Complex With Flavonoids As Ligands, Ethan Schroeder

Chemistry & Biochemistry Theses & Dissertations

For many years now, transition metal complexes have been used as favorable additional chemotherapeutic approaches to medicine that were previously unexplored in the literature. One well-known chemotherapeutic drug, cisplatin, has been applied, but is limited in use due to its toxicity to the cells and its undesirable side effects to humans. Newly developed cobalt-based complexes with ligands known as flavonoids are being used to fight cancer. Flavonoids, compounds mainly found in fruits and vegetables, are shown to have antioxidative and anticancer properties. Use of flavonoids as ligands in transition metal complexes, e.g., those with a Ru(II) metal center, have been …

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 …

S-Type Stars: Line List For The A²Π-X²Σ⁺ Band System Of Lao, P. F. Bernath, R. Dodangodage, J. Liévin

Chemistry & Biochemistry Faculty Publications

LaO bands are found in the spectra of cool S-type stars. The bands of the A²Π–X²Σ⁺ transition with v' ⩽ 3 and v'' ≤ 4 are rotationally analyzed, providing spectroscopic constants for the A²Π state. Line strengths are calculated using an ab initio transition dipole moment function, and radiative lifetimes for the A²Π state have also been computed. A line list for the A²Π–X²Σ⁺ transition of LaO is provided and can be used to determine LaO stellar abundances.

S-Type Stars: Lao Line List For The B²Σ⁺-X²Σ⁺ Band System, P. F. Bernath, Randika Dodangodage, J. Liévin

Chemistry & Biochemistry Faculty Publications

LaO bands are a characteristic feature in the spectrum of cool S-type stars. La is made primarily by the s-process during the asymptotic giant branch phase of stellar evolution. The B²Σ⁺–X²Σ⁺ and A²Π–X²Σ⁺ band systems can be used to determine the La abundances in cool S stars. The bands of the B²Σ+–X²Σ⁺ with v' and v" ⩽ 5 have been rotationally analyzed from an emission spectrum from a carbon furnace. Line strengths are calculated using an ab initio transition dipole …

Photodynamic Therapy Of Inorganic Complexes For The Treatment Of Cancer, Chloe B. Smith, Lindsay C. Days, Duaa R. Alajroush, Khadija Faye, Yara Khodour, Stephen J. Beebe, Alvin Holder

Chemistry & Biochemistry Faculty Publications

Photodynamic therapy (PDT) is a medicinal tool that uses a photosensitiser and a light source to treat several conditions, including cancer. PDT uses reactive oxygen species (ROS) such as cytotoxic singlet oxygen ¹O₂ to induce cell death in cancer cells. Chemotherapy has historically utilized the cytotoxic effects of many metals, especially transition-metal complexes. However, chemotherapy is a systemic treatment so all cells in a patient's body are exposed to the same cytotoxic effects. Transition metal complexes have also shown high cytotoxicity as PDT agents. PDT is a potential localized method for treating several cancer types by using inorganic …

Synthesis, Characterization, Dna Binding, Topoisomerase Inhibition, And Apoptosis Induction Studies Of A Novel Cobalt(Iii) Complex With A Thiosemicarbazone Ligand, Stephen J. Beebe, Michael J. Celestine, Jimmie L. Bullock, Shayna Sandhaus, Jessa Faye Arca, Donald M. Cropek, Tekettay A. Ludvig, Sydney R. Foster, Jasmine S. Clark, Floyd A. Beckford, Criszcele M. Tano, Elizabeth A. Tonsel-White, Raj K. Gurung, Courtney E. Stankavich, Yuk-Ching Tse-Dinh, William L. Jarrett, Alvin A. Holder

Bioelectrics Publications

In this study, 9-anthraldehyde-N(4)-methylthiosemicarbazone (MeATSC) 1 and [Co(phen)₂(O₂CO)]Cl·6H₂O 2 (where phen = 1,10-phenanthroline) were synthesized. [Co(phen)₂(O₂CO)]Cl·6H₂O 2 was used to produce anhydrous [Co(phen)₂(H₂O)₂(NO₃)₃ 3. Subsequently, anhydrous [Co(phen)₂(H₂O)₂] (NO₃)₃ 3 was reacted with MeATSC 1 to produce [Co(phen)₂(MeATSC)](NO₃)₃·1.5H₂O·C₂ H₅OH 4. The ligand, MeATSC 1 and all complexes were characterized by elemental analysis, FT IR, UV–visible, and multinuclear NMR …

