The electrochemistry of the heterobimetallic complexes (fulvalene)WFe(CO){sub 5} (30) and (fulvalene)WRu(CO){sub 5} (31) has been investigated. Compound 30 is reduced in two one-electron processes, and this behavior was exploited synthetically to prepare a tetranuclear dimer by selective metal reduction. Complex 31 displayed a distinction between the metals upon reoxidation of the dianion, allowing the formation of a dimer by selective metal anion oxidation. The redox behavior of 30 led to an investigation of the use of electrocatalysis to effect metal-specific ligand substitution. It was found that reduction of 30 with a catalytic amount of CpFe(C{sub 6}Me{sub 6}) (97) in the presence of excess P(OMe){sub 3} or PMe{sub 3} led to the formation of the zwitterions (fulvalene)[W(CO){sub 3}{sup {minus}}][Fe(CO)PR{sub 3}{sup +}] (107, R = P(OMe){sub 3}; 108, R = PMe{sub 3}). Compound 31 also displayed unique behavior with different reducing agents, as the monosubstituted zwitterion (fulvalene)[W(CO){sub 3}{sup {minus}}][Ru(CO){sub 2}(PMe{sub 3}){sup +}] was obtained when 97 was used while the disubstituted complex (fulvalene) [W(CO){sub 3}{sup {minus}}] [Ru(CO)(PMe{sub 3}){sub 2}{sup +}] was produced when Cp*Fe(C{sub 6}Me{sub 6}) was the catalyst. Potential synthetic routes to quatercyclopentadienyl complexes were also explored. Various attempts to couple heterobimetallic fulvalene compounds proved to be unsuccessful. 138 refs.

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We have improved and extended a novel ac calorimetric technique for measuring the heat capacity of adsorbates on evaporated metal films. Metallic substrates are of particular interest in current studies of the thermodynamics of adsorbed molecules. The method described in the present work is only calorimetric technique which allows measurements of molecules on simple metallic surfaces. Among other improvements, we have achieved significant progress in the preparation and characterization of the evaporated metal film. We have applied this novel technique to a study of hydrogen multilayers on gold and sapphire substrates. We have shown that samples of normal-hydrogen with a nominal coverage n of approximately 25 monolayers (ML) undergo a bulk-like orientational ordering transition. The transition is suppressed as the coverage is decreased, and no sign of the transition remains above 1.6 K for n {approx} 1 ML. For n {approx_lt} 8 ML, the peak in the heat capacity exhibits signs of finite-size effects. At higher coverages, finite-size effects are not observed, and the shape of the peak depends strongly on the substrate. We conclude that the peak is inhomogeneously broadened for n {approx_lt} 8 ML. This work represents the first measurements of the heat capacity due to orientational ordering …

Modern quantum chemistry deals with electronic structure calculations of unprecedented complexity and accuracy. They demand full power of high-performance computing and must be in tune with the given architecture for superior e#14;ciency. To make such applications resourceaware, it is desirable to enable their static and dynamic adaptations using some external software (middleware), which may monitor both system availability and application needs, rather than mix science with system-related calls inside the application. The present work investigates scienti#12;c application interlinking with middleware based on the example of the computational chemistry package GAMESS and middleware NICAN. The existing synchronous model is limited by the possible delays due to the middleware processing time under the sustainable runtime system conditions. Proposed asynchronous and hybrid models aim at overcoming this limitation. When linked with NICAN, the fragment molecular orbital (FMO) method is capable of adapting statically and dynamically its fragment scheduling policy based on the computing platform conditions. Signi#12;cant execution time and throughput gains have been obtained due to such static adaptations when the compute nodes have very di#11;erent core counts. Dynamic adaptations are based on the main memory availability at run time. NICAN prompts FMO to postpone scheduling certain fragments, if there is not enough …

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This study investigates effects of aging in air and argon at 170 C on Cu coupons which were pretinned with 75Sn-25Pb, 8Sn-92Pb, and 5Sn-95Pb solders. Coatings were applied using electroplating or hot dipping techniques. The coating thickness was controlled between 3 to 3{mu}m and the specimens were aged for 0 hours, 2 hours, 24 hours and 2 weeks. Wetting balance tests were used to evaluate the wettability of the test specimens. Microstructural development was evaluated using X-ray diffraction, energy dispersive X-ray and Auger spectroscopy, as well as optical and scanning electron microscopy. The wetting behavior of the test specimens is interpreted with respect to observed microstructural changes and as a function of aging time, solder composition, and processing conditions.

