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Exploration Of A Unique Uranium Mediated Carbon-Carbon Radical Coupling Reaction, Zhengjia Tong, Caleb J. Tatebe, John J. Kiernicki, Matthias Zeller, Suzanne C. Bart 2017 Purdue University

Exploration Of A Unique Uranium Mediated Carbon-Carbon Radical Coupling Reaction, Zhengjia Tong, Caleb J. Tatebe, John J. Kiernicki, Matthias Zeller, Suzanne C. Bart

The Summer Undergraduate Research Fellowship (SURF) Symposium

Designing an efficient nuclear fuel cycle has motivated decades of research on aqueous phase uranium chemistry. As such, studies are often limited by the formation of unreactive uranium oxides and/or solubility issues. Carrying out reactions in non-aqueous solvents addresses said problems and enables explorations into previously unattainable reactivity and fundamental properties of uranium. One such feat is the syntheses of uranium alkyls, as they permit research into bond interactions between uranium and carbon. Considering uranium’s oxophilicity, we investigated the relatively understudied uranium(III) alkyls—both their reactivity and reaction mechanism—towards oxygen-containing reagents. In an inert atmosphere, various ...


Controlled Electrochemical Synthesis Of Single One-Dimensional Metal Nanochains Across Microgap Electrodes., Amareshwari Konutham 2017 University of Louisville

Controlled Electrochemical Synthesis Of Single One-Dimensional Metal Nanochains Across Microgap Electrodes., Amareshwari Konutham

Electronic Theses and Dissertations

This study mainly focuses on the fabrication of single one dimensional (1D) NP chains across the 5-micron gap of Au two electrode devices (TED). This has been achieved by electrochemical deposition of Ag onto the two electrodes, soaking the TED in 0.1 M Cetyltrimethyl ammonium bromide for 2-3 hours, and then close monitoring of the current as a function of time while a voltage across the two Ag coated Au electrodes in air. One dimensional Ag nanoparticle chain formation occurred by oxidation of Ag to Ag+ at the positive electrode followed by movement of Ag+ ions to the negative ...


Cadmium Chloride Dimensionality Changes From Ortho-Substituted Anilines, Stephanie Cernicek 2017 University of Missouri-St. Louis

Cadmium Chloride Dimensionality Changes From Ortho-Substituted Anilines, Stephanie Cernicek

Dissertations

Inorganic-organic hybrid metal halide materials have been of great interest recently due to the useful properties offered by such a combination. The inorganic portions usually consisting of MX62- subunits, (M = Pb, Sn, Cd, Cu; X = Cl, Br, I) most often form 2-D perovskite layers where the metals are bridged by corner sharing halides. The organic portion, usually consisting of primary amines or anilines provides a template for the inorganic framework and in some cases, dictates the dimensionality (2-D, 1-D, 0-D) of the network. These materials have various applications in host-guest chemistry catalysis, and gas storage, or as superconductors ...


Magnetic Nanostructure Application In Sers Detection Of Melatonin And Resonance Raman Characterization Of Binding Of Catechol Moieties With Antibiotic, Siqi Sun 2017 University of South Florida

Magnetic Nanostructure Application In Sers Detection Of Melatonin And Resonance Raman Characterization Of Binding Of Catechol Moieties With Antibiotic, Siqi Sun

Graduate Theses and Dissertations

Raman spectroscopy provides characteristic peaks of the target molecules that can be observed with appropriate laser, spectrometer and detector. These characteristic peaks can reveal ‘fingerprint’ information of a molecule even in a myriad of cases and combinations. It makes Raman spectroscopy a highly sensitive and selective analytical technique. Raman spectroscopy has a variety of chemical, environmental and biological applications. In this dissertation, modified Raman method are applied in life sciences and pharmaceutical studies.

The major challenge against development of Raman spectroscopy is how to improve the intensity of Raman signal. Surface Enhance Raman Scattering (SERS) and resonance Raman(RR) are ...