Phosgene In The Upper Troposphere And Lower Stratosphere: A Marker For Product Gas Injection Due To Chlorine-Containing Very Short Lived Substances, Jeremy J. Harrison, Martyn P. Chipperfield, Ryan Hossaini, Christopher D. Boone, Sandip Dhomse, Wuhu Feng, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Abstract: Phosgene in the atmosphere is produced via the degradation of carbon tetrachloride, methyl chloroform, and a number of chlorine‐containing very short lived substances (VSLS). These VSLS are not regulated by the Montreal Protocol even though they contribute to stratospheric ozone depletion. While observations of VSLS can quantify direct stratospheric source gas injection, observations of phosgene in the upper troposphere/lower stratosphere can be used as a marker of product gas injection of chlorine‐containing VSLS. In this work we report upper troposphere/lower stratosphere measurements of phosgene made by the ACE‐FTS (Atmospheric Chemistry Experiment Fourier Transform Spectrometer) instrument and compare with results …

Depletion Of Ozone And Reservoir Species Of Chlorine And Nitrogen Oxide In The Lower Antarctic Polar Vortex Measured From Aircraft, T. Jurkat, C. Voigt, S. Kaufmann, J.-U. Grooß, H. Ziereis, A. Dörnbrack, P. Hoor, H. Bozem, A. Engel, H. Bönisch, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

Novel airborne in situ measurements of inorganic chlorine, nitrogen oxide species, and ozone were performed inside the lower Antarctic polar vortex and at its edge in September 2012. We focus on one flight during the Transport and Composition of the LMS/Earth System Model Validation (TACTS/ESMVal) campaign with the German research aircraft HALO (High-Altitude LOng range research aircraft), reaching latitudes of 65°S and potential temperatures up to 405 K. Using the early winter correlations of reactive trace gases with N₂O from the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS), we find high depletion of chlorine reservoir gases up to ∼40% …

The Role Of Sulfur Dioxide In Stratospheric Aerosol Formation Evaluated By Using In Situ Measurements In The Tropical Lower Stratosphere, A. W. Rollins, T. D. Thornberry, L. A. Watts, P. Yu, K. H. Rosenlof, M. Mills, E. Baumann, F. R. Giorgetta, T. V. Bui, M. Höpfner, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

Stratospheric aerosols (SAs) are a variable component of the Earth's albedo that may be intentionally enhanced in the future to offset greenhouse gases (geoengineering). The role of tropospheric-sourced sulfur dioxide (SO₂) in maintaining background SAs has been debated for decades without in situ measurements of SO₂ at the tropical tropopause to inform this issue. Here we clarify the role of SO₂ in maintaining SAs by using new in situ SO₂ measurements to evaluate climate models and satellite retrievals. We then use the observed tropical tropopause SO₂ mixing ratios to estimate the global flux of …

Synthesis And Mechanistic Investigations Of Transition Metal Complexes And Ligands For Chemotherapeutic Applications, Jimmie Lee Bullock Jr.

Chemistry & Biochemistry Theses & Dissertations

Transition metal complexes have played a critical role in antitumor therapy with many complexes incorporating platinum, ruthenium, and lanthanum having been investigated in preclinical and clinical trials. The best known transition metal therapeutic is cisplatin, which is utilized in nearly 50% of all cancer therapies, despite its significant toxic side effects. The toxic side effects of current FDA approved platinum-based chemotherapeutics are often overlooked due to the “special status” granted to these drugs due to their ability to fight, what is often considered an incurable disease with life expectancies often measured in months. Oncology drug development has therefore now focused …

Nitrous Oxide In The Atmosphere: First Measurements Of A Lower Thermospheric Source, Patrick E. Sheese, Kaley A. Walker, Chris D. Boone, Peter F. Bernath, Bernd Funke

