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Characterization of Surfaces Designed for Biomedical ApplicationsKristensen, Emma January 2006 (has links)
In order to develop blood biocompatible materials a heparin surface and a phosphorylcholine (PC) functionalized polymer surface were characterized using photoelectron spectroscopy (PES). The formation of the heparin surface was studied by quartz crystal microbalance with dissipation monitoring (QCM-D). This heparin surface consists of heparin conjugates deposited on a conditioning layer, applied once or twice. The PC functionalized polymer, poly(trimethylene carbonate), was linked to a silicon substrate through 3-amino- propyltrimethoxysilane (APTMS), also studied using PES. Synchrotron radiation based PES showed that the thicker heparin film resulted in complete coverage of the substrate, while the thinner did not. This could explain the difference in blood biocompatibility between the two films, as observed by others. It was also found that the heparin chains bend down towards the substrate (under vacuum). For the thinner heparin film the modifications, resulting from extensive irradiation of the sample, were studied with synchrotron radiation based PES. This was done at a pressure of about 10-7 mbar and in 0.5 mbar water vapor. It was found that the modification is slower under water vapor than at low pressures and that the damaged film incorporates water upon exposure. The heparin coating was found to be stable and wear resistant enough to still be present on artificial heart valves after three weeks testing in circulating plasma. It then had about the same antithrombin uptake as a non-tested surface. The film was, however, partly destroyed by the durability test and plasma proteins were deposited. The PC functionalized, APTMS linked polymer was found to be much shorter than could be expected from random reactions. One plausible explanation is an interaction between the PC group and the silane surface, favoring aminolysis close to the PC group. This is consistent with our finding that the PC group bends down towards the surface.
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The Studies of X-ray Photoelectron Spectroscopy for the Interface of Gallium-Gadolinium Oxide / Gallium ArsenicHuang, Kuang-Han 29 July 2000 (has links)
This work is to study the interface properties of Gallium-Gadolinium oxide / GaAs structures. The samples we probed were produced by depositing oxide films in situ on freshly grown n type GaAs (100) surface. Three different oxides were deposited : Ga2O3, Gd2O3, and (Ga2O3-Gd2O3) oxide mixture. Structural properties of the interfaces have been investigated by X-ray photoelectron spectroscopy (XPS). Using Ar+ sputtering to remove the oxide layer step by step, we are able to observe the depth profiles of these samples. No Asenic or Asenic oxides are observed at the interfaces of these samples. The Ga(3d) of Ga2O3 / GaAs interface shows three different oxidation states, whose binding energies are 21.5eV, 21.0eV and 20.3eV, respectively. The binding energy of O (1s) core level is about at 530eV. For (Ga2O3-Gd2O3) / GaAs, Ga(3d) peaks exhibit at 21.0eV and 20.3eV. Also, two O (1s) peaks were clearly observed: one is Ga-O at 532.2eV and the other is Gd-O at 530.1eV. For the Gd2O3 / GaAs, only one Ga(3d) peak shows at 20.3eV, and the O (1s) spectra exhibit two peaks related to Ga-O at 532eV and Gd-O at 530eV, similar to the data of (Ga2O3-Gd2O3) sample. In conclusion, the Ga2O3 / GaAs interface has a Ga2O3 and two non-fully oxidized GaxOy states (i.e. Ga+1, Ga+2). The (Ga2O3-Gd2O3) layer consists two non-fully oxidized GaxOy states. For the Gd2O3 / GaAs interface, the GaxOy (Ga+1) state is formed possibly by the competitive oxidation of Ga, which diffused from the GaAs substrate, with the Gd2O3.
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Probing the High-£e Dielectric-Semiconductor interfaces by X-ray Photoelectron SpectroscopyLiao, Yi-Ying 09 July 2002 (has links)
The purpose of this thesis is to probe microscopic compositions and electronic structures at the high-£edielectric-semiconductor interfaces. The samples are prepared by electron beam evaporation, including Y2O3/Si, (Ga2O3-Gd2O3)/GaAs, Gd2O3/GaAs, Gd2O3/GaN and (Ga2O3-Gd2O3)/GaN. The thermal annealing effects on the interfacial properties have been investigated by depth-profiling X-ray photoelectron spectroscopy (XPS) with synchrotron radiation beam.
