The ability to finely tune the size and shape of inorganic semiconducting nanocrystals is an area of great interest, as the more control one has, the more applications will be possible for their use. The first two basic shapes develped in nanocrystals were the sphere and the anistropic nanorod. the II_VI materials being used such as Cadmium Selenide (CdSe) and Cadmium Telluride (CdTe), exhibit polytypism, which allows them to form in either the hexagonally packed wurtzite or cubically packed zinc blende crystalline phase. The nanorods are wurtzite with the length of the rod growing along the c-axis. As this grows, stacking faults may form, which are layers of zinc blende in the otherwise wurtzite crystal. Using this polytypism, though, the first generation of branched crystals were developed in the form of the CdTe tetrapod. This is a nanocrystal that nucleates in the zincblend form, creating a tetrahedral core, on which four wurtzite arms are grown. This structure opened up the possibility of even more complex shapes and applications. This disseration investigates the advancement of branching control and further understanding the materials polytypism in the form of the stacking faults in nanorods.

Catalytic reactions of cyclohexene, benzene, n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene on platinum catalysts were monitored in situ via sum frequency generation (SFG) vibrational spectroscopy and gas chromatography (GC). SFG is a surface specific vibrational spectroscopic tool capable of monitoring submonolayer coverages under reaction conditions without gas-phase interference. SFG was used to identify the surface intermediates present during catalytic processes on Pt(111) and Pt(100) single-crystals and on cubic and cuboctahedra Pt nanoparticles in the Torr pressure regime and at high temperatures (300K-450K). At low pressures (<10{sup -6} Torr), cyclohexene hydrogenated and dehydrogenates to form cyclohexyl (C{sub 6}H{sub 11}) and {pi}-allyl C{sub 6}H{sub 9}, respectively, on Pt(100). Increasing pressures to 1.5 Torr form cyclohexyl, {pi}-allyl C{sub 6}H{sub 9}, and 1,4-cyclohexadiene, illustrating the necessity to investigate catalytic reactions at high-pressures. Simultaneously, GC was used to acquire turnover rates that were correlated to reactive intermediates observed spectroscopically. Benzene hydrogenation on Pt(111) and Pt(100) illustrated structure sensitivity via both vibrational spectroscopy and kinetics. Both cyclohexane and cyclohexene were produced on Pt(111), while only cyclohexane was formed on Pt(100). Additionally, {pi}-allyl c-C{sub 6}H{sub 9} was found only on Pt(100), indicating that cyclohexene rapidly dehydrogenates on the (100) surface. The structure insensitive production of cyclohexane was found …

Sum frequency generation (SFG) vibrational spectroscopy has been used to study the interfacial structure of several polypeptides and amino acids adsorbed to hydrophobic and hydrophilic surfaces under a variety of experimental conditions. Peptide sequence, peptide chain length, peptide hydrophobicity, peptide side-chain type, surface hydrophobicity, and solution ionic strength all affect an adsorbed peptide's interfacial structure. Herein, it is demonstrated that with the choice of simple, model peptides and amino acids, surface specific SFG vibrational spectroscopy can be a powerful tool to elucidate the interfacial structure of these adsorbates. Herein, four experiments are described. In one, a series of isosequential amphiphilic peptides are synthesized and studied when adsorbed to both hydrophobic and hydrophilic surfaces. On hydrophobic surfaces of deuterated polystyrene, it was determined that the hydrophobic part of the peptide is ordered at the solid-liquid interface, while the hydrophilic part of the peptide appears to have a random orientation at this interface. On a hydrophilic surface of silica, it was determined that an ordered peptide was only observed if a peptide had stable secondary structure in solution. In another experiment, the interfacial structure of a model amphiphilic peptide was studied as a function of the ionic strength of the solution, a …

