High-spatial and high-mass resolution laser desorption ionization (LDI) mass spectrometric (MS) imaging technology was developed for the attainment of MS images of higher quality containing more information on the relevant cellular and molecular biology in unprecedented depth. The distribution of plant metabolites is asymmetric throughout the cells and tissues, and therefore the increase in the spatial resolution was pursued to reveal the localization of plant metabolites at the cellular level by MS imaging. For achieving high-spatial resolution, the laser beam size was reduced by utilizing an optical fiber with small core diameter (25 μm) in a vacuum matrix-assisted laser desorption ionization-linear ion trap (vMALDI-LTQ) mass spectrometer. Matrix application was greatly improved using oscillating capillary nebulizer. As a result, single cell level spatial resolution of ~ 12 μm was achieved. MS imaging at this high spatial resolution was directly applied to a whole Arabidopsis flower and the substructures of an anther and single pollen grains at the stigma and anther were successfully visualized. MS imaging of high spatial resolution was also demonstrated to the secondary roots of Arabidopsis thaliana and a high degree of localization of detected metabolites was successfully unveiled. This was the first MS imaging on the root for …

This dissertation provides a general introduction to Inductively coupled plasma-mass spectrometry (ICP-MS) and laser ablation (LA) sampling, with an examination of analytical challenges in the employment of this technique. It discusses the origin of metal oxide ions (MO+) in LA-ICP-MS, as well as the effect of introducing helium and nitrogen to the aerosol gas flow on the formation of these polyatomic interferences. It extends the study of polyatomic ions in LA-ICP-MS to metal argide (MAr+) species, an additional source of possible significant interferences in the spectrum. It describes the application of fs-LA-ICP-MS to the determination of uranium isotope ratios in particulate samples.

Organic semiconductors have evolved rapidly over the last decades and currently are considered as the next-generation technology for many applications, such as organic light-emitting diodes (OLEDs) in flat-panel displays (FPDs) and solid state lighting (SSL), and organic solar cells (OSCs) in clean renewable energy. This dissertation focuses mainly on OLEDs. Although the commercialization of the OLED technology in FPDs is growing and appears to be just around the corner for SSL, there are still several key issues that need to be addressed: (1) the cost of OLEDs is very high, largely due to the costly current manufacturing process; (2) the efficiency of OLEDs needs to be improved. This is vital to the success of OLEDs in the FPD and SSL industries; (3) the lifetime of OLEDs, especially blue OLEDs, is the biggest technical challenge. All these issues raise the demand for new organic materials, new device structures, and continued lower-cost fabrication methods. In an attempt to address these issues, we used solution-processing methods to fabricate highly efficient small molecule OLEDs (SMOLEDs); this approach is costeffective in comparison to the more common thermal vacuum evaporation. We also successfully made efficient indium tin oxide (ITO)-free SMOLEDs to further improve the efficiency of …

A RANS/DES numerical procedure with an extended Lax-Wendroff control-volume scheme and turbulence model is described for the accurate simulation of internal/external axisymmetric flow with and without strong rotation. This new procedure is an extension, from Cartesian to cylindrical coordinates, of (1) a second order accurate multi-grid, control-volume integration scheme, and (2) a k-{omega} turbulence model. This paper outlines both the axisymmetric corrections to the mentioned numerical schemes and the developments of techniques pertaining to numerical dissipation, multi-block connectivity, parallelization, etc. Furthermore, analytical and experimental case studies are presented to demonstrate accuracy and computational efficiency. Notes are also made toward numerical stability of highly rotational flows.

Nucleon form factors allow a sensitive test for models of the nucleon. Recent experiments utilising polarisation observables have resulted, for the first time, in a model-independent determination of the neutron electric form factor GnE. This method employed an 80% longitudinally polarised, high intensity (10 uA) electon beam (883 MeV) that was quasi-elastically scattered off a liquid deuterium target in the reaction D (e, en)p. A neutron polarimeter was designed and installed to measure the ratio of transverse-to-longitudinal polarisation using neutron scattering asymmetries. This ratio allowed a determination of the neutron elastic form factor, GnE, free of the previous large systematic uncertainties associated with the deuterium wave function. The experiment took place in the A1 experimental hall at MAMI taking advantage of a high resolution magnetic spectrometer. A detailed investigation was carried out into the performance of the neutron polarimeter.

