The author`s group has previously shown that isocyanides are readily adsorbed from solutions to Au powder and bind to the Au surface in an end-on fashion through the terminal carbon. Later work demonstrated that the equilibrium constants for the reversible adsorption of electronically inequivalent isocyanides could be obtained using the Langmuir isotherm technique. This dissertation describes two projects completed which complement the initial findings of this group. Initially, several alkylisocyanides were synthesized to examine the effect of tail length on Au powder adsorption. It was observed that the length of the alkyl chain affected not only the Au surface binding affinity, but also the rate of surface saturation and saturation coverage values. Direct competition studies were also studied using a {sup 13}C-labeled isocyanide. These studies demonstrated the stabilization afforded by substrate-substrate packing forces in SAM`s formed by the longer chain isocyanides. In a second study, di and triisocyanides were synthesized to determine the effect that the length of the connecting link and the number of isocyanide groups (as points of attachment) have on Au adsorption stability. The work in this area describes the binding modes, relative binding affinities and surface coverage values for a series of flexible alkyl and xylyldiisocyanides …

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, …

Conjugated dienes were oxidized by hydrogen peroxide with methylrhenium trioxide (MTO) as catalyst. Methylrhenium bis-peroxide was the major reactive catalyst present. Hydroxyalkenes and trisubstituted silane were also tested. Mechanisms for each of these reactions are presented.

An extrusion process was developed that is able to consistently produce large quantities of Mo-Si-B rods without the presence of defects. Binder removal from the extruded rods was studied in detail and it was determined that heating rates on the order of 0.02{degree}/minute (1.2{degree}/hour) are necessary to remove the binder without the formation of defects. This low heating rate resulted in debinding times in excess of 70 hours (approximately 3 days). Wicking was investigated as a means to decrease the time necessary for binder removal. Using 0.05{micro}m alumina powder as a wicking agent, binder removal times were reduced to 10 hours with heating rates up to 1{degree}/minute employed without defect formation. Once the extrusion process was complete the oxidation properties of the Tl-MoSi{sub 2}-MoB extruded phase assemblage was investigated. It was determined that this composition exhibits catastrophic oxidation or pesting in the temperature range of 660--760 C, resulting in the material turning to dust. Outside of this temperature range the composition is oxidatively stable. Continuous mass measurements were taken at 1,300, 1,450, and 1,600 C to determine the oxidation rate constants of this material. Parabolic rate constants of 6.9 x 10{sup {minus}3}, 1.3 x 10{sup {minus}3}, and 9.1 x 10{sup …

A variety of experimental techniques were utilized to examine the high temperature phase equilibria in the Bi-Sr-Ca-Cu-O-Ag system. Quenching studies were used to determine the liquid solubility of Ag in the Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8} (Bi2212) melt and the details of the peritectic decomposition pathway of Bi2212 as a function on Ag content and oxygen partial pressure (PO{sub 2}). A liquid immiscibility region between oxide and Ag liquids in the 8--98 at% range was found above 900 C. Two eutectics were found in the Bi2212-Ag pseudobinary. On the oxide rich side, a eutectic exists at approximately 4 at% Ag. On the Ag rich side, a eutectic exists at approximately 98 at% Ag at a temperature of 15 C below the melting point of pure Ag. Six distinct solid phases were found to be in equilibrium with the partial melt within the Ag content and PO{sub 2} range studied. The stability of these solid phases were found to be highly sensitive to PO{sub 2}, and to a much lesser extent Ag content. High temperature x-ray diffraction (HTXRD) studies of this system are in conflict with these results. It is suggested that these discrepancies are due to experimental artifacts caused by …