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The ability of Solid Oxide Fuel Cells (SOFC) to directly and efficiently convert the chemical energy in hydrocarbon fuels to electricity places the technology in a unique and exciting position to play a significant role in the clean energy revolution. In order to make SOFC technology cost competitive with existing technologies, the operating temperatures have been decreased to the range where costly ceramic components may be substituted with inexpensive metal components within the cell and stack design. However, a number of issues have arisen due to this decrease in temperature: decreased electrolyte ionic conductivity, cathode reaction rate limitations, and a decrease in anode contaminant tolerance. While the decrease in electrolyte ionic conductivities has been countered by decreasing the electrolyte thickness, the electrode limitations have remained a more difficult problem. Nanostructuring SOFC electrodes addresses the major electrode issues. The infiltration method used in this dissertation to produce nanostructure SOFC electrodes creates a connected network of nanoparticles; since the method allows for the incorporation of the nanoparticles after electrode backbone formation, previously incompatible advanced electrocatalysts can be infiltrated providing electronic conductivity and electrocatalysis within well-formed electrolyte backbones. Furthermore, the method is used to significantly enhance the conventional electrode design by adding secondary …

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This dissertation documents the development of a broadband electron spectrometer (ESM) for GeV class Laser Wakefield Accelerators (LWFA), the production of high quality GeV electron beams (e-beams) for the first time in a LWFA by using a capillary discharge guide (CDG), and a statistical analysis of CDG-LWFAs. An ESM specialized for CDG-LWFAs with an unprecedented wide momentum acceptance, from 0.01 to 1.1 GeV in a single shot, has been developed. Simultaneous measurement of e-beam spectra and output laser properties as well as a large angular acceptance (> {+-} 10 mrad) were realized by employing a slitless scheme. A scintillating screen (LANEX Fast back, LANEX-FB)--camera system allowed faster than 1 Hz operation and evaluation of the spatial properties of e-beams. The design provided sufficient resolution for the whole range of the ESM (below 5% for beams with 2 mrad divergence). The calibration between light yield from LANEX-FB and total charge, and a study on the electron energy dependence (0.071 to 1.23 GeV) of LANEX-FB were performed at the Advanced light source (ALS), Lawrence Berkeley National Laboratory (LBNL). Using this calibration data, the developed ESM provided a charge measurement as well. The production of high quality electron beams up to 1 GeV …

Macromolecular interactions are essential for virtually all cellular functions including signal transduction processes, metabolic processes, regulation of gene expression and immune responses. This dissertation focuses on the characterization of two important macromolecular interactions involved in the relationship between Equine Infectious Anemia Virus (EIAV) and its host cell in horse: (1) the interaction between the EIAV Rev protein and its binding site, the Rev-responsive element (RRE) and (2) interactions between equine MHC class I molecules and epitope peptides derived from EIAV proteins. EIAV, one of the most divergent members of the lentivirus family, has a single-stranded RNA genome and carries several regulatory and structural proteins within its viral particle. Rev is an essential EIAV regulatory encoded protein that interacts with the viral RRE, a specific binding site in the viral mRNA. Using a combination of experimental and computational methods, the interactions between EIAV Rev and RRE were characterized in detail. EIAV Rev was shown to have a bipartite RNA binding domain contain two arginine rich motifs (ARMs). The RRE secondary structure was determined and specific structural motifs that act as cis-regulatory elements for EIAV Rev-RRE interaction were identified. Interestingly, a structural motif located in the high affinity Rev binding site is …

It is now widely accepted that the Standard Model assumption of massless neutrinos is wrong, due primarily to the observation of solar and atmospheric neutrino flavor oscillations by a small number of convincing experiments. The MINOS Far Detector, capable of observing both the outgoing lepton and associated showering products of a neutrino interaction, provides an excellent opportunity to independently search for an oscillation signature in atmospheric neutrinos. To this end, a MINOS data set from an 883 live day, 13.1 kt-yr exposure collected between July, 2003 and April, 2007 has been analyzed. 105 candidate charged current muon neutrino interactions were observed, with 120.5 {+-} 1.3 (statistical error only) expected in the absence of oscillation. A maximum likelihood analysis of the observed log(L/E) spectrum shows that the null oscillation hypothesis is excluded at over 96% confidence and that the best fit oscillation parameters are sin{sup 2} 2{theta}{sub 23} = 0.95{sub -0.32} and {Delta}m{sub 23}{sup 2} = 0.93{sub -0.44}{sup +3.94} x 10{sup -3} eV{sup 2}. This measurement of oscillation parameters is consistent with the best fit values from the Super-Kamiokande experiment at 68% confidence.