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 element techniques, the method involves an integration using the Standard Model matrix element for t{bar t} 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 …

Cerium gadolinium oxide (CGO) has been identified as an acceptable solid oxide fuel cell (SOFC) electrolyte at temperatures (500-700 C) where cheap, rigid, stainless steel interconnect substrates can be used. Unfortunately, both the high sintering temperature of pure CGO, >1200 C, and the fact that constraint during sintering often results in cracked, low density ceramic films, have complicated development of metal supported CGO SOFCs. The aim of this work was to find new sintering aids for Ce{sub 0.9}Gd{sub 0.1}O{sub 1.95}, and to evaluate whether they could be used to produce dense, constrained Ce{sub 0.9}Gd{sub 0.1}O{sub 1.95} films at temperatures below 1000 C. To find the optimal sintering aid, Ce{sub 0.9}Gd{sub 0.1}O{sub 1.95} was doped with a variety of elements, of which lithium was found to be the most effective. Dilatometric studies indicated that by doping CGO with 3mol% lithium nitrate, it was possible to sinter pellets to a relative density of 98.5% at 800 C--a full one hundred degrees below the previous low temperature sintering record for CGO. Further, it was also found that a sintering aid's effectiveness could be explained in terms of its size, charge and high temperature mobility. A closer examination of lithium doped Ce0.9Gd0.1O1.95 indicated that …

Results are reported on the reaction {gamma}p {yields} p{bar p}p with beam energy in the range 4.8-5.5 GeV. The data were collected at the Thomas Jefferson National Accelerator Facility in CLAS experiment E01-017(G6C). The focus of this study is an understanding of the mechanisms of photoproduction of proton-antiproton pairs, and to search for intermediate resonances, both narrow and broad, which decay to p{bar p}. The total measured cross section in the photon energy range 4.8-5.5 GeV is {sigma} = 33 {+-} 2 nb. Measurement of the cross section as a function of energy is provided. An upper limit on the production of a narrow resonance state previously observed with a mass of 2.02 GeV/c{sup 2} is placed at 0.35 nb. No intermediate resonance states were observed. Meson exchange production appears to dominate the production of the proton-antiproton pairs.

The risk of accidental detonation is present whenever any type of high explosives processing activity is performed. These activities are typically carried out indoors to protect processing equipment from the weather and to hide possibly secret processes from view. Often, highly strengthened reinforced concrete buildings are employed to house these activities. These buildings may incorporate several design features, including the use of lightweight frangible blowout panels, to help mitigate blast effects. These panels are used to construct walls that are durable enough to withstand the weather, but are of minimal weight to provide overpressure relief by quickly moving outwards and creating a vent area during an accidental explosion. In this study the behavior of blowout panels under various blast loading conditions was examined. External loadings from explosions occurring in nearby rooms were of primary interest. Several reinforcement systems were designed to help blowout panels resist failure from external blast loads while still allowing them to function as vents when subjected to internal explosions. The reinforcements were studied using two analytical techniques, yield-line analysis and modal analysis, and the hydrocode AUTODYN. A blowout panel reinforcement design was created that could prevent panels from being blown inward by external explosions. This design …

A series of in situ toughened, Al, B and C containing, silicon carbide ceramics (ABC-SiC) has been examined with Al contents varying from 3 to 7 wt%. With increasing Al additions, the grain morphology in the as-processed microstructures varied from elongated to bimodal to equiaxed, with a change in the nature of the grain-boundary film from amorphous to partially crystalline to fully crystalline. Fracture toughness and cyclic fatigue tests on these microstructures revealed that although the 7 wt.% Al containing material (7ABC) was extremely brittle, the 3 and particularly 5 wt.% Al materials (3ABC and 5ABC, respectively) displayed excellent crack-growth resistance at both ambient (25 C) and elevated (1300 C) temperatures. Indeed, no evidence of creep damage, in the form of grain-boundary cavitation, was seen at temperatures at 1300 C or below. The enhanced toughness of the higher Al-containing materials was associated with extensive crack bridging from both interlocking grains (in 3ABC) and uncracked ligaments (in 5ABC); in contrast, the 7ABC SiC showed no such bridging, concomitant with a marked reduction in the volume fraction of elongated grains. Mechanistically, cyclic fatigue-crack growth in 3ABC and 5ABC SiC involved the progressive degradation of such bridging ligaments in the crack wake, with …