Capillary electrophoresis has been widely accepted as a fast separation technique in DNA analysis. In this dissertation, a new sieving matrix is described for DNA analysis, especially DNA sequencing, genetic typing and mutation detection. A high-throughput 96 capillary array electrophoresis system was also demonstrated for simultaneous multiple genotyping. The authors first evaluated the influence of different capillary coatings on the performance of DNA sequencing. A bare capillary was compared with a DB-wax, an FC-coated and a polyvinylpyrrolidone dynamically coated capillary with PEO as sieving matrix. It was found that covalently-coated capillaries had no better performance than bare capillaries while PVP coating provided excellent and reproducible results. The authors also developed a new sieving Matrix for DNA separation based on commercially available poly(vinylpyrrolidone) (PVP). This sieving matrix has a very low viscosity and an excellent self-coating effect. Successful separations were achieved in uncoated capillaries. Sequencing of M13mp18 showed good resolution up to 500 bases in treated PVP solution. Temperature gradient capillary electrophoresis and PVP solution was applied to mutation detection. A heteroduplex sample and a homoduplex reference were injected during a pair of continuous runs. A temperature gradient of 10 C with a ramp of 0.7 C/min was swept throughout the …

Suppression of mass spectral peaks due to matrix problem is a major hurdle to overcome during identification work. So far, preliminary studies have been done in investigating solutions containing various percentages of nitric and hydrochloric acid. Since other anions would also be present in real samples, also needed to be examined is how the extent of suppression of metal complexes by Cl{sup {minus}} compares with suppression by other anions such as PO{sub 4}{sup 3{minus}} or SO{sub 4}{sup 2{minus}}. If suppression of other anions is as severe as that of the chloride ion, then it would be virtually impossible to analyze unknown samples containing large amount of such anions by direct infusion electrospray mass spectrometry. It seems like a separation step is needed to separate these matrix anions from the metal complexes prior to putting the solution through the electrospray. However, separation of inorganic complexes can be difficult and has not been studied thoroughly as LC separation of bioorganic compounds. Both zinc and copper chloro complexes have been observed to be more tolerant to higher amount of chloride ion present in a solution compared to the group I and II metal chloro complexes. Other transition metals including the lanthanide complexes need …

Surface plasmon resonance was utilized to enhance the electron transfer at silver/solution interfaces. Photoelectrochemical reductions of nitrite, nitrate, and CO{sub 2} were studied on electrochemically roughened silver electrode surfaces. The dependence of the photocurrent on photon energy, applied potential and concentration of nitrite demonstrates that the photoelectrochemical reduction proceeds via photoemission process followed by the capture of hydrated electrons. The excitation of plasmon resonances in nanosized metal structures resulted in the enhancement of the photoemission process. In the case of photoelectrocatalytic reduction of CO{sub 2}, large photoelectrocatalytic effect for the reduction of CO{sub 2} was observed in the presence of surface adsorbed methylviologen, which functions as a mediator for the photoexcited electron transfer from silver metal to CO{sub 2} in solution. Photoinduced reduction of microperoxidase-11 adsorbed on roughened silver electrode was also observed and attributed to the direct photoejection of free electrons of silver metal. Surface plasmon assisted electron transfer at nanostructured silver particle surfaces was further determined by EPR method.

The syntheses of silicon-containing compounds and the studies of their rearrangements have been active research areas in the Barton research group. Previously, the addition of disilanes to acetylenes was studied in the group and an intramolecular 2S + 2A mechanism has been proposed. In this thesis, the work is focused on the addition of disilanes to cumulenes. The syntheses of the precursors are discussed and the possible mechanisms for their thermal, photochemical and catalytic rearrangements are proposed. Conjugated organic polymers have been studied in the group since 1985 because of their potential for exhibiting high electroconductivity, photoconductivity, strong non-linear optical response and intense fluorescence. In the second section of this dissertation, the synthesis and property studies of poly(phenylene vinylene) analogues are discussed.

The processing of materials with unique electronic, mechanical, optical and thermal properties plays a crucial role in modern technology. The quality of these materials depend strongly on the microstructure and the solute/dopant fields in the solid product, that are strongly influenced by the intricate coupling of heat and mass transfer and melt flow in the growth systems. An integrated research program is developed that include precisely characterized experiments and detailed physical and numerical modeling of the complex transport and dynamical processes. Direct numerical simulation of the solidification process is carried out that takes into account the unsteady thermo-solutal convection in the vertical Bridgman crystal growth system, and accurately models the thermal interaction between the furnace and the ampoule by appropriately using experimentally measured thermal profiles. The flow instabilities and transitions and the nonlinear evolution following the transitions are investigated by time series and flow pattern analysis. A range of complex dynamical behavior is predicted with increasing thermal Rayleigh number. The route to chaos appears as: steady convection {r_arrow} transient mono-periodic {r_arrow} transient bi-periodic {r_arrow} transient quasi-periodic {r_arrow} transient intermittent oscillation-relaxation {r_arrow} stable intermittent oscillation-relaxation attractor. The spatio-temporal dynamics of the melt flow is found to be directly related to the …