The sudden release of toxic contaminants that reach indoor spaces can be hazardousto building occupants. To respond effectively, the contaminant release must be quicklydetected and characterized to determine unobserved parameters, such as release locationand strength. Characterizing the release requires solving an inverse problem. Designinga robust real-time sensor system that solves the inverse problem is challenging becausethe fate and transport of contaminants is complex, sensor information is limited andimperfect, and real-time estimation is computationally constrained.This dissertation uses a system-level approach, based on a Bayes Monte Carloframework, to develop sensor-system design concepts and methods. I describe threeinvestigations that explore complex relationships among sensors, network architecture,interpretation algorithms, and system performance. The investigations use data obtainedfrom tracer gas experiments conducted in a real building. The influence of individual sensor characteristics on the sensor-system performance for binary-type contaminant sensors is analyzed. Performance tradeoffs among sensor accuracy, threshold level and response time are identified; these attributes could not be inferred without a system-level analysis. For example, more accurate but slower sensors are found to outperform less accurate but faster sensors. Secondly, I investigate how the sensor-system performance can be understood in terms of contaminant transport processes and the model representation that is used to solve the …

Determining the composition of thin layers is increasingly important for a variety of industrial materials such as adhesives, coatings and microelectronics. Secondary ion mass spectrometry (SIMS), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), glow discharge optical emission spectroscopy (GDOES), glow discharge mass spectrometry (GDMS), and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) are some of the techniques that are currently employed for the direct analysis of the sample surface. Although these techniques do not suffer from the contamination problems that often plague sample dissolution studies, they do require matrix matched standards for quantification. Often, these standards are not readily available. Despite the costs of clean hoods, Teflon pipette tips and bottles, and pure acids, partial sample dissolution is the primary method used in the semiconductor industry to quantify surface impurities. Specifically, vapor phase decomposition (VPD) coupled to ICP-MS or total reflection x-ray fluorescence (TXRF) provides elemental information from the top most surface layers at detection sensitivities in the 10{sup 7}-10{sup 10}atoms/cm{sup 2} range. The ability to quantify with standard solutions is a main advantage of these techniques. Li and Houk applied a VPD-like technique to steel. The signal ratio of trace element to matrix element was used for quantification. Although …

The main focus of this dissertation is the design, development, and ground and microgravity validation of methods for monitoring drinking water quality on-board NASA spacecraft using clorimetric-solid phase extraction (C-SPE). The Introduction will overview the need for in-flight water quality analysis and will detail some of the challenges associated with operations in the absence of gravity. The ability of C-SPE methods to meet these challenges will then be discussed, followed by a literature review on existing applications of C-SPE and similar techniques. Finally, a brief discussion of diffuse reflectance spectroscopy theory, which provides a means for analyte identification and quantification in C-SPE analyses, is presented. Following the Introduction, four research chapters are presented as separate manuscripts. Chapter 1 reports the results from microgravity testing of existing C-SPE methods and procedures aboard NASA's C-9 microgravity simulator. Chapter 2 discusses the development of a C-SPE method for determining the total concentration of biocidal silver (i.e., in both dissolved and colloidal forms) in water samples. Chapter 3 presents the first application of the C-SPE technique to the determination of an organic analyte (i.e., formaldehyde). Chapter 4, which is a departure from the main focus of the thesis, details the results of an investigation …

