The iodine species formed either by adding hypochlorite to a basic iodide solution or by adding triiodide to sodium hydroxide, was identified as hypoiodite ion. The absorption spectrum of IO{sup -} was investigated in the wavelength range from 450 m{micro} to 280 m{micro}. The kinetics of the reaction I{sup -} + ClO{sup -} = IO{sup -} + Cl{sup -} was studied spectrophotometrically in alkaline solution. The forward rate law was found to be d(IO{sup -})/dt = k(I{sup -})(ClO{sup -})/OH{sup -}. At 25 C and an ionic strength of 1.00 M, k is 61 {+-} 3 sec{sup -1}. It was found spectrophotometrically that for certain ratios of the initial iodide to hydroxide concentrations, there was evidence of the presence of I{sub 3}{sup -}, I{sub 2}OH{sup -}, and I{sub 2}O{sup 2-} along with IO{sup -}. The equilibrium constants between IO{sup -} and these three species were evaluated by a graphical method. The formal potential of the cell: Pt:H{sub 2}:1 M NaOH : 1M NaOH, KI, NaIO : Au was found to be 1.297 v at 25 C. The equilibrium constant, K{sub 2} = (I{sub 3}{sup -})(OH{sup -}){sup 2}/(IO{sup -})(I{sup -}){sup 2}, of the reaction IO{sup -} + 2I{sup -} + H{sub 2}O …

Thesis presenting data taken on experimental nuclear magnetic moments for beta spectra of the mirror nuclei with A-19 to 39.

The Standard Model of particle physics, together with the Big Bang model of the early universe, constitute a framework which encompasses our current understanding of fundamental laws and beginning of our universe. Despite recent speculative trends, quantum field theory remains the theoretical tool of choice for investigating new physics either at high energy colliders, or in the early universe. In this dissertation, several field theoretic phenomena relevant to cosmology or particle physics are explored. A common theme in these explorations is the structure of the vacuum state in quantum field theory. First, we discuss first-order phase transitions in the early universe, in which the effective vacuum state of the universe shifts discontinuously as the temperature drops below some critical point. We find that the dynamics of a certain type of first-order phase transition can lead to production of primordial black holes, which could constitute the dark matter of our universe. Alternatively, supercooled first-order phase transitions may be the cause of an extended inflationary epoch in the early universe, which is generally regarded as necessary to solve several cosmological puzzles. We derive limits on such scenarios based on nearly model-independent percolation properties of the transition. We also study some nonperturbative aspects …

Mesoporous silica nanoparticles (MSNs) have attracted great interest for last two decades due to their unique and advantageous structural properties, such as high surface area, pore volume, stable mesostructure, tunable pore size and controllable particle morphology. The robust silica framework provides sites for organic modifications, making MSNs ideal platforms for adsorbents and supported organocatalysts. In addition, the pores of MSNs provide cavities/ channels for incorporation of metal and metal oxide nanoparticle catalysts. These supported metal nanoparticle catalysts benefit from confined local environments to enhance their activity and selectivity for various reactions. Biomass is considered as a sustainable feedstock with potential to replace diminishing fossil fuels for the production of biofuels. Among several strategies, one of the promising methods of biofuel production from biomass is to reduce the oxygen content of the feedstock in order to improve the energy density. This can be achieved by creating C-C bonds between biomass derived intermediates to increase the molecular weight of the final hydrocarbon molecules. In this context, pore size and organic functionality of MSNs are varied to obtain the ideal catalyst for a C-C bond forming reaction: the aldol condensation. The mechanistic aspects of this reaction in supported heterogeneous catalysts are explored. The …

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Signal transduction pathways are usually activated by external stimuli and are transient. The downstream changes such as transcription of the activated genes are also transient. Real-time detection of promoter activity is useful for understanding changes in gene expression, especially during cell differentiation and in development. A simple and reliable method for viewing gene expression in real time is not yet available. Reporter proteins such as fluorescent proteins and luciferase allow for non-invasive detection of the products of gene expression in living cells. However, current reporter systems do not provide for real-time imaging of promoter activity in living cells. This is because of the long time period after transcription required for fluorescent protein synthesis and maturation. We have developed an RNA reporter system for imaging in real-time to detect changes in promoter activity as they occur. The RNA reporter uses strings of RNA aptamers that constitute IMAGEtags (Intracellular MultiAptamer GEnetic tags), which can be expressed from a promoter of choice. The tobramycin, neomycin and PDC RNA aptamers have been utilized for this system and expressed in yeast from the GAL1 promoter. The IMAGEtag RNA kinetics were quantified by RT-qPCR. In yeast precultured in raffinose containing media the GAL1 promoter responded faster …