Structure And Activity Of Metallo-Peptides, Christian C. Tang 2017 University of South Florida

Structure And Activity Of Metallo-Peptides, Christian C. Tang

Graduate Theses and Dissertations

Metal ions are ubiquitously found in all living systems and play vital roles in supporting life forms by performing an array of biological activities. Such biological activities include binding and transforming organic molecules, and also acting as active centers and cofactors for catalysis of various acid-base and redox reactions in biological system. The main focus in bioinorganic chemistry is to elucidate the structural and functional roles of metals in biological systems. Among all transition metal ions, Cu2+ and Fe3+ are especially versatile and important due to their abilities to go through redox efficiently.

This dissertation can be divided ...


Superconducting Properties Of Rh 9 In 4 S 4 Single Crystals, Udhara S. Kaluarachchi, Qisheng Lin, Weiwei Xie, Valentin Taufour, S. L. Bud’ko, Gordon J. Miller, Paul C. Canfield 2017 Iowa State University

Superconducting Properties Of Rh 9 In 4 S 4 Single Crystals, Udhara S. Kaluarachchi, Qisheng Lin, Weiwei Xie, Valentin Taufour, S. L. Bud’Ko, Gordon J. Miller, Paul C. Canfield

Paul C. Canfield

The synthesis and crystallographic, thermodynamic, and transport properties of single crystalline Rh9In4S4 were studied. The resistivity, magnetization, and specific heat measurements all clearly indicate bulk superconductivity with a critical temperature, Tc∼2.25 K. The Sommerfeld coefficient γ and the Debye temperature (ΘD) were found to be 34 mJ mol−1 K−2 and 217 K, respectively. The observed specific heat jump, ΔC/γTc=1.66, is larger than the expected BCS weak coupling value of 1.43. Ginzburg-Landau (GL) ratio of the low-temperature GL-penetration depth, λGL≈5750 Å, to the GL-coherence length, ξGL≈94 Å, is large: κ ∼60 ...


Tin Dioxide-Carbon Heterostructures Applied To Gas Sensing: Structure-Dependent Properties And General Sensing Mechanism, Catherine Marichy, Patricia A. Russo, Mariangela Latino, Jean-Philippe Tessonnier, Marc-Georg Wilinger, Nicola Donato, Giovanni Neri, Nicola Pinna 2017 University of Aveiro

Tin Dioxide-Carbon Heterostructures Applied To Gas Sensing: Structure-Dependent Properties And General Sensing Mechanism, Catherine Marichy, Patricia A. Russo, Mariangela Latino, Jean-Philippe Tessonnier, Marc-Georg Wilinger, Nicola Donato, Giovanni Neri, Nicola Pinna

Jean-Philippe Tessonnier

Carbon materials such as carbon nanotubes (CNTs), graphene, and reduced graphene oxide (RGO) exhibit unique electrical properties, which are also influenced by the surrounding atmosphere. They are therefore promising sensing materials. Despite the existence of studies reporting the gas-sensing properties of metal oxide (MOx) coated nanostructured carbon, an incomplete understanding of their sensing mechanism remains. Here we report a systematic study on the preparation, characterization, and sensing properties of CNT and RGO composites with SnO2 coating. Atomic layer deposition (ALD) was applied to the conformal coating of the inner and outer walls of CNTs with thin films of SnO2 of ...


Role Of Co2 As A Soft Oxidant For Dehydrogenation Of Ethylbenzene To Styrene Over A High-Surface-Area Ceria Catalyst, Li Zhang, Zili Wu, Nicholas C. Nelson, Aaron D. Sadow, Igor I. Slowing 2017 Oak Ridge National Laboratory

Role Of Co2 As A Soft Oxidant For Dehydrogenation Of Ethylbenzene To Styrene Over A High-Surface-Area Ceria Catalyst, Li Zhang, Zili Wu, Nicholas C. Nelson, Aaron D. Sadow, Igor I. Slowing

Igor I. Slowing

Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during the ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. The high surface area ceria material was synthesized using a template-assisted method. The interactions among ethylbenzene, styrene, and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ diffuse reflectance infrared and Raman spectroscopy. CO2 as an oxidant not only favored the higher yield of styrene but also inhibited the deposition of coke during the ethylbenzene ODH ...


