4,659 Matching Results

Search Results

Magnetic nanoparticles for applications in oscillating magnetic field

Description: Enzymatic and thermochemical catalysis are both important industrial processes. However, the thermal requirements for each process often render them mutually exclusive: thermochemical catalysis requires high temperature that denatures enzymes. One of the long-term goals of this project is to design a thermocatalytic system that could be used with enzymatic systems in situ to catalyze reaction sequences in one pot; this system would be useful for numerous applications e.g. conversion of biomass to biofuel and other commodity products. The desired thermocatalytic system would need to supply enough thermal energy to catalyze thermochemical reactions, while keeping the enzymes from high temperature denaturation. Magnetic nanoparticles are known to generate heat in an oscillating magnetic field through mechanisms including hysteresis and relaxational losses. We envisioned using these magnetic nanoparticles as the local heat source embedded in sub-micron size mesoporous support to spatially separate the particles from the enzymes. In this study, we set out to find the magnetic materials and instrumental conditions that are sufficient for this purpose. Magnetite was chosen as the first model magnetic material in this study because of its high magnetization values, synthetic control over particle size, shape, functionalization and proven biocompatibility. Our experimental designs were guided by a series of theoretical calculations, which provided clues to the effects of particle size, size distribution, magnetic field, frequency and reaction medium. Materials of theoretically optimal size were synthesized, functionalized, and their effects in the oscillating magnetic field were subsequently investigated. Under our conditions, the materials that clustered e.g. silica-coated and PNIPAM-coated iron oxides exhibited the highest heat generation, while iron oxides embedded in MSNs and mesoporous iron oxides exhibited the least bulk heating. It is worth noting that the specific loss power of PNIPAM-coated Fe{sub 3}O{sub 4} was peculiarly high, and the heat loss mechanism of this material remains to be ...
Date: December 15, 2010
Creator: Peeraphatdit, Chorthip
Partner: UNT Libraries Government Documents Department

Input/Output of ab-initio nuclear structure calculations for improved performance and portability

Description: Many modern scientific applications rely on highly computation intensive calculations. However, most applications do not concentrate as much on the role that input/output operations can play for improved performance and portability. Parallelizing input/output operations of large files can significantly improve the performance of parallel applications where sequential I/O is a bottleneck. A proper choice of I/O library also offers a scope for making input/output operations portable across different architectures. Thus, use of parallel I/O libraries for organizing I/O of large data files offers great scope in improving performance and portability of applications. In particular, sequential I/O has been identified as a bottleneck for the highly scalable MFDn (Many Fermion Dynamics for nuclear structure) code performing ab-initio nuclear structure calculations. We develop interfaces and parallel I/O procedures to use a well-known parallel I/O library in MFDn. As a result, we gain efficient I/O of large datasets along with their portability and ease of use in the down-stream processing. Even situations where the amount of data to be written is not huge, proper use of input/output operations can boost the performance of scientific applications. Application checkpointing offers enormous performance improvement and flexibility by doing a negligible amount of I/O to disk. Checkpointing saves and resumes application state in such a manner that in most cases the application is unaware that there has been an interruption to its execution. This helps in saving large amount of work that has been previously done and continue application execution. This small amount of I/O provides substantial time saving by offering restart/resume capability to applications. The need for checkpointing in optimization code NEWUOA has been identified and checkpoint/restart capability has been implemented in NEWUOA by using simple file I/O.
Date: December 15, 2010
Creator: Laghave, Nikhil
Partner: UNT Libraries Government Documents Department

Developing new optical imaging techniques for single particle and molecule tracking in live cells

Description: Differential interference contrast (DIC) microscopy is a far-field as well as wide-field optical imaging technique. Since it is non-invasive and requires no sample staining, DIC microscopy is suitable for tracking the motion of target molecules in live cells without interfering their functions. In addition, high numerical aperture objectives and condensers can be used in DIC microscopy. The depth of focus of DIC is shallow, which gives DIC much better optical sectioning ability than those of phase contrast and dark field microscopies. In this work, DIC was utilized to study dynamic biological processes including endocytosis and intracellular transport in live cells. The suitability of DIC microscopy for single particle tracking in live cells was first demonstrated by using DIC to monitor the entire endocytosis process of one mesoporous silica nanoparticle (MSN) into a live mammalian cell. By taking advantage of the optical sectioning ability of DIC, we recorded the depth profile of the MSN during the endocytosis process. The shape change around the nanoparticle due to the formation of a vesicle was also captured. DIC microscopy was further modified that the sample can be illuminated and imaged at two wavelengths simultaneously. By using the new technique, noble metal nanoparticles with different shapes and sizes were selectively imaged. Among all the examined metal nanoparticles, gold nanoparticles in rod shapes were found to be especially useful. Due to their anisotropic optical properties, gold nanorods showed as diffraction-limited spots with disproportionate bright and dark parts that are strongly dependent on their orientation in the 3D space. Gold nanorods were developed as orientation nanoprobes and were successfully used to report the self-rotation of gliding microtubules on kinesin coated substrates. Gold nanorods were further used to study the rotational motions of cargoes during the endocytosis and intracellular transport processes in live mammalian cells. New rotational information ...
Date: December 15, 2010
Creator: Sun, Wei
Partner: UNT Libraries Government Documents Department