GdNi is a rare earth intermetallic material that exhibits very interesting magnetic properties. Spontaneous magnetostriction occurs in GdNi at T{sub C}, on the order of 8000ppm strain along the c-axis and only until very recently the mechanism causing this giant magnetostriction was not understood. In order to learn more about the electronic and magnetic structure of GdNi, single crystals are required for anisotropic magnetic property measurements. Single crystal processing is quite challenging for GdNi though since the rare-earth transition-metal composition yields a very reactive intermetallic compound. Many crystal growth methods are pursued in this study including crucible free methods, precipitation growths, and specially developed Bridgman crucibles. A plasma-sprayed Gd{sub 2}O{sub 3} W-backed Bridgman crucible was found to be the best means of GdNi single crystal processing. With a source of high-quality single crystals, many magnetization measurements were collected to reveal the magnetic structure of GdNi. Heat capacity and the magnetocaloric effect are also measured on a single crystal sample. The result is a thorough report on high quality single crystal processing and the magnetic properties of GdNi.

A study of B-meson decays to final states with a single charm baryon is presented based on data recorded by the BABAR detector at the Stanford Linear Accelerator Center. Although the B meson is the lightest bottom-flavored meson, it is heavy enough to decay to a baryon made of three quarks and an antibaryon made of three antiquarks. By studying the baryonic weak decays of the B meson, we can investigate baryon production mechanisms in heavy meson decays. In particular, we measure the rates of the decays B{sup -} {yields} {Lambda}{sub c}{sup +}{bar p}{pi}{sup -} and {bar B}{sup 0} {yields} {Lambda}{sub c}{sup +}{bar p}. Comparing these rates, we confirm an observed trend in baryonic B decays that the decay with the lower energy release, B{sup -} {yields} {Lambda}{sub c}{sup +}{bar p}{pi}{sup -}, is favored over {bar B}{sup 0} {yields} {Lambda}{sub c}{sup +}{bar p}. The dynamics of the baryon-antibaryon ({Lambda}{sub c}{sup +}{bar p}) system in the three-body decay also provide insight into baryon-antibaryon production mechanisms. The B{sup -} {yields} {Lambda}{sub c}{sup +}{bar p}{pi}{sup -} system is a laboratory for searches for excited {Sigma}{sub c} baryon states; we observe the resonant decays B{sup -} {yields} {Sigma}{sub c}(2455){sup 0}{bar p} and B{sup -} …

This dissertation presents the development of the novel mechanical testing technique of in situ nanoindentation in a transmission electron microscope (TEM). This technique makes it possible to simultaneously observe and quantify the mechanical behavior of nano-scale volumes of solids.

A series of organometallic compounds containing the tris(dimethylsilyl)methyl ligand are described. The potassium carbanions KC(SiHMe{sub 2}){sub 3} and KC(SiHMe{sub 2}){sub 3}TMEDA are synthesized by deprotonation of the hydrocarbon HC(SiHMe{sub 2}){sub 3} with potassium benzyl. KC(SiHMe{sub 2}){sub 3}TMEDA crystallizes as a dimer with two types of three-center-two-electron KH- Si interactions. Homoleptic Ln(III) tris(silylalkyl) complexes containing β-SiH groups M{C(SiHMe{sub 2}){sub 3}}{sub 3} (Ln = Y, Lu, La) are synthesized from salt elimination of the corresponding lanthanide halide and 3 equiv. of KC(SiHMe{sub 2}){sub 3}. The related reactions with Sc yield bis(silylalkyl) ate-complexes containing either LiCl or KCl. The divalent calcium and ytterbium compounds M{C(SiHMe{sub 2}){sub 3}}{sub 2}L (M = Ca, Yb; L = THF{sub 2} or TMEDA) are prepared from MI{sub 2} and 2 equiv of KC(SiHMe{sub 2}){sub 3}. The compounds M{C(SiHMe{sub 2}){sub 3}}{sub 2}L (M = Ca, Yb; L = THF{sub 2} or TMEDA) and La{C(SiHMe{sub 2}){sub 3}}{sub 3} react with 1 equiv of B(C{sub 6}F{sub 5}){sub 3} to give 1,3- disilacyclobutane {Me2Si-C(SiHMe2)2}2 and MC(SiHMe2)3HB(C6F5)3L, and La{C(SiHMe{sub 2}){sub 3}}{sub 2}HB(C{sub 6}F{sub 5}){sub 3}, respectively. The corresponding reactions of Ln{C(SiHMe{sub 2}){sub 3}}{sub 3} (Ln = Y, Lu) give the β-SiH abstraction product [{(Me{sub 2}HSi){sub 3}C}{sub 2}LnC(SiHMe{sub 2}){sub 2}SiMe{sub 2}][HB(C{sub 6}F{sub 5}){sub 3}] …

