Physical Sciences and Mathematics Commons^™

Anion Binding And Sensing Using Cs124-Sensitized Luminescent Terbium Complexes, Alessandro Rizzi, Minhee Lee, Wade Grabow, Olivia Brooks, Helena Nguyen, Neal Yakelis, Clarisse Vanderfeltz

Honors Projects

Two terbium complexes with varying degrees of intramolecular coordination, Tb:DO2A-Cs124 and Tb:DOTA-Cs124, were prepared. Their capacity to detect biologically and environmentally relevant anions through their luminescence changes was investigated. Tb:DOTA-Cs124 demonstrated exceptional selectivity as a sensor for nitrite, while Tb:DO2A-Cs124 detects nitrite, phosphates, and a range of carboxylate-containing anions.

Hydrothermal Synthesis Of Frustrated Lanthanide Pyrochlores And Transition Metal Double Perovskites And Germanates, Matthew S. Powell

All Dissertations

Magnetically frustrated materials hold promise of unique behavior allowing for the novel study of quantum phenomena. Such materials are poised to become an integral foundation for technological advancement in the post-Silicon Age. Crystalline materials are given special focus where the rigid lattice allows more detailed study of these quantized effects and frustration behavior. As opposed to polycrystalline powders, large single crystals can be preferentially aligned enabling the study of anisotropic behavior. Two cubic structure types have garnered significant interest due to their 3-D tetrahedral arrangement of symmetry-related metal centers with the potential for magnetic frustration: pyrochlores and perovskites.

The supercritical …

Exploring The Structure And Activity Of Metallo-Tetracyclines, Shahedul Islam

USF Tampa Graduate Theses and Dissertations

Copper as a key component of electron transport chain of eukaryotes is an essential transition metal ion. Copper homeostasis in mammals complex and tightly regulated. Its strong reactivity together with binding with biologically important chemicals can have important repercussions in human health and overall environment. Tetracycline as one of most abundantly used antibiotic of the world has become abundant in the environment as well. Herein in this dissertation we take the journey to explore the complexation of tetracycline with metals in the environment and the intricate interaction between copper and tetracycline by investigating their oxidative behavior once they are complexed. …

Understanding The Effects Of Ligand Environment On Important Properties Of Redox-Active Europium Using Computational Chemistry And T1-Weighted Magnetic Resonance Imaging, Brooke Anne Corbin

Wayne State University Dissertations

This thesis is a collection of seven chapters that describes a combination of literature research and experimental analyses into the study of inorganic complexes, with an emphasis on the photophysics and coordination of redox-active europium. The first chapter summarizes the key features of each chapter. The second and third chapters are detailed overviews, including historical context, current studies, and future goals of imaging science, with an emphasis on inorganic complexes. The fourth chapter describes the design of a screening procedure to study new ligand environments for redox-active europium using magnetic resonance imaging and a proof-of-concept experiment. The fifth chapter is …

First Homoleptic Rare Rarth Metal Complexes With Doubly-Reduced Dibenzocyclooctatetraene, James C. Mahoney

Legacy Theses & Dissertations (2009 - 2024)

A set of novel complexes of rare earth elements, M(III) = Y, La, Gd, Tb, and Dy, with the doubly-reduced dibenzo[a,e]cyclooctatetraene (DBCOT) anion has been synthesized and crystallographically characterized for the first time. Preparation of new complexes has been accomplished through the ligand-metathesis reaction of M(III) triiodides with K2(DBCOT) in THF at ambient conditions. Subsequent crystallization via slow solvent evaporation afforded single crystals of good quality. X-ray diffraction technique confirmed that all complexes are isomorphous and conform to the [M(DBCOT)(THF)4][M(DBCOT)2] composition. In their crystal structures, the monoanionic double-decker sandwiches, [M(DBCOT)2], weakly interact with the cationic counterparts, [M(DBCOT)(THF)4]+. In both parts, …

Fabrication Of Nd3+ And Yb3+ Doped Nir Emitting Nano Fluorescent Probe: A Candidate For Bioimaging Applications, D. Karthickraja, G. A. Kumar, D. K. Sardar, S. Karthi, Gamage C. Dannangoda, Karen S. Martirosyan, M. Prasath, M. Gowri, E. L. Girija