Optically Detected Magnetic Resonance Studies on π-conjugated semiconductor systems

Description: Optically Detected Magnetic Resonance (ODMR) techniques were used to investigate the dynamics of excitons and charge carriers in π-conjugated organic semiconductors. Degradation behavior of the negative spin-1/2 electroluminescence-detected magnetic resonance (ELDMR) was observed in Alq3 devices. The increase in the resonance amplitude implies an increasing bipolaron formation during degradation, which might be the result of growth of charge traps in the device. The same behavior of the negative spin-1/2 ELDMR was observed in 2wt% Rubrene doped Tris(8-hydroxyquinolinato)aluminium (Alq3) devices. However, with increasing injection current, a positive spin-1/2 ELDMR, together with positive spin 1 triplet powder patterns at {delta}m{sub S}={+-}1 and {delta}m{sub S}={+-}2, emerges. Due to the similarities in the frequency dependences of single and double modulated ELDMR and the photoluminescence-detected magnetic resonance (PLDMR) results in poly[2-methoxy-5-(2 -ethyl-hexyloxy)-1,4-phenyl ene vinylene] (MEH-PPV) films, the mechanism for this positive spin-1/2 ELDMR was assigned to enhanced triplet-polaron quenching under resonance conditions. The ELDMR in rubrene doped Alq3 devices provides a path to investigate charge distribution in the device under operational conditions. Combining the results of several devices with different carrier blocking properties and the results from transient EL, it was concluded trions not only exist near buffer layer but also exist in the electron transport layer. This TPQ model can also be used to explain the positive spin-1/2 PLDMR in poly(3-hexylthiophene) (P3HT) films at low temperature and in MEH-PPV films at various temperatures up to room temperature. Through quantitative analysis, TE-polaron quenching (TPQ) model is shown having the ability to explain most behaviors of the positive spin-1/2 resonance. Photocurrent detected magnetic resonance (PCDMR) studies on MEH-PPV devices revealed a novel transient resonance signal. The signal may originate from the higher concentration of deep traps near cathode. A quantitative analysis based on this assumption was carried out and found to be consistent with the experimental ...
Date: December 6, 2011
Creator: Chen, Ying
Partner: UNT Libraries Government Documents Department

Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols

Description: This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallic complexes. When amine N-oxides were used as an oxidant in the reaction of isocyanides with amines, the system was able to produce ureas from a variety of isocyanides, amines, and amine N-oxides. In addition, the rate was found to generally increase as the amine N-oxide concentration increased, and decrease with increased concentrations of the amine. Mechanistic studies revealed that the reaction likely involves transfer of an oxygen atom from the amine N-oxide to the adsorbed isocyanide to generate an isocyanate intermediate. Subsequent nucleophilic attack by the amine yields the urea. This is in contrast to the bulk gold-catalyzed reaction mechanism of isocyanides with amines and oxygen. Formation of urea in this case was proposed to proceed through a diaminocarbene intermediate. Moreover, formation of the proposed isocyanate intermediate is consistent with the reactions of metal carbonyl ligands, which are isoelectronic to isocyanides. Nucleophilic attack at coordinated CO by amine N-oxides produces CO{sub 2} and is analogous to the production of an isocyanate in this gold system. When the bulk gold-catalyzed oxidative dehydrogenation of amines was examined with amine N-oxides, the same products were afforded as when O{sub 2} was used as the oxidant. When the two types of oxidants were directly ...
Date: December 29, 2011
Creator: Klobukowski, Erik
Partner: UNT Libraries Government Documents Department

Al-Ca and Al-Fe metal-metal composite strength, conductivity, and microstructure relationships