Using the 5.8 {times} 10{sup 6} J/{psi} events collected by the MARK 3 experiment on the SPEAR e{sup +}e{sup {minus}} storage ring at SLAC, a mass independent amplitude analysis of the J/{psi} {yields} {gamma} K{sub s}K{sub s} and J/{psi} {yields} K{sup +}K{sup {minus}} decays is presented. For K{bar K} systems having mass less than 2 GeV/c{sup 2}, the efficiency-corrected spherical harmonic moments of the J/{psi} joint decay angular distribution are measured. Fits are then performed in each independent mass interval in order to extract the underlying helicity amplitude structure; amplitudes describing K{bar K} systems of spin zero and spin two are included simultaneously. For the first time, a large spin zero component in the {theta}(1720) mass region is observed; consistent results are obtained for the data samples corresponding to the individual decay modes. This structure is attributed to the production of an S wave resonance, the f{sub 0}(1710), of mass and width M = 1710 {plus_minus} 10 MeV/c{sup 2}, {Gamma} = 186 {plus_minus} 30 MeV/c{sup 2}, respectively, with branching fraction Bf(J/{psi} {yields} {gamma}f{sub 0}, f{sub 0} {yields} K{bar K}) = (6.47 {plus_minus} 1.14 {plus_minus} 0.84) {times} 10{sup {minus}4}. A small amount ({approximately}24%) of spin two component in this mass region …

Much of the previous work in the large data visualization area has solely focused on handling the scale of the data. This task is clearly a great challenge and necessary, but it is not sufficient. Applying standard visualization techniques to large scale data sets often creates complicated pictures where meaningful trends are lost. A second challenge, then, is to also provide algorithms that simplify what an analyst must understand, using either visual or quantitative means. This challenge can be summarized as improving the legibility or reducing the complexity of massive data sets. Fully meeting both of these challenges is the work of many, many PhD dissertations. In this dissertation, we describe some new techniques to address both the scale and legibility challenges, in hope of contributing to the larger solution. In addition to our assumption of simultaneously addressing both scale and legibility, we add an additional requirement that the solutions considered fit well within an interoperable framework for diverse algorithms, because a large suite of algorithms is often necessary to fully understand complex data sets. For scale, we present a general architecture for handling large data, as well as details of a contract-based system for integrating advanced optimizations into a …

The following document analyzes one hundred and seventy-seven bevatron tau mesons for Q value of the tau decay, tau spin and parity, and possible polarization effects.

For this study, a high throughput method for identifying and testing regulatory elements was examined. In addition, the validity of promoters predicted by FirstEF was tested. It was found that by combining computer based promoter and first exon predictions from FirstEF (Davuluri et al., 2001) with PCR-based cloning to generate luciferase reporter constructs, and by testing reporter activity in cultured mammalian cells plated in a 96 well format one could identify promoter activity in a relatively high throughput manner. The data generated in this study suggest that FirstEF predictions are sometimes incorrect. Therefore, having a strategy for defining which FirstEF predicted promoters to test first may accelerate the process. Initially testing promoters that are at a confirmed transcription start site for a gene, at a possible alternate transcription start site or in a region of conserved sequence would be the best candidates, while promoters predicted in gene desert regions may not be as easy to confirm. The luciferase assay lent itself very well to the high throughput search, however the subcloning did not always go smoothly. The numerous steps that this traditional subcloning method requires were time consuming and increased the opportunities for errors. A faster method that skips many …

The purpose of this study was to describe and to assess the development, current status, and contributions of Student Foundation programs in institutions of higher education in the United States.

This thesis describes the analysis of the semileptonic decay D{sup 0} {yields} {bar K}{sup 0} {pi}{sup -} {mu}{sup +}{nu} using FOCUS data. FOCUS is a fixed target experiment at Fermilab that studies the physics of the charm quark. Particles containing charm are produced by photon-gluon fusion from the collision of a photon beam on a BeO target. The experiment is characterized by excellent vertex resolution and particle identification. The spectrometer consists of three systems for track reconstruction (two silicon systems and one multiwire proportional chamber system) and two magnets of opposite polarity. The polarity of the magnet is such that the events of e{sup +}e{sup -} pairs produced in the target (which constitutes the main background) travel through a central opening in the detectors without interactions. Particle momentum is measured from the deflection angle in the magnets. Three multicell Cerenkov counters are used for charged particle identification (for e, {pi}, K, and p). Two different tracking systems located after several interaction lengths of shielding material are used for muon identification. The energy of neutral pions and electrons is measured in two electromagnetic calorimeters, while an hadron calorimeter is used for measuring the neutron energy. During the last four years the …