The work presented herein describes a fundamental investigations of carbon as electrode material by using the pyrolysis of photoresist to create an optically transparent material. The development of these carbon-based optically transparent electrodes (C-OTEs) enables investigations of molecular interactions within the electrical double layer, processes that are central to a wide range of important phenomena, including the impact of changes in the surface charge density on adsorption. The electrochemical importance of carbon cannot be understated, having relevance to separations and detection by providing a wide potential window and low background current in addition to being low cost and light weight. The interactions that govern the processes at the carbon electrode surface has been studied extensively. A variety of publications from the laboratories of McCreery and Kinoshita provide in depth summaries about carbon and its many applications in electrochemistry. These studies reveal that defects, impurities, oxidation, and a variety of functional groups create adsorption sites on carbon surfaces with different characteristics. The interest in C-OTEs was sparked by the desire to study and understand the behavior of individual molecules at electrified interfaces. It draws on the earlier development of Electrochemically Modulated Liquid Chromatography (EMLC), which uses carbon as the stationary phase. …

Ultra-sensitive native fluorescence detection of proteins with miniaturized one- and two-dimensional polyacrylamide gel electrophoresis was achieved with laser side-entry excitation, which provides both high excitation power and low background level. The detection limit for R-phycoerythrin protein spots in 1-D SDS-PAGE was as low as 15 fg, which corresponds to 40 thousand molecules only. The average detection limit of six standard native proteins was 5 pg per band and the dynamic range spanned more than 3 orders of magnitude. Approximately 150 protein spots from 30 ng of total Escherichia coli extraction were detected on a 0.8 cm x 1 cm gel in two-dimensional separation. Estrogen-DNA adducts as 4-OHE{sub 1}(E{sub 2})-1-N3Ade and 4-OHEI(E2)-2-NacCys were hypothesized as early risk assessment of prostate and breast cancers. Capillary electrophoresis, luminescence/absorption spectroscopy and LC-MS were used to characterize and detect these adducts. Monoclonal antibodies against each individual adduct were developed and used to enrich such compounds from urine samples of prostate and breast cancer patients as well as healthy people. Adduct 4-OHE{sub 1}-1-N3Ade was detected at much higher level in urine from subjects with prostate cancer patients compared to healthy males. The same adduct and 4-OHEI-2-NacCys were also detected at a much higher level in urine …

This dissertation focused on using electrospray ionization mass spectrometry to study cluster ions and toxic metal ions in biology. In Chapter 2, it was shown that primary, secondary and quarternary amines exhibit different clustering characteristics under identical instrument conditions. Carbon chain length also played a role in cluster ion formation. In Chapters 3 and 4, the effects of solvent types/ratios and various instrumental parameters on cluster ion formation were examined. It was found that instrument interface design also plays a critical role in the cluster ion distribution seen in the mass spectrum. In Chapter 5, ESI-MS was used to investigate toxic metal binding to the [Gln{sup 11}]-amyloid {beta}-protein fragment (1-16). Pb and Cd bound stronger than Zn, even in the presence of excess Zn. Hg bound weaker than Zn. There are endless options for future work on cluster ions. Any molecule that is poorly ionized in positive ion mode can potentially show an increase in ionization efficiency if an appropriate anion is used to produce a net negative charge. It is possible that drug protein or drug/DNA complexes can also be stabilized by adding counter-ions. This would preserve the solution characteristics of the complex in the gas phase. Once in …

In a data sample of approximately 1.3 fb{sup -1} collected with the D0 detector between 2002 and 2006, the orbitally excited charm state D{sub s1}{sup {+-}}(2536)has been observed with a measured mass of 2535.7 {+-} 0.6(stat) {+-} 0.5(syst) MeV/c{sup 2} via the decay mode B{sub s}{sup 0} {yields} D{sub s1}{sup -}(2536){mu}{sup +}{nu}X followed by D{sub s1}{sup {+-}}(2536) {yields} D*{sup {+-}}K{sub S}{sup 0}. By normalizing to the known branching ratio Br({bar b} {yields} D*{sup -} {mu}{sup +}{nu}X) and to the number of reconstructed D* mesons with an associated identified muon, a first-ever measurement is made of the product branching ratio ({bar b} {yields} D{sub s1}{sup -}(2536){mu}{sup +}{nu}X) {center_dot} Br(D{sub s1}{sup -} {yields} D*{sup -}K{sub S}{sup 0}). Assuming that D{sub s1}{sup -}(2536) production in semileptonic decay is entirely from B{sub s}{sup 0}, an extraction of the semileptonic branching ratio Br(B{sub s}{sup 0} {yields} D{sub s1}{sup -}(2536){mu}{sup +}{nu}X) is made. Comparisons are made with theoretical expectations.