Description: Deformation processed metal-metal composites (DMMC’s) are composites formed by mechanical working (i.e., rolling, swaging, or wire drawing) of two-phase, ductile metal mixtures. Since both the matrix and reinforcing phase are ductile metals, the composites can be heavily deformed to reduce the thickness and spacing of the two phases. Recent studies have shown that heavily drawn DMMCs can achieve anomalously high strength and outstanding combinations of strength and conductivity. In this study, Al-Fe wire composite with 0.07, 0.1, and 0.2 volume fractions of Fe filaments and Al-Ca wire composite with 0.03, 0.06, and 0.09 volume fractions of Ca filaments were produced in situ, and their mechanical properties were measured as a function of deformation true strain. The Al-Fe composites displayed limited deformation of the Fe phase even at high true strains, resulting in little strengthening effect in those composites. Al-9vol%Ca wire was deformed to a deformation true strain of 13.76. The resulting Ca second-phase filaments were deformed to thicknesses on the order of one micrometer. The ultimate tensile strength increased exponentially with increasing deformation true strain, reaching a value of 197 MPa at a true strain of 13.76. This value is 2.5 times higher than the value predicted by the rule of mixtures. A quantitative relationship between UTS and deformation true strain was determined. X-ray diffraction data on transformation of Al + Ca microstructures to Al + various Al-Ca intermetallic compounds were obtained at the Advanced Photon Source at Argonne National Laboratory. Electrical conductivity was measured over a range of true strains and post-deformation heat treatment schedules.
Date: December 1, 2011
Creator: Kim, Hyong June
Partner: UNT Libraries Government Documents Department

Metal thin film growth on multimetallic surfaces: From quaternary metallic glass to binary crystal

Description: The work presented in this thesis mainly focuses on the nucleation and growth of metal thin films on multimetallic surfaces. First, we have investigated the Ag film growth on a bulk metallic glass surface. Next, we have examined the coarsening and decay of bilayer Ag islands on NiAl(110) surface. Third, we have investigated the Ag film growth on NiAl(110) surface using low-energy electron diffraction (LEED). At last, we have reported our investigation on the epitaxial growth of Ni on NiAl(110) surface. Some general conclusions can be drawn as follows. First, Ag, a bulk-crystalline material, initially forms a disordered wetting layer up to 4-5 monolayers on Zr-Ni-Cu-Al metallic glass. Above this coverage, crystalline 3D clusters grow, in parallel with the flatter regions. The cluster density increases with decreasing temperature, indicating that the conditions of island nucleation are far-from-equilibrium. Within a simple model where clusters nucleate whenever two mobile Ag adatoms meet, the temperature-dependence of cluster density yields a (reasonable) upper limit for the value of the Ag diffusion barrier on top of the Ag wetting layer of 0.32 eV. Overall, this prototypical study suggests that it is possible to grow films of a bulk-crystalline metal that adopt the amorphous character of a glassy metal substrate, if film thickness is sufficiently low. Next, the first study of coarsening and decay of bilayer islands has been presented. The system was Ag on NiAl(110) in the temperature range from 185 K to 250 K. The coarsening behavior, has some similarities to that seen in the Ag(110) homoepitaxial system studied by Morgenstern and co-workers. At 185 K and 205 K, coarsening of Ag islands follows a Smoluchowski ripening pathway. At 205 K and 250 K, the terrace diffusion limited Ostwald ripening dominants. The experimental observed temperature for the transition from SR to OR is 205 ...
Date: December 15, 2010
Creator: Jing, Dapeng
Partner: UNT Libraries Government Documents Department

Plasminogen activator inhibitor 1: Mechanisms of its synergistic regulation by growth factors

Description: My research is on the synergistic regulation of PAI-1 by EGF and TGF-β. The mechanism of synergistic regulation of PAI-1 by EGF and TGF-β are addressed. Methods are described for effective identification of RNA accessible sites for antisense oligodexoxynucleotides (ODNs) and siRNA. In this study effective AS-ODN sequences for both Lcn2 and Bcl2 were identified by in vitro tiled microarray studies. Our results suggest that hybridization of ODN arrays to a target mRNA under physiological conditions might be used as a rapid and reliable in vitro method to accurately identify targets on mRNA molecules for effective antisense and potential siRNA activity in vivo.
Date: December 1, 2011
Creator: Song, Xiaoling
Partner: UNT Libraries Government Documents Department

Extending the frontiers of mass spectrometric instrumentation and methods

Description: The focus of this dissertation is two-fold: developing novel analysis methods using mass spectrometry and the implementation and characterization of a novel ion mobility mass spectrometry instrumentation. The novel mass spectrometry combines ion trap for ion/ion reactions coupled to an ion mobility cell. The long term goal of this instrumentation is to use ion/ion reactions to probe the structure of gas phase biomolecule ions. The three ion source - ion trap - ion mobility - qTOF mass spectrometer (IT - IM - TOF MS) instrument is described. The analysis of the degradation products in coal (Chapter 2) and the imaging plant metabolites (Appendix III) fall under the methods development category. These projects use existing commercial instrumentation (JEOL AccuTOF MS and Thermo Finnigan LCQ IT, respectively) for the mass analysis of the degraded coal products and the plant metabolites, respectively. The coal degradation paper discusses the use of the DART ion source for fast and easy sample analysis. The sample preparation consisted of a simple 50 fold dilution of the soluble coal products in water and placing the liquid in front of the heated gas stream. This is the first time the DART ion source has been used for analysis of coal. Steven Raders under the guidance of John Verkade came up with the coal degradation projects. Raders performed the coal degradation reactions, worked up the products, and sent them to me. Gregg Schieffer developed the method and wrote the paper demonstrating the use of the DART ion source for the fast and easy sample analysis. The plant metabolite imaging project extends the use of colloidal graphite as a sample coating for atmospheric pressure LDI. DC Perdian and I closely worked together to make this project work. Perdian focused on building the LDI setup whereas Schieffer focused on the MSn analysis ...
Date: December 15, 2010
Creator: Schieffer, Gregg
Partner: UNT Libraries Government Documents Department