Solving the global illumination problem is equivalent to determining the intensity of every wavelength of light in all directions at every point in a given scene. The complexity of the problem has led researchers to use approximation methods for solving the problem on serial computers. Rather than using an approximation method, such as backward ray tracing or radiosity, the authors have chosen to solve the Rendering Equation by direct simulation of light transport from the light sources. This paper presents an algorithm that solves the Rendering Equation to any desired accuracy, and can be run in parallel on distributed memory or shared memory computer systems with excellent scaling properties. It appears superior in both speed and physical correctness to recent published methods involving bidirectional ray tracing or hybrid treatments of diffuse and specular surfaces. Like progressive radiosity methods, it dynamically refines the geometry decomposition where required, but does so without the excessive storage requirements for ray histories. The algorithm, called Photon, produces a scene which converges to the global illumination solution. This amounts to a huge task for a 1997-vintage serial computer, but using the power of a parallel supercomputer significantly reduces the time required to generate a solution. Currently, …

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 …

Capillary electrophoresis (CE) is an effective method for separating ionic species according to differences in their electrophoretic mobilities. CE separations of amino acids by direct detection are difficult due to their similar electrophoretic mobilities and low absorbances. However, native amino acids can be separated by CE as cations at a low pH by adding an alkanesulfonic acid to the electrolyte carrier which imparts selectivity to the system. Derivatization is unnecessary when direct UV detection is used at 185 nm. Simultaneous speciation of metal cations such as vanadium (IV) and vanadium (V) can easily be performed without complexation prior to analysis. An indirect UV detection scheme for acidic conditions was also developed using guanidine as the background carrier electrolyte (BCE) for the indirect detection of metal cations. Three chapters have been removed for separate processing. This report contains introductory material, references, and general conclusions. 80 refs.

This work describes the continued development of a new separation technique, electrochemically-modulated liquid chromatography (EMLC), from column design, retention mechanisms to pharmaceutical applications. The introduction section provides a literature review of the technique as well as a brief overview of the research in each of the chapters. This section is followed by four chapters which investigate the issues of EMLC column design, the retention mechanism of monosubstituted aromatic compounds, and the EMLC-based applications to two important classes of pharmaceutical compounds (i.e., corticosteroids and benzodiazepines). These four sections have been removed to process separately for inclusion on the database. The dissertation concludes with a general summary, a prospectus, and a list of references cited in the General Introduction. 32 refs.

This thesis comprises three parts: Electrocatalysis of anodic oxygen-transfer reactions: aliphatic amines at mixed Ag-Pb oxide thin-film electrodes; oxidation of ammonia at anodized Ag-Pb eutectic alloy electrodes; and temperature effects on oxidation of ethylamine, alanine, and aquated ammonia.

An experimental investigation of soft x-ray production resulting from the interaction of intense near infra-red laser radiation with gases is presented in this thesis. Specifically, soft x-ray generation through high order harmonic generation or exploiting intense inverse bremsstrahlung heating is examined. Most of these studies are conducted with femtosecond, terawatt class Cr:LiSrAlF{sub 6} (LiSAF) laser, though results derived from studies with other laser systems are presented as well. The majority of this work is devoted to experimental investigations, however, theoretical and computational models are developed to interpret the data. These studies are motivated by the possibility of utilizing the physics of intense laser/matter interactions as a potential compact source of bright x-rays. Consequently, the thrust of many of the experiments conducted is aimed at characterizing the x-rays produced for possible use in applications. In general, the studies of this manuscript fall into three categories. First, a unique 130 fs, 8 TW laser that is based on chirped pulse amplification, is described, and its performance is evaluated. The generation of x-rays through high order harmonics is then discussed with emphasis on characterizing and optimizing harmonic generation. Finally, the generation of strong, incoherent x-ray radiation by the intense irradiation of large (>1,000 …