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Polyethylene is one of the most widely used plastics, and over 60 million tons are produced worldwide every year. Polyethylene is obtained by the catalytic polymerization of ethylene in gas and liquid phase reactors. The gas phase processes are more advantageous, and use fluidized-bed reactors for production of polyethylene. Since they operate so close to the melting point of the polymer, agglomeration is an operational concern in all slurry and gas polymerization processes. Electrostatics and hot spot formation are the main factors that contribute to agglomeration in gas-phase processes. Electrostatic charges in gas phase polymerization fluidized bed reactors are known to influence the bed hydrodynamics, particle elutriation, bubble size, bubble shape etc. Accumulation of electrostatic charges in the fluidized-bed can lead to operational issues. In this work a first-principles electrostatic model is developed and coupled with a multi-fluid computational fluid dynamic (CFD) model to understand the effect of electrostatics on the dynamics of a fluidized-bed. The multi-fluid CFD model for gas-particle flow is based on the kinetic theory of granular flows closures. The electrostatic model is developed based on a fixed, size-dependent charge for each type of particle (catalyst, polymer, polymer fines) phase. The combined CFD model is first verified …

Carbonyl and nitrile addition to uranyl (UO{sup 2}{sup 2+}) are studied. The competition between nitrile and water ligands in the formation of uranyl complexes is investigated. The possibility of hypercoordinated uranyl with acetone ligands is examined. Uranyl is studied with diactone alcohol ligands as a means to explain the apparent hypercoordinated uranyl. A discussion of the formation of mesityl oxide ligands is also included. A joint theory/experimental study of reactions of zwitterionic boratoiridium(I) complexes with oxazoline-based scorpionate ligands is reported. A computational study was done of the catalytic hydroamination/cyclization of aminoalkenes with zirconium-based catalysts. Techniques are surveyed for programming for graphical processing units (GPUs) using Fortran.

The stable boundary layer (SBL) in the atmosphere is of considerable interest because it is often the worse case scenario for air pollution studies and health effect assessments associated with the accidental release of toxic material. Traditional modeling approaches used in such studies do not simulate the non-steady character of the velocity field, and hence often overpredict concentrations while underpredicting spatial coverage of potentially harmful concentrations of airborne material. The challenge for LES is to be able to resolve the rather small energy-containing eddies of the SBL while still maintaining an adequate domain size. This requires that the subgrid-scale (SGS) parameterization of turbulence incorporate an adequate representation of turbulent energy transfer. Recent studies have shown that both upscale and downscale energy transfer can occur simultaneously, but that overall the net transfer is downscale. Including the upscale transfer of turbulent energy (energy backscatter) is particularly important near the ground and under stably-stratified conditions. The goal of this research is to improve the ability to realistically simulate the SBL. The large-eddy simulation (LES) approach with its subgrid-scale (SGS) turbulence model does a better job of capturing the temporally and spatially varying features of the SBL than do Reynolds-averaging models. The scientific objectives …

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This thesis showed that it is possible to achieve well ordered growth at low temperatures when chaing fluxes during the course of the deposition. It was also demonstrated that nucleation theory fails to predict or explain at least part of the results, in particular when deposition takes place at an initially low rate, with presumably a relatively low nucleation density, followed by a change to a high flux rate. This points to an inherent lack of nucleation theory; alternative explanations are presented based on flux-independent growth as reported by Roos (Surf. Sci. 302 (1994) 37).