Microstructures and oxidation behavior of some Molybdenum based alloys

Description: The advent of Ni based superalloys revolutionized the high temperature alloy industry. These materials are capable of operating in extremely harsh environments, comprising of temperatures around 1050 C, under oxidative conditions. Demands for increased fuel efficiency, however, has highlighted the need for materials that can be used under oxidative conditions at temperatures in excess of 1200 C. The Ni based superalloys are restricted to lower temperatures due to the presence of a number of low melting phases that melt in the 1250 - 1450 C, resulting in softening of the alloys above 1000 C. Therefore, recent research directions have been skewed towards exploring and developing newer alloy systems. This thesis comprises a part of such an effort. Techniques for rapid thermodynamic assessments were developed and applied to two different systems - Mo-Si alloys with transition metal substitutions (and this forms the first part of the thesis) and Ni-Al alloys with added components for providing high temperature strength and ductility. A hierarchical approach towards alloy design indicated the Mo-Ni-Al system as a prospective candidate for high temperature applications. Investigations on microstructures and oxidation behavior, under both isothermal and cyclic conditions, of these alloys constitute the second part of this thesis. It was seen that refractory metal systems show a marked microstructure dependence of oxidation.
Date: December 15, 2010
Creator: Ray, Pratik Kumar
Partner: UNT Libraries Government Documents Department

Gas atomized precursor alloy powder for oxide dispersion strengthened ferritic stainless steel

Description: Gas atomization reaction synthesis (GARS) was employed as a simplified method for producing precursor powders for oxide dispersion strengthened (ODS) ferritic stainless steels (e.g., Fe-Cr-Y-(Ti,Hf)-O), departing from the conventional mechanical alloying (MA) process. During GARS processing a reactive atomization gas (i.e., Ar-O{sub 2}) was used to oxidize the powder surfaces during primary break-up and rapid solidification of the molten alloy. This resulted in envelopment of the powders by an ultra-thin (t < 150 nm) metastable Cr-enriched oxide layer that was used as a vehicle for solid-state transport of O into the consolidated microstructure. In an attempt to better understand the kinetics of this GARS reaction, theoretical cooling curves for the atomized droplets were calculated and used to establish an oxidation model for this process. Subsequent elevated temperature heat treatments, which were derived from Rhines pack measurements using an internal oxidation model, were used to promote thermodynamically driven O exchange reactions between trapped films of the initial Cr-enriched surface oxide and internal Y-enriched intermetallic precipitates. This novel microstructural evolution process resulted in the successful formation of nano-metric Y-enriched dispersoids, as confirmed using high energy X-ray diffraction and transmission electron microscopy (TEM), equivalent to conventional ODS alloys from MA powders. The thermal stability of these Y-enriched dispersoids was evaluated using high temperature (1200°C) annealing treatments ranging from 2.5 to 1,000 hrs of exposure. In a further departure from current ODS practice, replacing Ti with additions of Hf appeared to improve the Y-enriched dispersoid thermal stability by means of crystal structure modification. Additionally, the spatial distribution of the dispersoids was found to depend strongly on the original rapidly solidified microstructure. To exploit this, ODS microstructures were engineered from different powder particle size ranges, illustrating microstructural control as a function of particle solidification rate. The consolidation of ultra-fine powders (dia. ≤ 5μm) resulted in ...
Date: December 13, 2011
Creator: Rieken, Joel
Partner: UNT Libraries Government Documents Department