Chemistry & Biochemistry Faculty Publications

Nitrous oxide (N₂O) is an important anthropogenic greenhouse gas, as well as one of the most significant anthropogenic ozone-depleting substances in the stratosphere. The satellite-based instrument Atmospheric Chemistry Experiment-Fourier Transform Spectrometer has been observing the Earth's limb since 2004 and derives profiles of N₂O volume mixing ratios in the upper troposphere to the lower thermosphere. The resulting climatology shows that N₂O is continuously produced in the lower thermosphere via energetic particle precipitation and enhanced N₂O is present at all latitudes, during all seasons. The results are consistent with an N₂O …

Synthesis, Characterisation, Electrochemical, And Spectroscopic Studies Of Cobaloximes: Unique Clues Of Cobalt(I) Species In Various Solvents, Michael John Celestine

Chemistry & Biochemistry Theses & Dissertations

With the dwindling amount of fossil fuels in the world’s reserve is said to run out in the future. The use of alternative fuels such as hydrogen can be produced from renewable sources. One source is the use of first row transition metal complexes that can harness the power of the sun to reduce protons to hydrogen. In this thesis we investigated a well-known hydrogen evolution catalyst in a quest to understand the behavior of different oxidation states that occur during the catalytic cycle.

In an attempt to synthesize a binuclear ruthenium(II) complex, [{Ru(phen)2}2{µmes(1,4-phO-Izphen)3}](PF6)4, as a possible photosensitizer for the …

Interesting Properties Of P-, D-, And F-Block Elements When Coordinated With Dipicolinic Acid And Its Derivatives As Ligands: Their Use As Inorganic Pharmaceuticals, Michael J. Celestine, Jimmie L. Bullock, Shivani Boodram, Varma H. Rambaran, Alvin A. Holder

Chemistry & Biochemistry Faculty Publications

This is a review of the literature concerning the interesting properties of p-, d-, and f-block elements when coordinated with 2,6-pyridinedicarboxylic acid (dipicolinic acid, H₂dipic) and its derivatives as ligands, with a focus on their use as inorganic pharmaceuticals. Some of the complexes reported were used as insulin-like, bioimaging contrasting agents, antimicrobial agents, and anticancer agents.

Density Functional Theory Modeling Of It-Stacking And Electrophilic Donor-Acceptor Interactions With Application To Therapeutic Targeting Of Zinc-Finger Proteins, Patricia Beall Lutz

Chemistry & Biochemistry Theses & Dissertations

Several viruses, including viruses that cause cancer, contain conserved zinc finger (ZF) proteins that are essential for viral reproduction, making them attractive drug targets for cancer and viral treatment. ZFs are small protein domains that have Zn²⁺ tetrahedrally coordinated to at least 2 Cys and His. They form three classes of ZFs depending on the amino acid ligands, CCHH, CCCH, and CCCC. Zn²⁺ is stable towards redox reactions; however, the Cys thiolates are redox active. Oxidation of the Cys thiolates release Zn²⁺, and the ZF loses its tertiary structure and can no longer bind DNA or …

Brust-Schiffrin Synthesis Of Catalytic Bipodal Pdpt Nanoparticles With Some Mechanistic Insights, Sangbum Han, Vara P. Sheela, Wei Cao, Balasubramanian Ramjee

Applied Research Center Publications

Brust–Schiffrin reduction of Pd and Pt precursors in the presence of resorcinarene amine surfactant led to the formation of substantially Pt rich, PdPt bimetallic nanoparticles of a V-shape or variants on the V-shape. New insights into this reaction are provided on the basis of reversed Brust–Schiffrin syntheses, DLS, UV-vis, and NMR analysis. Based on our experiments we conclude that the resorcinarene amine surfactant is part of the inverse micelle formed from TOABr and it also selectively complexes with the Pd salts prior to their reduction. Remarkably, the composition of the bipodal nanoparticles could be varied substantially by varying the reaction …

Tunable Gold Nanostructures With Nanocapsules As Template Reaction Vessels, Balasubramanian Ramjee, Srujana Prayakarao, Sangbum Han, Wei Cao

Chemistry & Biochemistry Faculty Publications

Hollow, polymeric, thiol-ene resorcinarene nanocapsules can act as template reaction vessels for the synthesis of gold nanoshells or spherical aggregates of gold nanoparticles depending on the reaction conditions. The spherical nanoparticle aggregates were evaluated as catalysts in the biphasic reduction of 4-nitrophenol.

