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Synthesis And Characterization Of Terbium(Iii) Complexes: Can We Manipulate The Emission Signature?, Ryan Gagnon

Belmont University Research Symposium (BURS)

Successful Lewis acid/base reactions of terbium(III) nitrate with 2,2’-bipyrdine (22’bpy), 1,10-phenanthroline (phen), and 2,6-pyridine dimethanol (pydm) have yielded the products: Tb(22’bpy)₂(NO₃)₃, Tb(phen)₂(NO₃)_3, and [Tb(pydm)₃](NO₃)₃, respectively. In accord with the well-known antenna-effect, the absorption spectrum of each complex is similar to the spectrum of the free ligand, while the emission spectrum of the complex is identical for the free terbium(III) ion. In contrast, the substitution of a ligand containing a third-row nonmetal strategically placed near the terbium may force interaction between the 3p nonmetal …

O-Sulfonamidophenol Ligands And Derivatives For F-Element Sensing, Complexation, And Extraction From Alkaline High-Level Waste, Oluwaseun William Adedoyin

FIU Electronic Theses and Dissertations

The accumulated (>100 Mgal) alkaline high-level waste (HLW), which is a legacy of nuclear weapons manufacturing during the cold war era, is an issue of environmental concern that has presented reprocessing challenges, due to its complex physicochemical properties and the presence of ¹³⁷Cs, ⁹⁰Sr, and long-lived actinides.

This study is focused on o-sulfonamidophenol derivatives bearing electron-rich O- and N- donor sites (when deprotonated in alkaline conditions) for effective complexation, sensing, and extraction of f-elements from highly alkaline solutions. Using Ln(III) as experimental surrogates for An(III), a family of o-sulfonamidophenol ligands (L1H₂ – L4H_{2 …}

Geochemistry, Petrology, And Palynology Of The Princess No. 3 Coal, Greenup County, Kentucky, Madison M. Hood, Cortland F. Eble, James C. Hower, Shifeng Dai

Center for Applied Energy Research Faculty and Staff Publications

The high volatile C bituminous-rank, Bolsovian-age Princess No. 3 coal, a correlative of the heavily-mined Hazard No. 7 coal and the Peach Orchard and Coalburg Lower Split coals, was investigated three sites at a mine in Greenup County, Kentucky. The coal exhibits a “dulling upwards” trend, with decreasing vitrinite and a greater tendency towards dull clarain and bone lithotypes towards the top of the coal. The relatively vitrinite-rich basal lithotype is marked by a dominance of lycopod tree spores. The palynology transitions upwards to a middle parting co-dominated by tree fern and small lycopod spores and an upper bench dominated …

Rare Earth-Bearing Particles In Fly Ash Carbons: Examples From The Combustion Of Eastern Kentucky Coals, James C. Hower, John G. Groppo Jr.

Center for Applied Energy Research Faculty and Staff Publications

Graphitic carbons from the combustion of bituminous coals and, perhaps, other coal ranks, tend to capture iron and a number of hazardous elements, including As, Hg, and Se. Rare earth elements in fly ashes occur in minerals, such as monazite, xenotime, and davidite. They also occur in sub-nm particles, probably in a mineral form, within the Al–Si glass on the investigated fly ashes. Just as graphitic carbons can capture Fe and hazardous elements, the carbons surrounding the fly ash glass and magnetic particles captures or encapsulates a broad suite of rare earth elements.

Dipicolinamide Ligands And Analogs For Lanthanides (Ln), Actinides (An) And Mercury (Hg) For Application To Nuclear Fuel Cycle Separations And Waste Management, Ingrid Lehman-Andino

FIU Electronic Theses and Dissertations

Spent nuclear fuel (SNF) – or used nuclear fuel (UNF) – contains long-lived minor actinides such as ²⁴¹Am, ²⁴⁵Cm, and ²³⁷Np, together with fission products that include lanthanides. Minor actinides are responsible for much of the radiotoxicity and heat generation that limits the capacity of geological repositories. Thus, removing minor actinides from UNF can reduce storage time required for decay to natural levels of activity by several orders of magnitude. Actinide(An)/Lanthanide(Ln) separation processes via solvent extraction by selective complexation with organic or aqueous ligands have to overcome difficulties due to similarities in their ionic radii for the …