Imaging gene expression in real-time using aptamers

Description: Signal transduction pathways are usually activated by external stimuli and are transient. The downstream changes such as transcription of the activated genes are also transient. Real-time detection of promoter activity is useful for understanding changes in gene expression, especially during cell differentiation and in development. A simple and reliable method for viewing gene expression in real time is not yet available. Reporter proteins such as fluorescent proteins and luciferase allow for non-invasive detection of the products of gene expression in living cells. However, current reporter systems do not provide for real-time imaging of promoter activity in living cells. This is because of the long time period after transcription required for fluorescent protein synthesis and maturation. We have developed an RNA reporter system for imaging in real-time to detect changes in promoter activity as they occur. The RNA reporter uses strings of RNA aptamers that constitute IMAGEtags (Intracellular MultiAptamer GEnetic tags), which can be expressed from a promoter of choice. The tobramycin, neomycin and PDC RNA aptamers have been utilized for this system and expressed in yeast from the GAL1 promoter. The IMAGEtag RNA kinetics were quantified by RT-qPCR. In yeast precultured in raffinose containing media the GAL1 promoter responded faster than in yeast precultured in glucose containing media. IMAGEtag RNA has relatively short half-life (5.5 min) in yeast. For imaging, the yeast cells are incubated with their ligands that are labeled with fluorescent dyes. To increase signal to noise, ligands have been separately conjugated with the FRET (Förster resonance energy transfer) pairs, Cy3 and Cy5. With these constructs, the transcribed aptamers can be imaged after activation of the promoter by galactose. FRET was confirmed with three different approaches, which were sensitized emission, acceptor photobleaching and donor lifetime by FLIM (fluorescence lifetime imaging microscopy). Real-time transcription was measured by FLIM-FRET, which ...
Date: December 13, 2011
Creator: Shin, Il Chung
Partner: UNT Libraries Government Documents Department

Devitrification kinetics and phase selection mechanisms in Cu-Zr metallic glasses

Description: Metallic glasses have been a promising class of materials since their discovery in the 1960s. Indeed, remarkable chemical, mechanical and physical properties have attracted considerable attention, and several excellent reviews are available. Moreover, the special group of glass forming alloys known as the bulk metallic glasses (BMG) become amorphous solids even at relatively low cooling rates, allowing them to be cast in large cross sections, opening the scope of potential applications to include bulk forms and net shape structural applications. Recent studies have been reported for new bulk metallic glasses produced with lower cooling rates, from 0.1 to several hundred K/s. Some of the application products of BMGs include sporting goods, high performance springs and medical devices. Several rapid solidification techniques, including melt-spinning, atomization and surface melting have been developed to produce amorphous alloys. The aim of all these methods is to solidify the liquid phase rapidly enough to suppress the nucleation and growth of crystalline phases. Furthermore, the production of amorphous/crystalline composite (ACC) materials by partial crystallization of amorphous precursor has recently given rise to materials that provide better mechanical and magnetic properties than the monolithic amorphous or crystalline alloys. In addition, these advances illustrate the broad untapped potential of using the glassy state as an intermediate stage in the processing of new materials and nanostructures. These advances underlie the necessity of investigations on prediction and control of phase stability and microstructural dynamics during both solidification and devitrification processes. This research presented in this dissertation is mainly focused on Cu-Zr and Cu-Zr-Al alloy systems. The Cu-Zr binary system has high glass forming ability in a wide compositional range (35-70 at.% Cu). Thereby, Cu-Zr based alloys have attracted much attention according to fundamental research on the behaviors of glass forming alloys. Further motivation arising from the application of this system ...
Date: December 15, 2010
Creator: Kalay, Ilkay
Partner: UNT Libraries Government Documents Department

Dislocation dynamics simulations of plasticity at small scales

Description: As metallic structures and devices are being created on a dimension comparable to the length scales of the underlying dislocation microstructures, the mechanical properties of them change drastically. Since such small structures are increasingly common in modern technologies, there is an emergent need to understand the critical roles of elasticity, plasticity, and fracture in small structures. Dislocation dynamics (DD) simulations, in which the dislocations are the simulated entities, offer a way to extend length scales beyond those of atomistic simulations and the results from DD simulations can be directly compared with the micromechanical tests. The primary objective of this research is to use 3-D DD simulations to study the plastic deformation of nano- and micro-scale materials and understand the correlation between dislocation motion, interactions and the mechanical response. Specifically, to identify what critical events (i.e., dislocation multiplication, cross-slip, storage, nucleation, junction and dipole formation, pinning etc.) determine the deformation response and how these change from bulk behavior as the system decreases in size and correlate and improve our current knowledge of bulk plasticity with the knowledge gained from the direct observations of small-scale plasticity. Our simulation results on single crystal micropillars and polycrystalline thin films can march the experiment results well and capture the essential features in small-scale plasticity. Furthermore, several simple and accurate models have been developed following our simulation results and can reasonably predict the plastic behavior of small scale materials.
Date: December 15, 2010
Creator: Zhou, Caizhi
Partner: UNT Libraries Government Documents Department

Fabrication and characterization of submicron polymer waveguides by micro-transfer molding

Description: Various methods exist for fabrication of micron and submicron sized waveguide structures. However, most of them include expensive and time consuming semiconductor fabrication techniques. An economical method for fabricating waveguide structures is introduced and demonstrated in this thesis. This method is established based on previously well-developed photonic crystal fabrication method called two-polymer microtransfer molding. The waveguide in this work functions by a coupler structure that diffracts the incident light into submicron polymer rods. The light is then guided through the rods. Characterization is done by collecting the light that has been guided through the waveguide and exits the end of these submicron polymer bars. The coupling and waveguiding capabilities are demonstrated using two light sources, a laser and white light.
Date: December 15, 2009
Creator: Wu, Te-Wei
Partner: UNT Libraries Government Documents Department

Transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates: Catalysts for asymmetric olefin hydroamination and acceptorless alcohol decarbonylation

Description: The research presented and discussed in this dissertation involves the synthesis of transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates, and their application in catalytic enantioselective olefin hydroamination and acceptorless alcohol decarbonylation. Neutral oxazolinylboranes are excellent synthetic intermediates for preparing new borate ligands and also developing organometallic complexes. Achiral and optically active bis(oxazolinyl)phenylboranes are synthesized by reaction of 2-lithio-2-oxazolide and 0.50 equiv of dichlorophenylborane. These bis(oxazolinyl)phenylboranes are oligomeric species in solid state resulting from the coordination of an oxazoline to the boron center of another borane monomer. The treatment of chiral bis(oxazolinyl)phenylboranes with sodium cyclopentadienide provide optically active cyclopentadienyl-bis(oxazolinyl)borates H[PhB(C{sub 5}H{sub 5})(Ox{sup R}){sub 2}] [Ox{sup R} = Ox{sup 4S-iPr,Me2}, Ox{sup 4R-iPr,Me2}, Ox{sup 4S-tBu]}. These optically active proligands react with an equivalent of M(NMe{sub 2}){sub 4} (M = Ti, Zr, Hf) to afford corresponding cyclopentadienyl-bis(oxazolinyl)borato group 4 complexes {PhB(C{sub 5}H{sub 4})(Ox{sup R}){sub 2}}M(NMe{sub 2}){sub 2} in high yields. These group 4 compounds catalyze cyclization of aminoalkenes at room temperature or below, providing pyrrolidine, piperidine, and azepane with enantiomeric excesses up to 99%. Our mechanistic investigations suggest a non-insertive mechanism involving concerted C−N/C−H bond formation in the turnover limiting step of the catalytic cycle. Among cyclopentadienyl-bis(oxazolinyl)borato group 4 catalysts, the zirconium complex {PhB(C{sub 5}H{sub 4})(Ox{sup 4S-iPr,Me2}){sub 2}}Zr(NMe{sub 2}){sub 2} ({S-2}Zr(NMe{sub 2}){sub 2}) displays highest activity and enantioselectivity. Interestingly, {S-2}Zr(NMe{sub 2}){sub 2} also desymmetrizes olefin moieties of achiral non-conjugated aminodienes and aminodiynes during cyclization. The cyclization of aminodienes catalyzed by {S-2}Zr(NMe{sub 2}){sub 2} affords diastereomeric mixture of cis and trans cylic amines with high diasteromeric ratios and excellent enantiomeric excesses. Similarly, the desymmetrization of alkyne moieties in {S-2}Zr(NMe{sub 2}){sub 2}-catalyzed cyclization of aminodiynes provides corresponding cyclic imines bearing quaternary stereocenters with enantiomeric excesses up to 93%. These stereoselective desymmetrization reactions are significantly affected by concentration of the substrate, temperature, and the presence of a ...
Date: December 17, 2012
Creator: Manna, Kuntal
Partner: UNT Libraries Government Documents Department

Study of the Two-pion Photoproduction on the Deuteron

Description: Understanding the structure of baryons in terms of the fundamental interaction of the constituent quarks and gluons is one of the primary challenges in strong interaction physics. This interaction is governed by Quantum Chromodynamics (QCD), which is a theory for understanding the dynamics of strong. QCD displays the asymptotic freedom of hadrons at very short distances and also the confinement of quarks and gluons inside hadrons. However, solutions of this QCD theory in the non-perturbative domain of the interaction are extremely difficult to achieve, mainly because confinement happens on the hadronic scale on which the coupling constant is large and prevents any perturbative approach. Thus leaving us with strategies such as lattice QCD or formulating QCD sum rules to get around this problem. In exclusive hadron production the yN interaction is recognized for being a powerful method for investigating hadrons and the mysteries that still exist within the strong interaction. From reactions with the nucleon, the strong interaction can be investigated through the transition amplitudes to the N and Delta resonances. More specifically, if an electromagnetic interaction is well known then the intermediate resonance states may be evaluated through meson photoproduction. To gain more detailed insight into this interaction, we look to probe the baryon structure of the nucleon and the photo-excited resonance decays through photon scattering off a deuteron producing two pions in the final state. This photoproduction process off the deuteron will be used to investigate known baryon resonances in the two pion channel. The two pion final state will be investigated for unraveling new information into the photo-coupling strengths. We want to explore final state interactions, search for properties of known resonances, and to explore the possibility of seeing missing states that are predicted by quark models but have not yet been found experimentally. Using the CEBAF ...
Date: December 1, 2012
Creator: Graham, Lewis P.
Partner: UNT Libraries Government Documents Department