Physics and Astronomy Faculty Publications and Presentations

The intentional design of rare earth doped luminescent architecture exhibits unique optical properties and it can be considered as a promising and potential probe for optical imaging applications. Calcium fluoride (CaF2) nanoparticles doped with optimum concentration of Nd3+ and Yb3+ as sensitizer and activator, respectively, were synthesized by wet precipitation method and characterized by x-ray diffraction (XRD) and photoluminescence. In spite of the fact that the energy transfer takes place from Nd3+ to Yb3+, the luminescence intensity was found to be weak due to the lattice defects generated from the doping of trivalent cations (Nd3+ and Yb3+) for divalent host …

Synthesis, Structures, Optical And Electronic Properties Of Functional Inorganic And Hybrid Materials, Sura Menda Ginting

Graduate Research Theses & Dissertations

Synthesis of complex functional inorganic and hybrid material is desirable because complex composition allows more degree of freedom and tunable materials where the properties differ from those of their parent components. As a test of concept, we have synthesized a series of LnMOFs with the general formula of [Ln(NDC)(DMA)2(NO3)]n (Ln=Ce, Nd, Sm, Eu, Tb, Yb). These materials are isostructural, adopting the orthorhombic P b c a space group. They are relatively stable under drying and heating treatment and have more metal coordination numbers compared to transition metal MOFs. There are theoretically sizable channels and free space inside the structure, allowing …

Geoenergetic Features Of Lanthanoids And Radioactive Elements In Irrigated Soils, A. Turdaliyev Doctor Of Biological Sciences, K. Asqarov Teacher, N. Xodjibolayeva Teacher

Scientific journal of the Fergana State University

The paper studies the geoenergetic features of the lanthanides and radioactive elements in the genetic horizons of irrigated meadow saz soils of Central Fergana. moreover, the number of these elements was determined depending on their geoenergetic features in the soil profile, and the geochemical Clark spectra of these elements were developed.

Visible And Ultraviolet Upconversion And Near Infrared Downconversion Luminescence From Lanthanide Doped La2zr2o7 Nanoparticles, Santosh K. Gupta, Mitzy A. Penilla Garcia, Jose P. Zuniga, Maya Abdou, Yuanbing Mao

Chemistry Faculty Publications and Presentations

Single materials which have a multitude of photophysical processes by selective doping are in high demand in the community of material science due to their multifunctional applications. Upconversion (UC) and downconversion (DC) luminescence properties of lanthanide doped nanoparticles (NPs) are imperative for their broad application potentials. Here, we describe two series of either doubly or triply doped La2Zr2O7 NPs synthesized by a molten salt method. For the former, La2Zr2O7:Yb,Er NPs display bright red and moderate green UC (VUC) and NIR-B DC (NDC) at around 1550 nm, which are highly desirable for in-vivo bioimaging applications. For the latter, La2Zr2O7:Gd,Yb,Tm NPs demonstrate …

Luminescence Antenna Behavior In Lanthanide Complexes And Luminescence Sensing In Group 11 Iodides, Francis Barnes

Electronic Theses and Dissertations

In this thesis luminescent materials are studied. The luminescent materials studied are lanthanide complexes and group 11 iodide sensing abilities. Emission intensity of the lanthanide complexes through direct excitation of the lanthanide ion are relatively weak. To overcome this, three unique organic ligands were utilized to synthesize lanthanide nitrate complexes in which higher emission intensity can be observed via the antenna effect. Increased emission intensity resulted for Eu^III and Tb^III complexes for each ligand except triphenylphosphane oxide (only the Tb^III complex demonstrated increased emission intensity). Latva’s empirical rule allows for the antenna effect to occur, in which …

A Family Of Cyclooctatetraenyl Lanthanide(Iii) Chloridebridged Dimers : Synthesis, Characterization, And Magnetic Properties, Joshua Sky Greenough

Legacy Theses & Dissertations (2009 - 2024)

Historically, the 10π-aromatic ligand, cyclooctatetraene (COT), has played a pivotal role