Mass-Analyzed Threshold Ionization Of Lanthanide Imide Lnnh (Ln = La And Ce) Radicals From N–H Bond Activation Of Ammonia, Yuchen Zhang, Silver Nyambo, Dong-Sheng Yang

Chemistry Faculty Publications

Ln (Ln = La and Ce) atom reactions with ammonia are carried out in a pulsed laser vaporization supersonic molecular beam source. Lanthanide-containing species are observed with time-of-flight mass spectrometry, and LnNH molecules are characterized by mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical calculations. The theoretical calculations include density functional theory for both Ln species and a scalar relativity correction, electron correlation, and spin-orbit coupling for the Ce species. The MATI spectrum of LaNH exhibits a single vibronic band system with a strong origin band and two weak vibronic progressions, whereas the spectrum of CeNH displays two band systems …

Exploring Rapid Radiochemical Separations At The University Of Tennessee Radiochemistry Center Of Excellence, Howard L. Hall, John D. Auxier Ii

Faculty Publications and Other Works -- Institute for Nuclear Security

The University of Tennessee formed its Radiochemistry Center of Excellence (RCoE) in 2013 with support from the U.S. National Nuclear Security Administration. One of the major thrusts of the RCoE is to develop deeper understanding of rapid methods for radiochemical separations that are relevant to both general radiochemical analyses as well as post-detonation nuclear forensics. Early work has included the development and demonstration of rapid separations of lanthanide elements in the gas phase, development of a gas-phase separation front-end for ICP-TOF-MS analysis, and the development of realistic analytical surrogates for post-detonation debris to support methods development.

An Analytical Method For Detecting Toxic Metal Cations Using Cyclotriveratrylene Derivative Capped Gold Nanoparticles, Zachary R. Osner, Richard C. Holz, Daniel P. Becker

Chemistry Faculty Research and Publications

Cyclotriveratrylene-oxime (CTV-oxime) derivatives that terminate with a dithiolate linker were synthesized enabling the supramolecular scaffold to adhere to gold nanoparticles (AuNPs) with the bowl-shaped cavity of the CTV scaffold exposed for utilization in host–guest chemistry. Exposure of these CTV functionalized AuNPs to varying concentrations of di- and trivalent metal cations resulted in the formation of large CTV-AuNP polymeric clusters and an accompanying a shift in the plasmon resonance. These interactions between the CTV-AuNPs and the metal cations in solution provides proof-of-concept that supramolecular functionalized AuNPs can be used as a simple and straightforward, on-site detection system for toxic metal cations …

An Analytical Method For Detecting Toxic Metal Cations Using Cyclotriveratrylene Derivative Capped Gold Nanoparticles, Zachary R. Osner, Richard C. Holz, Daniel P. Becker Ph.D.

Chemistry: Faculty Publications and Other Works

Cyclotriveratrylene-oxime (CTV-oxime) derivatives that terminate with a dithiolate linker were synthesized enabling the supramolecular scaffold to adhere to gold nanoparticles (AuNPs) with the bowl-shaped cavity of the CTV scaffold exposed for utilization in host–guest chemistry. Exposure of these CTV functionalized AuNPs to varying concentrations of di- and trivalent metal cations resulted in the formation of large CTV-AuNP polymeric clusters and an accompanying a shift in the plasmon resonance. These interactions between the CTV-AuNPs and the metal cations in solution provides proof-of-concept that supramolecular functionalized AuNPs can be used as a simple and straightforward, on-site detection system for toxic metal cations …

Spectroscopic Properties Of Lanthanide (Iii) Compounds In Aqueous And Ionic Media, Orissa A. Burghard, Sayandev Chatterjee, Zheming Wang, Samuel A. Bryan

STAR Program Research Presentations

Lanthanide containing materials are receiving increasing attention due to their wide range of potential applications including bioanalytical imaging, dye-sensitized solar cells, nano-biotechnology and catalysis. The unique spectroscopic properties (intense and sharp emission bands with high color purity and high quantum efficiency) of lanthanides make them strong candidates for use as bio-markers or selective detectors. The attractiveness of lanthanides as future imaging agents as well as recent interest in their potential use in biological media has increased the need to understand the behavior of lanthanides in the presence of other ions or in ionic media.

The complexity of the biological media …