The depth-profiling XPS data show the O-H bonding in all the measured oxide layers. For Y2O3/Si, the hydroxide can be removed by surface desorption at 300¢J, while a Y-Si-O-H state maintained at the interface. The data suggests that the Y-Si-O-H state is possibly formed in the deposition process. For (Ga2O3-Gd2O3)/GaAs, the hydroxide can be removed by surface desorption at 100¢J, and GaOx and GaOy intermediary states have been observed. For Gd2O3/GaAs, the hydroxide can be removed by surface desorption at 250¢J, and a GaOx intermediary state has been observed, and no arsenic oxides have been detected. For Gd2O3/GaN and (Ga2O3-Gd2O3)/GaN, a GaOx intermediary state and little N-O bonding have been observed. Comparing the XPS relative intensity of the N 1s states, (Ga2O3-Gd2O3)/GaN shows a more stable interface than Gd2O3/GaN.
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Surface processes ruthenium film growth, silicon nanocrystal synthesis, and methylene partial oxidation /Smith, Kristen Colleen. January 2001 (has links)
Thesis (Ph. D.)--University of Texas at Austin, 2001. / Vita. Includes bibliographical references. Available also from UMI Company.
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Surface processes : ruthenium film growth, silicon nanocrystal synthesis, and methylene partial oxidationSmith, Kristen Colleen 06 April 2011 (has links)
Not available / text
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Relationships between Gas-Phase Ionization Energies and Solution-Phase Oxidation Potentials: Applications to the Electrocatalytic Production of Hydrogen from Weak AcidsSakamoto, Takahiro January 2010 (has links)
The transfer of electrons to and from a molecule is one of the more fundamental and important chemical processes. One such important example is the reduction-oxidation (redox) cycles in catalysts and enzymes. In the hydrogenase enzymes, adding and removing electrons is one of the key processes for generating H₂ from water molecules. Finding a direct free energy relation between the vertical ionization energies (IE(V)) measured spectroscopically by gas-phase photoelectron spectroscopy and the oxidation potentials (E(1/2)) measured thermodynamically in solution by cyclic voltammetry (CV) for molecules is an important aspect for developing effective catalysts. In this study, a series of organometallic compounds such as metallocenes were used for investigating the free energy relationships and catalysts inspired by the active sites of [FeFe]-hydrogenases enzymes were evaluated for their ability to produce H₂ from electrocatalytic reduction of weak acids. The first part of the dissertation explores metallocenes of the form (η⁵-C₅H₅)₂M (M= Fe, Ru, Os, Co, Ni) as the model for developing the free energy relation between gas phase ionization energies (IE(V)) and solution oxidation potentials (E(1/2)). It was found that computing the electronic properties of Cp₂Fe, Cp₂Ru, and Cp₂Os using VWN-Stoll and OPBE density functional theory (DFT) functional was successful with root mean square deviation (RMSD) of 0.02 eV between the experimental and calculated ionization energies. However, calculated ionization energies of Cp₂Co and Cp₂Ni were less successful with RMSD of 0.3 eV between the experimental and calculated ionization energies. Introduction of the B3LYP or M06 hybrid DFT functionals yielded much improved results (0.1 eV) over the previous combinations of DFT functional for Cp2Co and Cp2Ni. The energy relation between the two experimental measurements was established and further computational studies revealed that the solvation energy was the largest energy contribution between IE(V) and E(1/2) in the five studied metallocenes. The RMSD of the calculated oxidation potentials, after adjusting for the error in gas-phase ionization energies, was 0.09 V. The second part of the dissertation explores a series of catalysts inspired by the active sites of [FeFe]-hydrogenase enzymes; μ-(2,3-pyrazinedithiolato)diironhexacarbonyl (PzDT-cat), Fe₂(μ-X₂C₅H₈O)(CO)₆ (where X = S, Se, Te), and Fe₂(μ-1,3-SC₃H₆X)(CO)₆ (where X = Se and Te) for their ability to produce H₂ from weak acids utilizing the computational techniques and knowledge gained from the metallocene study. Even though the overall electronic perturbation from μ-(1,2-benzenedithiolato)diironhexacarbonyl (BDT-cat) to μ-(2,3-pyridinedithiolato)diironhexacarbonyl (PyDT-cat) to PzDT-cat is found to be small, the reduction potential of PzDT-cat was found to be 0.15 V less negative than that of BDT-cat resulting in less energy required for initiating electrocatalytic H₂ production over the BDT-cat and PyDT-cat. Lower reorganization energy has been achieved by substitutions of larger chalcogens at the Fe₂S₂ core. However, the electrocatalytic production of H₂ from acetic acid in acetonitrile was found to be diminished upon going from analogous S to Se to Te species. This is ascribed to the increase in the Fe–Fe bond distance with a corresponding increase in the size of the chalcogen atoms from S to Se to Te, disfavoring the formation of a carbonyl-bridged structure in the anion which is thought to be critical to the mechanism of H₂ production.