Silanol-Assisted Carbinolamine Formation In An Amine-Functionalized Mesoporous Silica Surface: Theoretical Investigation By Fragmentation Methods, Ana P. de Lima Batista, Federico Zahariev, Igor I. Slowing, Ataualpa A. C. Braga, Fernando R. Ornellas, Mark S. Gordon 2017 Instituto de Química

Silanol-Assisted Carbinolamine Formation In An Amine-Functionalized Mesoporous Silica Surface: Theoretical Investigation By Fragmentation Methods, Ana P. De Lima Batista, Federico Zahariev, Igor I. Slowing, Ataualpa A. C. Braga, Fernando R. Ornellas, Mark S. Gordon

Igor I. Slowing

The aldol reaction catalyzed by an amine-substituted mesoporous silica nanoparticle (amine-MSN) surface was investigated using a large molecular cluster model (Si392O958C6NH361) combined with the surface integrated molecular orbital/molecular mechanics (SIMOMM) and fragment molecular orbital (FMO) methods. Three distinct pathways for the carbinolamine formation, the first step of the amine-catalyzed aldol reaction, are proposed and investigated in order to elucidate the role of the silanol environment on the catalytic capability of the amine-MSN material. The computational study reveals that the most likely mechanism involves the silanol groups actively participating in the reaction, forming and breaking covalent bonds in the carbinolamine ...


Tuning Complexity By Lithiation: A Family Of Intergrowth Structures Using Condensed Hypho-Icosahedra In The Li-Doped Ca–Zn System, Qisheng Lin, Ran Zhu, Gordon J. Miller 2017 The Ames Laboratory

Tuning Complexity By Lithiation: A Family Of Intergrowth Structures Using Condensed Hypho-Icosahedra In The Li-Doped Ca–Zn System, Qisheng Lin, Ran Zhu, Gordon J. Miller

Gordon Miller

Cluster chemistry of intermetallics with valence electron counts (VECs) in the range of 2.0–3.0 is intriguing. Lithiation of polar intermetallics in this VEC region is found to be an effective chemical route to produce new complex structures with different stability mechanisms. In this work, two new complex intermetallic structures have been discovered in the Ca–Li–Zn system: Ca12LixZn59–xand Ca15LixZn75–x. Ca12LixZn59–x, x ≈ 5.65(3)–14.95(3), forms in the trigonal space group Rm, with a = 9.074(1)–9.1699(2) Å, c ...


Superconducting Properties Of Rh 9 In 4 S 4 Single Crystals, Udhara S. Kaluarachchi, Qisheng Lin, Weiwei Xie, Valentin Taufour, S. L. Bud’ko, Gordon J. Miller, Paul C. Canfield 2017 Iowa State University

Superconducting Properties Of Rh 9 In 4 S 4 Single Crystals, Udhara S. Kaluarachchi, Qisheng Lin, Weiwei Xie, Valentin Taufour, S. L. Bud’Ko, Gordon J. Miller, Paul C. Canfield

Gordon Miller

The synthesis and crystallographic, thermodynamic, and transport properties of single crystalline Rh9In4S4 were studied. The resistivity, magnetization, and specific heat measurements all clearly indicate bulk superconductivity with a critical temperature, Tc∼2.25 K. The Sommerfeld coefficient γ and the Debye temperature (ΘD) were found to be 34 mJ mol−1 K−2 and 217 K, respectively. The observed specific heat jump, ΔC/γTc=1.66, is larger than the expected BCS weak coupling value of 1.43. Ginzburg-Landau (GL) ratio of the low-temperature GL-penetration depth, λGL≈5750 Å, to the GL-coherence length, ξGL≈94 Å, is large: κ ∼60 ...