Angle-resolved photoemission spectroscopy (ARPES) studies of cuprate superconductors

Description: This dissertation is comprised of three different angle-resolved photoemission spectroscopy (ARPES) studies on cuprate superconductors. The first study compares the band structure from two different single layer cuprates Tl{sub 2}Ba{sub 2}CuO{sub 6+{delta}} (Tl2201) T{sub c,max} {approx} 95 K and (Bi{sub 1.35}Pb{sub 0.85})(Sr{sub 1.47}La{sub 0.38})CuO{sub 6+{delta}} (Bi2201) T{sub c,max} {approx} 35 K. The aim of the study was to provide some insight into the reasons why single layer cuprate's maximum transition temperatures are so different. The study found two major differences in the band structure. First, the Fermi surface segments close to ({pi},0) are more parallel in Tl2201 than in Bi2201. Second, the shadow band usually related to crystal structure is only present in Bi2201, but absent in higher T{sub c} Tl2201. The second study looks at the different ways of doping Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8+{delta}} (Bi2212) in-situ by only changing the post bake-out vacuum conditions and temperature. The aim of the study is to systematically look into the generally overlooked experimental conditions that change the doping of a cleaved sample in ultra high vacuum (UHV) experiments. The study found two major experimental facts. First, in inadequate UHV conditions the carrier concentration of Bi2212 increases with time, due to the absorption of oxygen from CO{sub 2}/CO molecules, prime contaminants present in UHV systems. Second, in a very clean UHV system at elevated temperatures (above about 200 K), the carrier concentration decreases due to the loss of oxygen atoms from the Bi-O layer. The final study probed the particle-hole symmetry of the pseudogap phase in high temperature superconducting cuprates by looking at the thermally excited bands above the Fermi level. The data showed a particle-hole symmetric pseudogap which symmetrically closes away from the nested FS before the node. The data is consistent with a charge density wave (CDW) origin of the ...
Date: December 15, 2010
Creator: Palczewski, Ari Deibert
Partner: UNT Libraries Government Documents Department

Reducing the losses of optical metamaterials

Description: The field of metamaterials is driven by fascinating and far-reaching theoretical visions, such as perfect lenses, invisibility cloaking, and enhanced optical nonlinearities. However, losses have become the major obstacle towards real world applications in the optical regime. Reducing the losses of optical metamaterials becomes necessary and extremely important. In this thesis, two approaches are taken to reduce the losses. One is to construct an indefinite medium. Indefinite media are materials where not all the principal components of the permittivity and permeability tensors have the same sign. They do not need the resonances to achieve negative permittivity, {var_epsilon}. So, the losses can be comparatively small. To obtain indefinite media, three-dimensional (3D) optical metallic nanowire media with different structures are designed. They are numerically demonstrated that they are homogeneous effective indefinite anisotropic media by showing that their dispersion relations are hyperbolic. Negative group refraction and pseudo focusing are observed. Another approach is to incorporate gain into metamaterial nanostructures. The nonlinearity of gain is included by a generic four-level atomic model. A computational scheme is presented, which allows for a self-consistent treatment of a dispersive metallic photonic metamaterial coupled to a gain material incorporated into the nanostructure using the finite-difference time-domain (FDTD) method. The loss compensations with gain are done for various structures, from 2D simplified models to 3D realistic structures. Results show the losses of optical metamaterials can be effectively compensated by gain. The effective gain coefficient of the combined system can be much larger than the bulk gain counterpart, due to the strong local-field enhancement.
Date: December 15, 2010
Creator: Fang, Anan
Partner: UNT Libraries Government Documents Department

Influence of microstructure on stress corrosion cracking of mild steel in synthetic caustic-nitrate nuclear waste solution

Description: The influence of alloy microstructure on stress corrosion cracking of mild steel in caustic-nitrate synthetic nuclear waste solutions was studied. An evaluation was made of the effect of heat treatment on a representative material (ASTM A 516 Grade 70) used in the construction of high activity radioactive waste storage tanks at Savannah River Plant. Several different microstructures were tested for susceptibility to stress corrosion cracking. Precracked fracture specimens loaded in either constant load or constant crack opening displacement were exposed to a variety of caustic-nitrate and nitrate solutions. Results were correlated with the mechanical and corrosion properties of the microstructures. Crack velocity and crack arrest stress intensity were found to be related to the yield strength of the steel microstructures. Fractographic evidence indicated pH depletion and corrosive crack tip chemistry conditions even in highly caustic solutions. Experimental results were compatible with crack growth by a strain- assisted anodic dissolution mechanism; however, hydrogen embrittlement also was considered possible. (auth)
Date: December 1, 1975
Creator: Sarafian, P.G.
Partner: UNT Libraries Government Documents Department