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Materials for high-pressure turbine blades must be able to operate in the high-temperature gases (above 1000 C) emerging from the combustion chamber. Accordingly, the development of nickel-based superalloys has been constantly motivated by the need to have improved engine efficiency, reliability and service lifetime under the harsh conditions imposed by the turbine environment. However, the melting point of nickel (1455 C) provides a natural ceiling for the temperature capability of nickel-based superalloys. Thus, surface-engineered turbine components with modified diffusion coatings and overlay coatings are used. Theses coatings are capable of forming a compact and adherent oxide scale, which greatly impedes the further transport of reactants between the high-temperature gases and the underlying metal and thus reducing attack by the atmosphere. Typically, these coatings contain {beta}-NiAl as a principal constituent phase in order to have sufficient aluminum content to form an Al{sub 2}O{sub 3} scale at elevated temperatures. The drawbacks to the currently-used {beta}-based coatings, such as phase instabilities, associated stresses induced by such phase instabilities, and extensive coating/substrate interdiffusion, are major motivations in this study to seek next-generation coatings. The high-temperature oxidation resistance of novel Pt + Hf-modified {gamma}-Ni + {gamma}-Ni{sub 3}Al-based alloys and coatings were investigated in this study. …

High-throughput screening (HTS) techniques have been applied to many research fields nowadays. Robot microarray printing technique and automation microtiter handling technique allows HTS performing in both heterogeneous and homogeneous formats, with minimal sample required for each assay element. In this dissertation, new HTS techniques for enzyme activity analysis were developed. First, patterns of immobilized enzyme on nylon screen were detected by multiplexed capillary system. The imaging resolution is limited by the outer diameter of the capillaries. In order to get finer images, capillaries with smaller outer diameters can be used to form the imaging probe. Application of capillary electrophoresis allows separation of the product from the substrate in the reaction mixture, so that the product doesn't have to have different optical properties with the substrate. UV absorption detection allows almost universal detection for organic molecules. Thus, no modifications of either the substrate or the product molecules are necessary. This technique has the potential to be used in screening of local distribution variations of specific bio-molecules in a tissue or in screening of multiple immobilized catalysts. Another high-throughput screening technique is developed by directly monitoring the light intensity of the immobilized-catalyst surface using a scientific charge-coupled device (CCD). Briefly, the surface …

The search for new super-hard materials has usually focused on strongly bonded, highly symmetric crystal structures similar to diamond. The two hardest single-phase materials, diamond and cubic boron nitride (cBN), are metastable, and both must be produced at high temperatures and pressures, which makes their production costly. In 2000, a superhard composite based on a low-symmetry, boron-rich compound was reported. Since then, many advances have been made in the study of this AlMgB{sub 14}-TiB{sub 2} composite. The composite has been shown to exhibit hardness greater than either of its constituent phases, relying on its sub-micron microstructure to provide hardening and strengthening mechanisms. With possible hardness around 40 GPa, an AlMgB{sub 14} - 60 vol% TiB{sub 2} approaches the hardness of cBN, yet is amenable to processing under ambient pressure conditions. There are interesting aspects of both the AlMgB{sub 14} and TiB{sub 2} phases. AlMgB{sub 14} is comprised of a framework of boron, mostly in icosahedral arrangements. It is part of a family of 12 known compounds with the same boron lattice, with the metal atoms replaced by Li, Na, Y or a number of Lanthanides. Another peculiar trait of this family of compounds is that every one contains a certain …