Comprehensive Silica Removal With Ferric Compounds For Industrial Wastewater Reuse, Ehren D. Baca 2017 University of New Mexico

Comprehensive Silica Removal With Ferric Compounds For Industrial Wastewater Reuse, Ehren D. Baca

Civil Engineering ETDs

Cooling towers, integrated circuit (IC) manufacture and reverse osmosis (RO) generate copious amounts of wastewater high in colloidal and reactive silica inhibiting on-site or synergistic reuse. Silica present in cooling water can reach solubility limits via evaporation and form impervious scale on heat transfer surfaces that decreases efficiency. When water is treated by RO operating at high rejection, silica forms difficult-to-remove scale on the membrane feed side in the form of glassy patches and communities of aggregate particles, inhibiting aspirations for zero liquid discharge. Current methods for silica scale mitigation include abundant dosing with chemical antiscalents or complex operating schemes ...


Evaluation Of A Filtration Sorbent For Remediation Of Arsenic In Groundwater, Clement Do 2017 California State University - San Bernardino

Evaluation Of A Filtration Sorbent For Remediation Of Arsenic In Groundwater, Clement Do

Electronic Theses, Projects, and Dissertations

A commercially available product, PURA PhosLock, was identified and evaluated for use as a sorbent to remove dissolved arsenic (As) from drinking water. Although marketed as a product to remove phosphate in aquaria, it is composed of iron oxide hydroxide (i.e., FeO(OH)), which is also known to adsorb dissolved As species from water. Arsenic was measured using standard methods and Graphite Furnace Atomic Absorption Spectroscopy. A first rough filtration test was performed to see if the PhosLock adsorbed As well. About 50 g of PhosLock was used to filter 10 L of tap water containing 100 ppb As ...


Design And Fabrication Of Nanostructures For The Enhancement Of Photovoltaic Devices, Richard M. Prevost III 2017 University of New Orleans

Design And Fabrication Of Nanostructures For The Enhancement Of Photovoltaic Devices, Richard M. Prevost Iii

University of New Orleans Theses and Dissertations

In 2012 the net world electricity generation was 21.56 trillion kilowatt hours. Photovoltaics only accounted for only 0.1 trillion kilowatt hours, less than 1 % of the total power. Recently there has been a push to convert more energy production to renewable sources. In recent years a great deal of interest has been shown for dye sensitized solar cells. These devices use inexpensive materials and have reported efficiencies approaching 12% in the lab. Here methods have been studied to improve upon these, and other, devices. Different approaches for the addition of gold nanoparticles to TiO2 films were studied ...


Oxidative C-C Bond Formation Reactivity Of High Valent Nickel And Palladium Complexes, Michael Benjamin Watson 2017 Washington University in St. Louis

Oxidative C-C Bond Formation Reactivity Of High Valent Nickel And Palladium Complexes, Michael Benjamin Watson

Arts & Sciences Electronic Theses and Dissertations

The development of both palladium and nickel catalysis over the past several decades has led to the ability to perform a multitude of C-C coupling, C-Heteroatom coupling, and C-H functionalization reactions. These reactions typically utilize a catalytic cycle involving Pd0/II/IV and Ni0/II. While using these types of catalytic cycles one can create a multitude of different hard to make bonds, it is always important to keep expanding what we view as potential catalytic intermediates to keep developing new cycles capable of new transformations. One such way to expand our knowledge of these catalytic cycles is to look ...


Reactions Of Nitric Oxide With Beta-Hydroxylimino Esters, Elayna M. Mahone 2017 University of Wyoming

Reactions Of Nitric Oxide With Beta-Hydroxylimino Esters, Elayna M. Mahone

Honors Theses AY 16/17

Nitric oxide (NO) and its one electron reduction product nitroxyl (HNO) are known to act as vasodilators in mammals, including humans, and are considered a possible cure to cardiovascular diseases. However, their instability and high reactivity with atmospheric oxygen preclude the direct use of them as drugs. Recent work has shown that NO donor molecules can be used as pro-drugs to deliver NO to the appropriate bio-sites. Therefore, there is considerable research interest in the synthesis and studies of donors capable of releasing either of the molecules under physiological conditions.As part of our research effort towards the synthesis of ...