The research described in this dissertation consists of four major areas: (1) sequence analysis of protamine 2 from Muroid rodents to identify potential zinc-binding domain(s) of protamine 2; (2) structural studies of the protamine 2-zinc complex from Syrian Gold hamster sperm and spermatids to elucidate the role of zinc during spermiogenesis; (3) structural studies of an unique protamine 2-zinc complex from chinchilla sperm; and (4) Nuclear Magnetic Resonance (NMR) studies of soluble complexes of hairpin oligonucleotides with synthetic arginine-rich peptides or protamine 1 isolated from bull sperm. First, zinc was quantitated in spermatids and sperm by Proton-Induced X-ray Emission (PIXE) to determine whether zinc is present in the early stages of spermiogenesis. The PIXE results revealed the zinc content varies proportionately with the amount of protamine 2 in both spermatid and sperm nuclei. An exception was chinchilla sperm containing twice the amount of protamine 2 than zinc. Further analyses by PIXE and X-ray Absorption Spectroscopy (XAS) of zinc bound to protamines isolated from hamster sperm confirmed the majority of the zinc is bound to protamine and identified the zinc ligands of protamine 2 in hamster spermatids and sperm in vivo. These studies established that zinc is bound to the protamine …

The overall purpose of these experiments is to contribute to the development of ion injector technology in order to produce a driver for use in a heavy-ion-fusion (HIF) power generating facility. The overall beam requirements for HIF are quite demanding; a short list of the constraints is the following: (1) Low cost (a large portion of overall cost will come from the beam system); (2) Bright, low emittance beam; (3) Total beam energy 5MJ; (4) Spot size 3mm (radius); (5) Pulse Duration 10ns; (6) Current on target 40kA; (7) Repetition Rate 5Hz; (8) Standoff from target 5m; and (9) Transverse Temp < 1 keV. The reasons for employing ion beams in inertial fusion systems become obvious when the repetition rate required is considered. While laser drivers are useful in producing a proof-of-concept, they will be incapable of application in power generation. Consequently attempts in the U.S. to achieve a power generating system make use of linear ion accelerators. It is apparent that the accelerator system requires the highest quality input as obtainable. Therefore injector design is an essential portion of the entire inertial fusion system. At Lawrence Berkeley and Lawrence Livermore National Laboratories experiments are being conducted using two injector …

Collagen is a key structural protein in the body; several pathological conditions lead to changes in collagen. Among imaging modalities that can be used in vivo, second harmonic generation (SHG) microscopy has a key advantage: it provides {approx}1 {micro}m resolution information about collagen structure as a function of depth. A new technique--polarization-modulated SHG--is presented: it permits simultaneous measurement of collagen orientation, of a lower bound on the magnitude of the second order nonlinear susceptibility tensor, and of the ratio of the two independent elements in this tensor. It is applied to characterizing SHG in collagen and to determining effects of biologically relevant changes in collagen structure. The magnitude of the second harmonic signal in two dimensional images varies with position even in structurally homogeneous tissue; this phenomenon is due to interference between second harmonic light generated by neighboring fibrils, which are randomly oriented parallel or anti-parallel to each other. Studies in which focal spot size was varied indicated that regions where fibrils are co-oriented are less than {approx}1.5 {micro}m in diameter. A quartz reference was used to determine the spot size as well as a lower limit (d{sub xxx} > 0.3 pm/V) for the magnitude of the second order nonlinear …

Single-molecule methods have the potential to provide information about conformational dynamics and molecular interactions that cannot be obtained by other methods. Removal of ensemble averaging provides several benefits, including the ability to detect heterogeneous populations and the ability to observe asynchronous reactions. Single-molecule diffusion methodologies using fluorescence resonance energy transfer (FRET) are developed to monitor conformational dynamics while minimizing perturbations introduced by interactions between molecules and surfaces. These methods are used to perform studies of the folding of Chymotrypsin Inhibitor 2, a small, single-domain protein, and of single-stranded DNA (ssDNA) homopolymers. Confocal microscopy is used in combination with sensitive detectors to detect bursts of photons from fluorescently labeled biomolecules as they diffuse through the focal volume. These bursts are analyzed to extract fluorescence resonance energy transfer (FRET) efficiency. Advances in data acquisition and analysis techniques that are providing a more complete picture of the accessible molecular information are discussed. Photon Arrival-time Interval Distribution (PAID) analysis is a new method for monitoring macromolecular interactions by fluorescence detection with simultaneous determination of coincidence, brightness, diffusion time, and occupancy (proportional to concentration) of fluorescently-labeled molecules undergoing diffusion in a confocal detection volume. This method is based on recording the time of arrival of …