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This study of the RAgSb{sub 2} series of compounds arose as part of an investigation of rare earth intermetallic compounds containing antimony with the rare earth in a position with tetragonal point symmetry. Materials with the rare earth in a position with tetragonal point symmetry frequently manifest strong anisotropies and rich complexity in the magnetic properties, and yet are simple enough to analyze. Antimony containing intermetallic compounds commonly possess low carrier densities and have only recently been the subject of study. Large single grain crystals were grown of the RAgSb{sub 2} (R=Y, La-Nd, Sm, Gd-Tm) series of compounds out of a high temperature solution. This method of crystal growth, commonly known as flux growth is a versatile method which takes advantage of the decreasing solubility of the target compound with decreasing temperature. Overall, the results of the crystal growth were impressive with the synthesis of single crystals of LaAgSb{sub 2} approaching one gram. However, the sample yield diminishes as the rare earth elements become smaller and heavier. Consequently, no crystals could be grown with R=Yb or Lu. Furthermore, EuAgSb{sub 2} could not be synthesized, likely due to the divalency of the Eu ion. For most of the RAgSb{sub 2} compounds, …

The interaction of superconductivity with magnetism has been one of the most interesting and important phenomena in solid state physics since the 1950`s when small amounts of magnetic impurities were incorporated in superconductors. The discovery of the magnetic superconductors RNi{sub 2}B{sub 2}C (R = rare earth, Y) offers a new system to study this interaction. The wide ranges of superconducting transition (T{sub c}) and antiferromagnetic (AF) ordering temperatures (T{sub N}) (0 K {le} T{sub c} {le} 16 K, 0 K {le} T{sub N} {le} 20 K) give a good opportunity to observe a variety of interesting phenomena. Single crystals of high quality with appropriate size and mass are crucial in examining the anisotropic intrinsic properties. Single crystals have been grown successfully by an unusual high temperature flux method and characterized thoroughly by X-ray, electrical transport, magnetization, neutron scattering, scanning electron microscopy, and other measurements.

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This work is concerned with the development of approximate methods to describe relatively large chemical systems. This effort has been divided into two primary directions: First, we have extended and applied a semiclassical transition state theory (SCTST) originally proposed by Miller to obtain microcanonical and canonical (thermal) rates for chemical reactions described by a nonseparable Hamiltonian, i.e. most reactions. Second, we have developed a method to describe the fluctuations of decay rates of individual energy states from the average RRKM rate in systems where the direct calculation of individual rates would be impossible. Combined with the semiclassical theory this latter effort has provided a direct comparison to the experimental results of Moore and coworkers. In SCTST, the Hamiltonian is expanded about the barrier and the ``good`` action-angle variables are obtained perturbatively; a WKB analysis of the effectively one-dimensional reactive direction then provides the transmission probabilities. The advantages of this local approximate treatment are that it includes tunneling effects and anharmonicity, and it systematically provides a multi-dimensional dividing surface in phase space. The SCTST thermal rate expression has been reformulated providing increased numerical efficiency (as compared to a naive Boltzmann average), an appealing link to conventional transition state theory (involving a …

Chapter 1 of this thesis describes the various stages of tumor development and a multitude of diagnostic techniques used to detect cancer. Chapter 2 gives an overview of the aspects of hole burning spectroscopy important for its application to the study of cellular systems. Chapter 3 gives general descriptions of cellular organelles, structures, and physical properties that can serve as possible markers for the differentiation of normal and cancerous cells. Also described in Chapter 3 are the principles of cryobiology important for low temperature spectroscopy of cells, characterization of MCF-10F (normal) and MCF-7 (cancer) cells lines which will serve as model systems, and cellular characteristics of aluminum phthalocyanine tetrasulfonate (APT), which was used as the test probe. Chapters 4 and 5 are previously published papers by the author pertaining to the results obtained from the application of hole burning to the study of cellular systems. Chapter 4 presents the first results obtained by spectral hole burning of cellular systems and Chapter 5 gives results for the differentiation of MCF-10F and MCF-7 cells stained with APT by an external applied electric (Stark) field. A general conclusion is presented in Chapter 6. Appendices A and B provide additional characterization of the cell/probe …