Effects Of Processing Parameters On Properties Of Novel Silica-Filled Polysiloxane Materials, Kyle W. Schwenker 2017 Pittsburg State University

Effects Of Processing Parameters On Properties Of Novel Silica-Filled Polysiloxane Materials, Kyle W. Schwenker

Electronic Thesis Collection

Polysiloxanes are a class of materials that possess high temperature stability and the ability to remain flexible at extremely low temperatures. Their elastomers generally exhibit low strength and have poor mechanical properties unless reinforced with fillers. Reinforcement can be accomplished by compounding reinforcing silica fillers with polysiloxanes via twin-screw extrusion compounding that vigorously mixes the fillers into a polymer matrix. In this thesis, a lab-scale twin-screw extruder was utilized to compound thermoplastic materials to determine the effects of processing on thermoplastics material properties, as well as to determine the extruder’s compounding effectiveness. Processing via lab-scale twin-screw extrusion did not ...


Ion Separations: Achieving Selectivity Through Rational Design In Solvent Extraction And Crystallization Systems, Neil Justin Williams 2017 University of Tennessee, Knoxville

Ion Separations: Achieving Selectivity Through Rational Design In Solvent Extraction And Crystallization Systems, Neil Justin Williams

Doctoral Dissertations

The selective separation of ions from aqueous solutions has been a difficult challenge to address in the separation sciences. The difficulties associated with selective separations of ions are due to a multitude of chemical and physical differences between them. Additionally, the term ions encompass both positively charged cations and their counter parts the negatively charge anions. The work covered in this dissertation discusses the difficulties encountered during the selective separation of both oxoanions and cations. Apart from the Introduction Chapter 1 and Conclusion Chapter 10, the selective separations oxoanions and cations will be discussed separately with the dissertation being divided ...


Synthesis And Characterization Of Novel Single-Site Titanosilicates With Targeted Connectivites And Geometries As Selective Oxidation Catalysts, Lena Elenchin 2017 University of Tennessee, Knoxville

Synthesis And Characterization Of Novel Single-Site Titanosilicates With Targeted Connectivites And Geometries As Selective Oxidation Catalysts, Lena Elenchin

Doctoral Dissertations

The primary focus of this research was to synthesize and characterize two families of titanosilicate catalysts, first generation and second generation, that were single site, atomically dispersed with targeted connectivities to the silicate matrices but had different geometries about the active sites. First generation catalysts have tetrahedral active sites, while second generation catalysts have altered geometries for a more accessible active site, but maintain the same targeted connectivities.

A building block methodology is employed to prepare single site, isolated, atomically dispersed titanium active sites within a silicate matrix. The synthetic approach uses a molecular precursor, i.e., building block and ...


Structural Comparison Of Copper(Ii) Thiocyanate Pyridine Complexes, Joseph V. Handy 2017 College of WIlliam & Mary

Structural Comparison Of Copper(Ii) Thiocyanate Pyridine Complexes, Joseph V. Handy

Undergraduate Honors Theses

Twenty-one novel complexes of copper(II) thiocyanate pyridine were synthesized in methanol from the source material Cu(NO­3)2•2.5H2O and a diverse series of substituted pyridines (XPy). These complexes typically formed according to the formula trans-[Cu(NCS)2(XPy)2], with square-planar geometries that exhibited thiocyanate bridging via long Cu–S bonds. The length of this long bridging bond appears to loosely correlate to the substitution position of the pyridine ligand used, and resulted in square planar molecules forming edge-sharing chain networks of Jahn-Teller distorted octahedra. Several other structural types were also observed, resulting ...


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