Synthesis And Reductive Chemistry Of Bimetallic And Trimetallic Rare-Earth Metallocene Hydrides With (C5h4sime3)1− Ligands, Megan T. Dumas, Guo P. Chen, Jasper Y. Hu, Mitchell A. Nascimento, Jeremy M. Rawson, Joseph W. Ziller, Filipp Furche, William J. Evans

Chemistry and Biochemistry Publications

The reductive chemistry of [Cp'₂Ln(μ–H)(THF)_x]_y [Ln = Y, Dy, Tb; Cp' = (C₅H₄SiMe₃)¹⁻; x = 2, 0 and y = 2, 3] was examined to determine if these hydrides would be viable precursors for 4fⁿ5d¹ Ln²⁺ ions that could form 5d¹-5d¹ metal–metal bonded complexes. The hydrides were prepared by reaction of the chlorides, [Cp'₂Ln(μ–Cl)]₂, 1-Ln, with allylmagnesium chloride to form the allyl complexes, [Cp'₂Y(η³–C₃H_{5 …}

Investigation Of Host-Sensitized Luminescence Of Trivalent Lanthanide Doped Yttrium Phosphate Using Vuv Spectroscopy, Zachary Way

All Master's Theses

Host-sensitized luminescence of yttrium phosphate doped with trivalent lanthanide elements prepared via two synthetic approaches was studied using VUV spectroscopy. A correlation between an unusually intense 150 nm excitation intensity and the ground state energy level of select trivalent lanthanide elements was proposed. Using spectroscopy, the host-to-activator transfer efficiencies of YPO₄:Ln³⁺ (Ln³⁺ = Sm³⁺, Eu³⁺ and Tb³⁺) were evaluated for two synthetic approaches. Electron-hole pair trapping efficiencies and S_loss values were calculated using published kinetic models.

Development Of An F-Element Separation Chemistry Using Solid Electrolytes, Kristian Guy Myhre

Doctoral Dissertations

The f‒elements (lanthanides and actinides) have numerous applications and are critically important to many industries, including the energy, security, and medical industries. One of the barriers to increased use and availability of the f‒elements is the difficulty in separating them from each other due to their similar chemistries. This is especially true of the trivalent f‒elements (lanthanides and minor actinides). The development of separation techniques that maximize the differences in the physicochemical properties of the f‒elements is therefore an important area of research. For these reasons, an effort was undertaken to explore the use of solid …

Notes On Contributions To The Science Of Rare Earth Element Enrichment In Coal And Coal Combustion Byproducts, James C. Hower, Evan J. Granite, David B. Mayfield, Ari S. Lewis, Robert B. Finkelman

Center for Applied Energy Research Faculty and Staff Publications

Coal and coal combustion byproducts can have significant concentrations of lanthanides (rare earth elements). Rare earths are vital in the production of modern electronics and optics, among other uses. Enrichment in coals may have been a function of a number of processes, with contributions from volcanic ash falls being among the most significant mechanisms. In this paper, we discuss some of the important coal-based deposits in China and the US and critique classification systems used to evaluate the relative value of the rare earth concentrations and the distribution of the elements within the coals and coal combustion byproducts.

Europium(Ii)-Containing Complexes For Responsive Magnetic Resonance Imaging, Levi Alexander Ekanger

Wayne State University Dissertations

The research projects described in this dissertation are focused on studying the oxidation of EuII-containing complexes within the context of responsive MRI. Prior to this research, EuII had not been explored within the context of oxidation-responsive MRI nor had the use of this ion been reported in vivo. The results of these studies enable predictions about the oxidation-responsive behavior of EuII-containing complexes in vitro and in vivo.

The EuII-containing cryptate 1.33 was used to evaluate EuII-based positive contrast enhancement after intravenous, intraperitoneal, and subcutaneous injections. The transitory behavior of the positive contrast enhancement correlated with reported levels of oxygenation and …

Use Of 17o-Nmr Spectroscopy To Study The Coordination Chemistry Of Trivalent Lanthanide Ions In Solution, Zhijin Lin