The United States Environmental Protection Agency`s (EPA) Data Quality Objectives (DQO) process was applied to two environmental monitoring networks for the purpose of optimizing field quality control sampling to give the highest quality monitoring data with minimal impact on resources. The DQO process, developed primarily to aid in cleanup and restoration activities, is a systematic approach to designing sampling, and analysis programs with improved efficiency, cost savings, and measureable and traceable data quality. The two monitoring- networks studied had not been subjected to the systematic review and analysis of the DQO process defined by the EPA. The two monitoring networks studied had relied upon field duplicates or replicates as the main source of field quality control data. Sometimes, both duplicate and routine sample were analyzed by the same analytical laboratory; at other times they were analyzed by different laboratories. This study identified some potential inconsistencies between analytical data and reporting limits from two different laboratories. Application of the EPA DQO process resulted in recommendations for changes in the field quality control sampling program, allowed new insight into the monitoring data, and raised several issues that should be the subject of further investigation.

When the field of modern publishing was on a collision course with telecommunications, publishing organizations had to come up to speed in fields that were, heretofore, completely foreign and technologically forbidding to them. For generations, the technology of publishing centered on offset lithography, typesetting, and photography--fields that saw evolutionary and incremental change from the time of Guttenberg. But publishing now includes making information available over the World Wide Web--Internet publishing--with its ever-accelerating rate of technological change and dependence on computers and networks. Clearly, we need a methodology to help anyone in the field of Internet publishing plan for the future, and there is a well-known, well-tested technique for just this purpose--Scenario Planning. Scenario Planning is an excellent tool to help organizations make better decisions in the present based on what they identify as possible and plausible scenarios of the future. Never was decision making more difficult or more crucial than during the years of this study, 1996-1999. This thesis takes the position that, by applying Scenario Planning, the Technical Information Department at LLNL, a large government laboratory (and organizations similar to it), could be confident that moving into the telecommunications business of Internet publishing stood a very good chance of …

Optical second harmonic generation has proven to be a powerful tool for studying interfaces. The symmetry properties of the process allow for surface sensitivity not available with other optical methods. In this thesis, we take advantage of these symmetry properties SHG to study a variety of interesting systems not previously studied with this technique. We show that optical second harmonic generation is an effective surface probe with a submonolayer sensitivity for media without inversion symmetry. We demonstrate the technique at a gallium arsenide surface, exploiting the different symmetry properties of the bulk and surface of the crystal to isolate the surface contribution. We also demonstrate that optical second harmonic generation can be used to determine the anisotropic orientational distribution of a surface monolayer of molecules. We apply the technique to study homogeneously aligned liquid crystal cells. To further explore the LC-polymer interface, we used SHG to study the surface memory effect. The surface memory effect is the rendering of an isotropic interface anisotropic by putting it in contact with an anisotropic bulk. Last, we describe some preliminary measurements of a time-resolved spectroscopic study of the phenomenon of second harmonic generation in a gas. The construction of a 500 microjoule pulsed, …

This Ph.D. Thesis describes several separation and detection schemes for the analysis of small volume and amount of samples, such as intracellular components and single enzymes developed during research. Indirect Laser-induced fluorescence detection and capillary electrophoresis were used to quantify lactate and pyruvate in single red blood cells. The assay of specific enzyme activities was achieved by monitoring the highly fluorescent enzymatic reaction product, NADH. LDH activity was found not to be a unique marker for diagnosis of leukemia. Reactions of single LDH-1 molecules were investigated by monitoring the reaction product with LIF detection.

This thesis involved the construction of (1) a grammar that incorporates knowledge on base invariancy and secondary structure in a molecule and (2) a parser engine that uses the grammar to position bases into the structural subunits of the molecule. These concepts were combined with a novel pinning technique to form a tool that semi-automates insertion of a new species into the alignment for the 16S rRNA molecule (a component of the ribosome) maintained by Dr. Carl Woese`s group at the University of Illinois at Urbana. The tool was tested on species extracted from the alignment and on a group of entirely new species. The results were very encouraging, and the tool should be substantial aid to the curators of the 16S alignment. The construction of the grammar was itself automated, allowing application of the tool to alignments for other molecules. The logic programming language Prolog was used to construct all programs involved. The computational linguistics approach used here was found to be a useful way to attach the problem of insertion into an alignment.