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LOCAL ELECTRONIC PROPERTIES OF ORGANIC SEMICONDUCTOR INTERFACESBlumenfeld, Michael Lewis January 2010 (has links)
Understanding organic semiconductor interfaces is critical to developing organic photovoltaics (OPV). OPV interfaces are disordered due to weak intermolecular interactions, resulting in diverse charge transfer micro-environments. I present experimental data isolating high-order intermolecular interactions controlling interfacial energy level alignment and describe new instrumental capabilities providing access to the local electronic and kinetic landscape at organic semiconductor interfaces. Interface formation between vanadyl naphthalocyanine (VONc) and highly ordered pyrolytic graphite (HOPG) is investigated. Ultraviolet photoemission spectroscopy (UPS) shows that the VONc binding energy (BE) decouples from the work function, shifting in an opposite direction and contradicting the standard interface dipole model. This effect is quantitatively described using an electrostatic depolarization model and confirmed by simulations which show an inhomogeneous potential at the interface. New data and literature values suggest orthogonality between polarizability and molecular dipole in polar porphyrazines. Their potential for interface engineering is discussed. The electron-rich Au(111)/VONc interface is investigated. The organic layer induces a large interface dipole in Au(111) which can be fit to a depolarization model. Ionization potential and depolarization data suggest that the second VONc layer on Au(111) adopts a tilted geometry. Electrostatic differences between Au(111)/VONc and HOPG/VONc are discussed, demonstrating that interface dipole contributions are not interchangeable. The surface states of the Au(111)/VONc interface are characterized by angle resolved 2-photon photoemission to determine the magnitude of the perturbation. The measured free-electron-like effective mass and BE destabilization of the Shockley state is attributed to step edges caused by lifting the Au(111) (22 x √3) reconstruction. The Shockley state is accessible primarily through resonance with the n = 1 image state. Another resonance between the image state and a molecular state of VONc is tentatively identified. Design and construction of a confocal fluorescence microscope capable of single molecule detection in ultrahigh vacuum is described. Initial images and fluorescence trajectories demonstrate the ability to measure charge transfer kinetics between an individual organic semiconductor molecule and well-characterized insulating surfaces. Progress towards completion of a scanning photoionization microscope is presented. The microscope demonstrates diffraction-limited imaging capabilities using fs-laser-generated photoelectron current as contrast. Recommendations are given towards achieving spectral resolution and for future experimental systems.
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X-Ray Photoemission Spectroscopy Characterization of Fe(II)- and Fe(III)-Phthalocyanine Molecular FilmsDroschke, Sonja January 2015 (has links)
This thesis investigates the electronic structure of iron phthalocyanine (Fe(II)Pc) andiron phthalocyanine chloride (Fe(III)PcCl) immobilized on surfaces. For this purposetwo different deposition methods are used and compared: smearing the molecularpowder under atmosphere condition and evaporation of a molecular layer inultra-high vacuum. The electronic states of FePc and FePcCl are probed withphotoelectron spectroscopy (PES) and compared in relation to the ionic state of thecentral metal (Fe). The PE spectra show that evaporation of FePcCl at around 350°Cresults in dissociation of the chlorine from the FePc molecule, which is stable at thistemperature. Mass spectroscopic measurements during heating of FePcCl in ultra-highvacuum (UHV) show a clear Cl signal for temperature still below 250°C. Theoreticalcalculations of the binding energy for Cl in FePcCl seem to indicate dissociation of theCl from the molecules.
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An investigation of cellulose nitrates and double based propellant by spectroscopic techniques with particular reference to E.S.C.AStephenson, Peter John January 1981 (has links)
No description available.
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Photo-induced reversible changes in wettability on light sensitive pyrimidine-coated surfacesAbbott, Scott John January 2000 (has links)
Thin coatings of photoresponsive, pyrimidine-terminated molecules, attached to gold or quartz substrates in contact with water, undego photodimerisation and wettability changes when irradiated with UV light at 280 and 240mm. Spin-casting and chemisorption techniques were used to prepare the thin films. / Thesis (PhDApSc)--University of South Australia, 2000.
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