Alkali metal aluminohydrides have high potential as solid hydrogen storage materials. They have been known for their irreversible dehydrogenation process below 100 atm until Bogdanovic et al [1, 2] succeeded in the re-hydrogenation of NaAlH{sub 4} below 70 atm. They achieved 4 wt.% H{sub 2} reversible capacity by doping NaAlH{sub 4} with Ti and/or Fe organo-metalic compounds as catalysts. This suggests that other alkali and, possibly alkaline earth metal aluminohydrides can be used for reversible hydrogen storage when modified by proper dopants. In this research, Zr{sub 27}Ti{sub 9}Ni{sub 38}V{sub 5}Mn{sub 16}Cr{sub 5}, LaNi{sub 4.85}Sn{sub 0.15}, Al{sub 3}Ti, and PdCl{sub 2} were combined with LiAlH{sub 4} by ball-milling to study whether or not LiAlH{sub 4} is capable to both absorb and desorb hydrogen near ambient conditions. X-ray powder diffraction, differential thermal analysis, and scanning electron microscopy were employed for sample characterizations. All four compounds worked as catalysts in the dehydrogenation reactions of both LiAlH{sub 4} and Li{sub 3}AlH{sub 6} by inducing the decomposition at lower temperature. However, none of them was applicable as catalyst in the reverse hydrogenation reaction at low to moderate hydrogen pressure.

Fe{sub 2}VAl has recently been discovered to have a negative temperature coefficient of resistivity, moderately enhanced specific heat coefficient, and a large DOS at the Fermi level by photoemission. This triggered a round of heated research to understand the ground state of this material, both theoretically and experimentally. here they report a comprehensive characterization of Fe{sub 2}VAl. X-ray diffraction exhibited appreciable antisite disorder in all of our samples. FTIR spectroscopy measurements showed that the carrier density and scattering time had little sample-to-sample variation or temperature dependence for near-stoichiometric samples. FTIR and DC resistivity suggest that the transport properties of Fe{sub 2}VAl are influenced by both localized and delocalized carriers, with the former primarily responsible for the negative temperature coefficient of resistivity. Magnetization measurements reveal that near-stoichiometric samples have superparamagnetic clusters with at least two sizes of moments. X-ray photoemission from Fe core level showed localized magnetic moments on site-exchanged Fe. They conclude that in Fe{sub 2}VAl, antisite disorder causes significant modification to the semi-metallic band structure proposed by LDA calculations. With antisite disorder considered, they are now able to explain most of the physical properties of Fe{sub 2}VAl.

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We present the results of a search in p{bar p} collisions at {radical}s = 1.8 TeV for anomalous production of events containing a photon with large transverse energy and a lepton (e or {mu}) with large transverse energy, using 86 pb{sup -1} of data collected at the Collider Detector at Fermilab during the 1994-95 collider run at the Fermilab Tevatron. The presence of large missing transverse energy (E{sub T}), additional photons, or additional leptons in these events is also analyzed. The results are consistent with standard model expectations, with the possible exception of photon-lepton events with large E{sub T}, for which the probability of a statistical fluctuation of the standard model expectation up to and above the observed level is 0.7%.

One of the major highlights of the technology development for the National Ignition Facility (NIF) is the optics. NIF will be the largest laser ever built, requiring 7500 large optics (over one foot across) and more than 30,000 small optics. The design, manufacture, and assembly of these important pieces have called for innovative ways to make optics of higher quality than ever before, and to do so at unprecedented speeds. The most obvious role of NIF optics is to steer the 192 laser beams through the 700-foot-long building onto a dime-size laser-fusion target. The less obvious optic roles are using NIF laser glass to create laser light out of normal light, and using KDP crystals to convert that laser light to the correct frequency; both of which are technically challenging requirements. The Optics Processing Laboratory and Optics Assembly Building enable the final preparation and mounting of these amazing optics for their use in NIF.