Wayne State University Dissertations

Trivalent lanthanide (Ln3+)-containing complexes have a number of important applications in molecular imaging, catalysis, medical diagnosis, information storage, and environmental sensing. The properties of Ln3+-containing complexes that are useful for these applications are influenced by coordination chemistry, including the number of coordinated ligands and ligand-exchange rates. The coordination numbers for water molecules bound to Eu3+ and Tb3+ have been studied by luminescence-decay measurements; however, the coordination numbers of other important oxygen-containing functional groups such as ketones, esters, ethers, sulfonyls, amides, phosphine oxides, and aldehydes have not been as thoroughly studied in solution because of the lack of hydroxyl groups that …

Lanthanide-Based Precatalysts For Carbon-Carbon Bond-Forming Reactions In Aqueous Media, Derek James Averill

Wayne State University Dissertations

The formation of carbon-carbon bonds is of great interest to synthetic chemists because these bonds make up the majority of biologically active compounds. The Mukaiyama aldol reaction is a Lewis-acid-catalyzed carbon-carbon bond-forming reaction that has the ability to produce optically active β-hydroxy carbonyls which can be found in many pharmaceuticals and natural products. Because of precatalyst instability towards hydrolysis, anhydrous solvents are commonly used. Recent efforts have focused on water-tolerant versions of enantioselective Mukaiyama aldol reactions because of the financial and environmental benefits of using aqueous media. Consequently, the Lewis-acidic and water-tolerant features of Ln³⁺ ions have aroused great …

Synthesis And Characterization Of Fluorophores For The Detection Of Lanthanides And Actinides, Robinson I. Roacho

Open Access Theses & Dissertations

A series of fluorophores based in the boron dipyrromethene (BODIPY) family were synthesized and characterized. These fluorophores have the capacity of being introduced to a carbamoyl methyl phosphine oxide (CMPO) lanthanide/actinide extractant. These blue, green and red emission fluorophores show high thermal/moisture stability and high fluorescence efficiencies. The fluorescence intensity seems to be dependent on the restricted rotation about the C(8)-C bond in 8-Ph-BODIPY. By taking advantage of this feature, a hydroxyl- containing BODIPY with high fluorescence intensity was synthesized to be incorporated to a CMPO carboxylic acid via esterification. Unfortunately, we did not observe an optical response upon the …

Synthesis And Computational Studies Of A New Class Of Lanthanide Niobate Cluster : [Ln4(H2O)8(So4)5(Nbo3)2]+3h2O; Ln= Dy, Tb, Brady D. Garabato

Masters Theses & Specialist Projects

Polyoxoniobates (PONbs) are a small family of highly electron-rich clusters. The development of new solids composed of these clusters have applications in green energy and electronics. However, the high charge environment of PONbs typically requires alkaline synthetic conditions that are unsuitable for introducing other metals and organic molecules, making synthesis of new systems difficult. To date, very few transition metals and organic ligands have been incorporated into these PONb solids, and lanthanide metal inclusion, which generally improves photoconductivity due to longlived f-orbital excitations, has not yet been fully realized. Here, the synthesis of a new class of lanthanide niobate cluster …

Luminescence Studies : Part I. Lanthanide Nanogumbos Part Ii. Near Infrared Photothermal Nanogumbos, Jonathan Carver Dumke

LSU Doctoral Dissertations

Group of Uniform Materials Based on Organic Salts (GUMBOS) are a class of molten salts that have been focused to be specifically tailored towards applications. Primitively, from Davy to Walden molten salts were desirable for organic synthesis due to the properties. GUMBOS have been synthesized into nanoparticles (nanoGUMBOS) by various methods to be used for lanthanide luminescence and hyperthermal cancer therapeutics. Lanthanide photochemistry has been frequently studied for its high luminescence intensity, narrow emission band, and stable luminescent lifetime decay. Aerosol-derived europium nanoGUMBOS were characterized using electron microscopy (39.5 ± 8.4 nm), XPS, and spectroscopic techniques. Spectroscopic measurements indicated intense …

Synthesis And Characterization Of Magnetic Solids Featuring 3d-4f Heterometallic Oxides Comprised Of Spin Chains And 3d-6p Noncentrosymmetric Oxides Templated By Acentric Salt Units, Jennings West