Transition metal silicides are being considered for future engine turbine components at temperatures up to 1600 C. Although significant improvement in high temperature strength, room temperature fracture toughness has been realized in the past decade, further improvement in oxidation resistance is needed. Oxidation mechanism of Ti{sub 5}Si{sub 3}-based alloys was investigated. Oxidation behavior of Ti{sub 5}Si{sub 3}-based alloy strongly depends on the atmosphere. Presence of Nitrogen alters the oxidation behavior of Ti{sub 5}Si{sub 3} by nucleation and growth of nitride subscale. Ti{sub 5}Si{sub 3.2} and Ti{sub 5}Si{sub 3}C{sub 0.5} alloys exhibited an excellent oxidation resistance in nitrogen bearing atmosphere due to limited dissolution of nitrogen and increased Si/Ti activity ratio. MoSi{sub 2} coating developed by pack cementation to protect Mo-based Mo-Si-B composites was found to be effective up to 1500 C. Shifting coating composition to T1+T2+Mo{sub 3}Si region showed the possibility to extend the coating lifetime above 1500 C by more than ten times via formation of slow growing Mo{sub 3}Si or T2 interlayer without sacrificing the oxidation resistance of the coating. The phase equilibria in the Nb-rich portion of Nb-B system has been evaluated experimentally using metallographic analysis and differential thermal analyzer (DTA). It was shown that Nb{sub ss} …

The authors measure the asymmetry between positive and negative same-sign muon pairs originating from semileptonic decays of pairs of B hadrons. Low transverse momentum dimuon pairs are evaluated to determine B hadron content using a log likelihood fit to two-dimensional impact parameter significance templates. Corrections are made for asymmetries arising from the detector, trigger, and hadrons which are reconstructed as muons. Using 1.1 million muon pairs from data corresponding to an integrated luminosity of 1.6 fb{sup -1}, they find 210,000 same-sign muon pairs with both muon candidates coming from B decays. After corrections, they measure a semileptonic asymmetry from neutral B mixing of A{sub SL} = 0.0080 {+-} 0.0090(stat) {+-} 0.0068(syst). This asymmetry can be interpreted as a constraint on the complex phase of the CKM matrix element V{sub ts} by using the B{sup 0} neutral mixing contribution measured at the B factories. They measure the CP violating asymmetry from B{sub s} mixing to be A{sub SL}{sup s} = 0.020 {+-} 0.028.

A measurement of the top quark mass in t{bar t} {yields} l + jets candidate events, obtained from p{bar p} collisions at {radical}s = 1.96 TeV at the Fermilab Tevatron using the CDF II detector, is presented. The measurement approach is that of a matrix element method. For each candidate event, a two dimensional likelihood is calculated in the top pole mass and a constant scale factor, 'JES', where JES multiplies the input particle jet momenta and is designed to account for the systematic uncertainty of the jet momentum reconstruction. As with all matrix elements techniques, the method involves an integration using the Standard Model matrix element for tt production and decay. however, the technique presented is unique in that the matrix element is modified to compensate for kinematic assumptions which are made to reduce computation time. Background events are dealt with through use of an event observable which distinguishes signal from background, as well as through a cut on the value of an event's maximum likelihood. Results are based on a 955 pb{sup -1} data sample, using events with a high-p{sub T} lepton and exactly four high-energy jets, at least one of which is tagged as coming from a …

The thesis is organized as follows: Chapter 1 describes the theoretical framework of non-leptonic B{sub (s)}{sup 0} {yields} H{sup +}h{prime}{sup -} decays, with a simple overview of the CP violation mechanism within the Standard Model and of the most used phenomenological approaches in the evaluation of strong interaction contributions. The chapter contains also a review of the theoretical expectations and the current experimental measurements along with a discussion about the importance of studying such decays. Chapter 2 contains a general description of the Tevatron collider and of the CDF II detector. Chapter 3 is devoted to the description of the data sample used for the measurement and the method used in extracting the signal from the background. Particular attention is dedicated to the on-line trigger selection, which is crucial to collect a sample enriched in B{sub (s)}{sup 0} {yields} h{sup +}h{prime}{sup -} decays. Chapter 4 shows how the information from kinematics and particle identification was used to achieve a statistical discrimination amongst modes to extract individual measurements. The available resolutions in mass or in particle identification are separately insufficient for an event-by-event separation of B{sub (s)}{sup 0} {yields} h{sup +}h{prime}{sup -} modes. The choice of observables and the technique used …