Diffusion Compton profondement virtuelle dans le Hall A au Jefferson Laboratory

Description: Generalized Parton Distributions (GPDs), introduced in the late 90s, provide a universal description of hadrons in terms of the underlying degrees of freedom of Quantum Chromodynamics: quarks and gluons. GPDs appear in a wide variety of hard exclusive reactions and the advent of high luminosity accelerator facilities has made the study of GPDs accessible to experiment. Deeply Virtual Compton Scattering (DVCS) is the golden process involving GPDs. The first dedicated DVCS experiment ran in the Hall A of Jefferson Lab in Fall 2004. An electromagnetic calorimeter and a plastic scintillator detector were constructed for this experiment, together with specific electronics and acquisition system. The experiment preparation, data taking and analysis are described in this document. Results on the absolute cross section difference for opposite beam helicities provide the first measurement of a linear combination of GPDs as a function of the momentum transfer to the nucleon.
Date: December 1, 2005
Creator: Camacho, Carlos Munoz
Partner: UNT Libraries Government Documents Department

Measurement of the neutron ({sup 3}He) spin structure functions at low Q{sup 2}: A CONNECTION BETWEEN THE BJORKEN AND GERASIMOV-DRELL-HEARN SUM RULE

Description: This dissertation presents results of experiment E94-010 performed at Jefferson Laboratory (simply known as JLab) in Hall A. The experiment aimed to measure the low Q{sup 2} evolution of the Gerasimov-Drell-Hearn (GDH) integral from Q{sup 2} = 0.1 to 0.9 GeV{sup 2}. The GDH sum rule at the real photon point provides an important test of Quantum Chromodynamics (QCD). The low Q{sup 2} evolution of the GDH integral contests various resonance models, Chiral Perturbation Theory ({chi}#31;PT) and lattice QCD calculations, but more importantly, it helps us understand the transition between partonic and hadronic degrees of freedom. At high Q{sup 2}, beyond 1 GeV{sup 2}, the difference of the GDH integrals for the proton and the neutron is related to the Bjorken sum rule, another fundamental test of QCD. In addition, results of the measurements for the spin structure functions g{sub 1} and g{sub 2}, cross sections, and asymmetries are presented. E94-010 was the first experiment of its kind at JLab. It used a high-pressure, polarized {sup 3}He target with a gas pressure of 10 atm and average target polarization of 35%. For the first time, the polarized electron source delivered an average beam polarization of 70% with a beam current of 15 {micro}#22;A. The limit on the beam current was only imposed by the target. The experiment required six different beam energies from 0.86 to 5.1 GeV. This was the first time the accelerator ever reached 5.1 GeV. Both High-Resolution Spectrometers of Hall A, used in singles mode, were positioned at 15.5#14;{deg} each.
Date: December 1, 2002
Creator: Djawotho, Pibero
Partner: UNT Libraries Government Documents Department

Charge Transfer and Support Effects in Heterogeneous Catalysis

Description: The kinetic, electronic and spectroscopic properties of two‐dimensional oxide‐supported catalysts were investigated in order to understand the role of charge transfer in catalysis. Pt/TiO{sub 2} nanodiodes were fabricated and used as catalysts for hydrogen oxidation. During the reaction, the current through the diode, as well as its I‐V curve, were monitored, while gas chromatography was used to measure the reaction rate. The current and the turnover rate were found to have the same temperature dependence, indicating that hydrogen oxidation leads to the non‐adiabatic excitation of electrons in Pt. A fraction of these electrons have enough energy to ballistically transport through Pt and overcome the Schottky barrier at the interface with TiO{sub 2}. The yield for this phenomenon is on the order of 10{sup ‐4} electrons per product molecule formed, similar to what has been observed for CO oxidation and for the adsorption of many different molecules. The same Pt/TiO{sub 2} system was used to compare currents in hydrogen oxidation and deuterium oxidation. The current through the diode under deuterium oxidation was found to be greater than under hydrogen oxidation by a factor of three. Weighted by the difference in turnover frequencies for the two isotopes, this would imply a chemicurrent yield 5 times greater for D{sub 2} compared to H{sub 2}, contrary to what is expected given the higher mass of D{sub 2}. Reversible changes in the rectification factor of the diode are observed when switching between D{sub 2} and H{sub 2}. These changes are a likely cause for the differences in current between the two isotopes. In the nanodiode experiments, surface chemistry leads to charge flow, suggesting the possibility of creating charge flow to tune surface chemistry. This was done first by exposing a Pt/Si diode to visible light while using it as a catalyst for H{sub 2} oxidation. ...
Date: December 21, 2011
Creator: Hervier, Antoine
Partner: UNT Libraries Government Documents Department