Capillary zone electrophoresis (CZE), a powerful separation method based on the differential migration of charged species under the influence of an electric field, has been widely used for separations covering from small ions to big biomolecules. Chapter 1 describes the method, then discusses detection of the separated analytes by laser induced fluorescence and by chemical derivatization, and the use of O-phthaldialdehyde (OPA) as a post-column reagent. Chapter 2 describes a post-column reactor which uses two narrow bore capillaries connected coaxially. This reactor differs from other coaxial reactors in terms of capillary dimensions, reagent flow control, ease of construction and most importantly, better limits of detection. The derivatization reagent is electroosmotically driven into the reaction capillary and the reagent flow rate is independently controlled by a high voltage power supply. Amino acids, amines and proteins, derivatized by OPA/2-mercaptoethanol using this post-column reactor coupled with LIF detection, show low attomole mass limits of detection, and for the first time, the authors demonstrate single cell capability with a post-column derivatization scheme. The single cell capability shows that this reactor could find applications in assaying non-fluorescent or electrochemically inactive components in individual biological cells in the future.

In the first part of the thesis, the electric resistivity, Seebeck coefficient, and Hall effect were measured in X{sub y}(Y{sub 2}S{sub 3}){sub 1-y} (X = Cu, B, or Al), for y = 0.05 (Cu, B) or 0.025-0.075 for Al, in order to determine their potential as high- temperature (HT)(300-1000 C) thermoelectrics. Results indicate that Cu, B, Al- doped Y{sub 2}S{sub 3} are not useful as HT thermoelectrics. In the second part, phase stability of {gamma}-cubic LaSe{sub 1.47-1.48} and NdSe{sub 1.47} was measured periodically during annealing at 800 or 1000 C for the same purpose. In the Nd selenide, {beta} phase increased with time, while the Nd selenide showed no sign of this second phase. It is concluded that the La selenide is not promising for use as HT thermoelectric due to the {gamma}-to-{beta} transformation, whereas the Nd selenide is promising.

Fermilab Experiment 769 used a charge-selected, hadron beam of mean energy 250 GeV/c, composed of pions, kaons, and protons, impinging on beryllium, aluminum, copper and tungsten targets. Using a sample of approximately 4000 {Xi}{sub s}{sup {minus}} {yields} {Lambda}{sup 0}{pi}{sup {minus}} decays, measurements of the charm baryon forward cross sections times branching ratio {pi}{sup {+-}}N {yields} {Xi}{sub c}{sup +}X and {pi}{sup {+-}}N {yields} {Xi}{sub c}{sup 0}X are presented. Upper limits on {alpha} x BR are also determined for the states {Xi}{sub c}{sup +} {yields} {Xi}{sub s}{sup {minus}}{pi}{sup +}{pi}{sup +} and {Xi}{sub c}{sup 0} {yields} {Xi}{sub s}{sup {minus}}{pi}{sup +} produced in (p, {pi}{sup +}, {pi}{sup {minus}}, K{sup +}, K{sup {minus}})-nucleon interactions.

Research into laser-driven inertial confinement fusion is now entering a critical juncture with the construction of the National Ignition Facility (NIF) at Lawrence Livermore National Laboratory (LLNL). Many of the remaining unanswered questions concerning NIF involve interactions between lasers and plasmas. With the eventual goal of fusion power in mind, laser-plasma interactions relevant to laser fusion schemes is an important topic in need of further research. This work experimentally addresses some potential shortcuts and pitfalls on the road to laser-driven fusion power. Current plans on NIF have 192 laser beams directed into a small cylindrical cavity which will contain the fusion fuel; to accomplish this the beams must cross in the entrance holes, and this intersection will be in the presence of outward-flowing plasma. To investigate the physics involved, interactions of crossing laser beams in flowing plasmas are investigated with experiments on the Nova laser facility at LLNL. It was found that in a flowing plasma, energy is transferred between two crossing laser beams, and this may have deleterious consequences for energy balance and ignition in NIF. Possible solutions to this problem are presented. A recently-proposed alternative to standard laser-driven fusion, the ''fast ignitor'' concept, is also experimentally addressed in …