All Dissertations

The studies and syntheses presented in this dissertation were primarily aimed at exploring new magnetic solids comprised of special framework oxides with novel magnetic properties. Low-dimensional magnetic behavior has been of great interest, especially pertaining to molecular solids having single magnetic domains where slow relaxation and quantum properties of magnetization are evident. In attempts to mimic molecular magnets and achieve reduced dimensionality of, in this case 3d-;4f magnetic sublattices, diamagnetic oxyanions, XO_mn-, and A-site cations (A = alkali and alkaline-earth metals) were used as nonmagnetic spacers in hopes of disrupting or confining magnetic interactions in certain dimensions. The …

Euknatao5: Crystal Growth, Structure And Photoluminescence Property, Irina Roof, Mark Smith, Sangmoon Park, Hans Conrad Zur Loye

Hans Conrad zur Loye

The synthesis, structure determination, and intrinsic luminescent properties of a new tantalate, EuKNaTaO5, are reported. Single crystals of the title compound were grown out of a reactive KOH/NaOH eutectic melt. Luminescence in many materials is activated by doping a rare earth cation into the solid matrix; we report undoped, all-rare earth EuKNaTaO5, which exhibits bright orange room temperature photoluminescence.

Preparation And Characterization Of Extraction Chromatography Resins Using N-Donor Extractants For Trivalent Actinide And Lanthanide Separations, Christopher L. Klug

UNLV Theses, Dissertations, Professional Papers, and Capstones

Actinide and lanthanide elements exist in the geosphere and biosphere due to both natural abundances and anthropogenic activities. The investigation of the presence and transport of actinides through the environment is of great scientific interest. In order to prepare environmental samples for precise measurements, the individual actinides must be separated from the chemically similar lanthanides, and from neighboring actinides. Existing extraction chromatography resins are either poorly suited for this separation, have bleeding problems, are not reusable, or fail the CHON principle. In an effort to resolve these issues, malonamides and N-donor extractants from the BTP and BTBP classes of solvent …

A Lanthanide-Based Chemosensor For Bioavailable Fe3+ Using A Fluorescent Siderophore: An Assay Displacement Approach, Karen M. Orcutt, William Scott Jones, Andrea Mcdonald, David Schrock, Karl J. Wallace

Faculty Publications

The measurement of trace analytes in aqueous systems has become increasingly important for understanding ocean primary productivity. In oceanography, iron (Fe) is a key element in regulating ocean productivity, microplankton assemblages and has been identified as a causative element in the development of some harmful algal blooms. The chemosenor developed in this study is based on an indicator displacement approach that utilizes time-resolved fluorescence and fluorescence resonance energy transfer as the sensing mechanism to achieve detection of Fe3+ ions as low as 5 nM. This novel approach holds promise for the development of photoactive chemosensors for ocean deployment.

Synthesis, Crystal Growth, Magnetic And Transport Properties Of Ln-M-X (Ln=Lanthanide, M=Transition Metal, X=In, Ga) Compounds, Willa Maria Williams

LSU Doctoral Dissertations

ABSTRACT This dissertation focuses on the structural stability, magnetic and transport properties of ternary lanthanide compounds grown using indium and gallium flux. Single crystals of TbRhIn5 were synthesized using indium flux. TbRhIn5 is isostructural to the well known LnnMIn3n+2 (n = 1, 2, ∞; Ln = La, Ce; M = Rh, Ir) and adopts the HoCoGa5 structure type and crystallizes in the space group P4/mmm, Z = 1. Lattice parameters are a = 4.6000(6) Å and c = 7.4370(11) Å, V = 157.29(6) Å3. A sharp antiferromagnetic transition is observed at TN = 48 K for TbRhIn5. Single crystals of …

Direct Detection Of Homocysteine And Syntheses Of Lanthanide Complexes As Biosensors, Weihua Wang

LSU Doctoral Dissertations

At elevated levels, homocysteine (Hcy) is a risk factor for cardiovascular diseases and Alzheimer’s disease. It’s also implicated in a number of other diseases such as neural tube defects, pregnancy complications, and renal failures. The monitoring of Hcy levels in plasma is of current concern. To date, the biochemical mechanism by which Hcy is involved in disease states is unclear. Herein, we describe highly selective colorimetric methods for the direct determination of Hcy. Inexpensive, commercially available materials are reported. The results show potential application for the detection of Hcy in human blood plasma. Additionally, new HPLC postcolumn detection methods for …