Computational Investigation Of The Bioactive Selenium Compounds Ebselen And Selenious Acid, Sonia Antony

Chemistry & Biochemistry Theses & Dissertations

Selenium, a toxic element, is required in trace quantities for the proper functioning of biological systems. The experimental mechanistic study of the reactions of ebselen and selenious acid is difficult due to complexity of the reaction mixtures and the presence of short-lived intermediates. Computational modeling of the reactivity of these species can give us an insight into their mechanisms, but the process is complicated by proton exchanges associated with the mechanistic steps. In gas phase modeling, this may be corrected to a certain level using the solvent assisted proton exchange (SAPE) method. SAPE is a modeling technique that mimics solvent …

A Three Dimensional Green's Function Solution Technique For The Transport Of Heavy Ions In Laboratory And Space, Candice Rockell Gerstner

Mathematics & Statistics Theses & Dissertations

In the future, astronauts will be sent into space for longer durations of time compared to previous missions. The increased risk of exposure to ionizing radiation, such as Galactic Cosmic Rays and Solar Particle Events, is of great concern. Consequently, steps must be taken to ensure astronaut safety by providing adequate shielding. The shielding and exposure of space travelers is controlled by the transport properties of the radiation through the spacecraft, its onboard systems and the bodies of the individuals themselves. Meeting the challenge of future space programs will therefore require accurate and efficient methods for performing radiation transport calculations …

Localized Surface Plasmon Resonance Of Single Silver Nanoparticles Studied By Dark-Field Optical Microscopy And Spectroscopy, Wei Cao, Tao Huang, Xiao-Hong Nancy Xu, Hani E. Elsayed-Ali

Electrical & Computer Engineering Faculty Publications

Localized surface plasmon resonance (LSPR) of Ag nanoparticles (NPs) with different shapes and disk-shaped Ag NP pairs with varying interparticle distance is studied using dark-field optical microscopy and spectroscopy (DFOMS). Disk-, square-, and triangular-shaped Ag NPs were fabricated on indium tin oxide-coated glass substrates by electron beam lithography. The LSPR spectra collected from single Ag NPs within 5×5 arrays using DFOMS exhibited pronounced redshifts as the NP shape changed from disk to square and to triangular. The shape-dependent experimental LSPR spectra are in good agreement with simulations using the discrete dipole approximation model, although there are small deviations in the …

Argon Eximer Emission From High-Pressure Microdischarges In Mental Capillaries, R. Mohan Sankaran, Konstantinos P. Giapis, Mohamed Moselhy, Karl H. Schoenbach

Bioelectrics Publications

We report on argon excimer emission from high-pressure microdischarges formed inside metal capillaries with or without gas flow. Excimer emission intensity from a single tube increases linearly with gas pressure between 400 and 1000 Torr. Higher discharge current also results in initial intensity gains until gas heating causes saturation or intensity drop. Argon flow through the discharge intensifies emission perhaps by gas cooling. Emission intensity was found to be additive in prealigned dual microdischarges, suggesting that an array of microdischarges could produce a high-intensity excimer source.

Resonant Energy Transfer From Argon Dimers To Atomic Oxygen In Microhollow Cathode Discharges, M. Moselhy, R. H. Stark, K. H. Schoenbach, U. Kogelschatz

Bioelectrics Publications

The emission of atomic oxygen lines at 130.2 and 130.5 nm from a microhollow cathode discharge in argon with oxygen added indicates resonant energy transfer from argon dimers to oxygen atoms. The internal efficiency of the vacuum-ultraviolet (VUV) radiation was measured as 0.7% for a discharge in 1100 Torr argon with 0.1% oxygen added. The direct current VUV point source operates at voltages below 300 V and at current levels of milliamperes.