Photoemission intensities from the molecular orbitals of c(2x2)CO/Pt(111) over a wide photon energy range were measured and analyzed by the same methods developed for structural studies using core levels. The 4{sigma} orbital center of gravity is found to be concentrated between the C and O atoms, while that of the 5{sigma} orbital lies between the C atom and the Pt surface. The C 1s photoelectron diffraction was used to determine the adsorption geometry. The earlier ambiguity that multiple scattering is needed to correctly model a {chi} curve while single scattering is sufficient for understanding major peaks in the ARPEFS-FTS is clarified by studying the clean Ni(111) surface. In the normal emission case, several different combinations of scattering events have similar path length differences (PLDs), and can either cancel each other or enhance the corresponding FT peak. In the off-normal case the degeneracy is greatly reduced due to the lower degree of symmetry. In normal emission AR PEFS, up to third order multiple scattering is needed to describe fully both the {chi} curve and its FT spectrum. To improve the spectral resolution in the ARPEFS-FT analysis, several new spectral analysis methods are introduced. With both autocorrelation autoregression (ACAR) and autocorrelation eigenvector …

This dissertation describes recent developments in solid state nuclear magnetic resonance (NMR), for the most part involving the use of dynamic-angle spinning (DAS) NMR to study quadrupolar nuclei. Chapter 1 introduces some of the basic concepts and theory that will be referred to in later chapters, such as the density operator, product operators, rotations, coherence transfer pathways, phase cycling, and the various nuclear spin interactions, including the quadrupolar interaction. Chapter 2 describes the theory behind motional averaging experiments, including DAS, which is a technique where a sample is spun sequentially about two axis oriented at different angles with respect to the external magnetic field such that the chemical shift and quadrupolar anisotropy are averaged to zero. Work done on various rubidium-87 salts is presented as a demonstration of DAS. Chapter 3 explains how to remove sidebands from DAS and magic-angle spinning (MAS) experiments, which result from the time-dependence of the Hamiltonian under sample spinning conditions, using rotor-synchronized {pi}-pulses. Data from these experiments, known as DAH-180 and MAH-180, respectively, are presented for both rubidium and lead salts. In addition, the applicability of this technique to double rotation (DOR) experiments is discussed. Chapter 4 concerns the addition of cross-polarization to DAS (CPDAS). …

The chemical-properties of rutherfordium (Rf) and its group 4 homologs were studied by sorption on glass support surfaces coated with cobalt(II)ferrocyanide and by solvent extraction with tributylphosphate (TBP) and triisooctylamine (TIOA). The surface studies showed that the hydrolysis trend in the group 4 elements and the pseudogroup 4 element, lb, decreases in the order Rf>Zr{approx}Hf>Th. This trend was attributed to relativistic effects which predicted that Rf would be more prone to having a coordination number of 6 than 8 in most aqueous solutions due to a destabilization of the 6d{sub 5/2} shell and a stabilization of the 7p{sub l/2} shell. This hydrolysis trend was confirmed in the TBP/HBr solvent extraction studies which showed that the extraction trend decreased in the order Zr>Hf>Rf?Ti for HBr, showing that Rf and Ti did not extract as well because they hydrolyzed more easily than Zr and Hf. The TIOA/HF solvent extraction studies showed that the extraction trend for the group 4 elements decreased in the order Ti>Zr{approx}Hf>Rf, in inverse order from the trend of ionic radii Rf>Zr{approx}Hf>Ti. An attempt was made to produce {sup 263}Rf (a) via the {sup 248}Cm({sup 22}Ne, {alpha}3n) reaction employing thenoyltrifluoroacetone (TTA) solvent extraction chemistry and (b) via the {sup …

Radioactive metal waste makes up a significant portion of the waste currently being sent for disposal. Recovery of this metal as a valuable resource is possible through the use of decontamination technologies. Through the development and use of expert systems a comparison can be made of laser decontamination, a technology currently under development at Ames Laboratory, with currently available decontamination technologies for applicability to the types of metal waste being generated and the effectiveness of these versus simply disposing of the waste. These technologies can be technically and economically evaluated by the use of expert systems techniques to provide a waste management decision making tool that generates, given an identified metal waste, waste management recommendations. The user enters waste characteristic information as input and the system then recommends decontamination technologies, determines residual contamination levels and possible waste management strategies, carries out a cost analysis and then ranks, according to cost, the possibilities for management of the waste. The expert system was developed using information from literature and personnel experienced in the use of decontamination technologies and requires validation by human experts and assignment of confidence factors to the knowledge represented within.

This report discusses the following topics: Circular magnetic x-ray dichroism at the ER L{sub 3} Edge; angular dependence of circular magnetic x-ray dichroism in rare earth compounds: and circular magnetic x-ray dichroism in crystalline and amorphous GDFE{sub 2}.