Xenon Excimer Emission From Pulsed Microhollow Cathode Discharges, M. Moselhy, R. H. Stark, K. H. Schoenbach, U. Kogelschatz

Bioelectrics Publications

By applying electrical pulses of 20 ns duration to xenon microplasmas, generated by direct current microhollow cathode discharges, we were able to increase the xenon excimer emission by more than an order of magnitude over direct current discharge excimer emission. For pulsed voltages in excess of 500 V, the optical power at 172 nm was found to increase exponentially with voltage. Largest values obtained were 2.75 W of vacuum-ultraviolet optical power emitted from a single microhollow cathode discharge in 400 Torr xenon with a 750 V pulse applied to a discharge. Highest radiative emittance was 15.2 W/cm². The …

Copper Complexation And Speciation In The Western South And Equatorial Atlantic Ocean, John A. Consolvo

Chemistry & Biochemistry Theses & Dissertations

Presented here are the first data on copper complexation and speciation in the South Atlantic Ocean. Samples were collected at six vertical profile stations and along the surface (1m) transect during the 1996 IOC Baseline Contaminant Survey. Copper complexation measurements were made for the surface transect (1m) samples and three of the six vertical profile stations (1m - ~500m) using differential pulse anodic stripping voltammetry (DPASV) with a thin mercury film, rotating glassy carbon disk electrode (TMFRGCDE).

A strong organic copper complexing ligand (L₁; log K' _cuL1/cu2+ > 11. 8 ± 0 .4) was detected in 57% of all …

Microhollow Cathode Discharge Excimer Lamps, Karl H. Schoenbach, Ahmed El-Habachi, Mohamed M. Moselhy, Wenhui Shi, Robert H. Stark

Bioelectrics Publications

Microhollow cathode discharges are high-pressure, nonequilibrium gas discharges between a hollow cathode and a planar or hollow anode with electrode dimensions in the 100 μm range. The large concentration of high-energy electrons, in combination with the high-gas density favors excimer formation. Excimer emission was observed in xenon and argon, at wavelengths of 128 and 172 nm, respectively, and in argon fluoride and xenon chloride, at 193 and 308 nm. The radiant emittance of the excimer radiation was found to increase monotonically with pressure. However, due to the decrease in source size with pressure, the efficiency (ratio of excimer radiant power …

Zinc Speculation And Ligand Fluxes In Chesapeake Bay And Elizabeth River Pore Waters, Duncan Glover Byers

Chemistry & Biochemistry Theses & Dissertations

Presented here are the first data on the vertical concentrations, complexation, speciation, and fluxes of total dissolved zinc and zinc complexing ligands, and zinc speciation in sediment pore waters in the Chesapeake Bay and Elizabeth River, Virginia.

Sediment pore waters were collected in mid and southern Chesapeake Bay in November 1997 and in the Elizabeth River (Pinner's Point) in March, April, and July 1998. Flux experiments were conducted in Elizabeth River sediment cores in April and July 1998. [TDZn] and zinc complexation were determined using differential pulse anodic stripping voltammetry at a hanging mercury drop electrode (DPASV-HMDE).

[TDZn] in the …

Generation Of Intense Excimer Radiation From High-Pressure Hollow Cathode Discharges, Ahmed El-Habachi, Karl H. Schoenbach

Bioelectrics Publications

By reducing the diameter of the cathode opening in a hollow cathode discharge geometry to values on the order of 100 μm, we were able to operate these discharges in noble gases in a direct current mode up to atmospheric pressure. High-pressure discharges in xenon were found to be strong sources of excimer radiation. Highest intensities at a wavelength of 172 nm were obtained at a pressure of 400 Torr. At this pressure, the vacuum ultraviolet (VUV) radiant power of a single discharge operating at a forward voltage of 220 V and currents exceeding 2 mA reaches values between 6% …

Microhollow Cathode Discharges, K. H. Schoenbach, R. Verhappen, R. Tessnow, F. E. Peterkin, W. W. Byszewski

Bioelectrics Publications

The current–voltage characteristics of hollow cathode discharges and their predischarges in argon under dc and pulsed conditions were found to have a positive slope at pressures up to approximately 50 Torr, and currents up to 20 mA, at a hole diameter of 0.7 mm. In this range of pressure and current, parallel operation of hollow cathode discharges, without ballast, was demonstrated. Scaling to higher pressure is possible by reducing the hole diameter. Pulsed experiments with an array of cathode rings of 75 μm diameter allowed us to obtain parallel operation of more than 50 discharges at a pressure of 350 …