In this study, a bidentate ligand, 6-ferrocenyl-2,2&#039 / -bipyridine, was prepared by the reaction of lithiated ferrocene with bipyridine. The ligand was identified by 1H, 13C- NMR and HMQC and UV-Vis spectroscopies. Then, bidentate molecule was reacted with pentacarbonylbis-(trimethylsilylethyne)tungsten(0). The ligand substitution reaction in CH2Cl2 yielded the new complex, tetracarbonyl(6-ferrocenyl-2,2&#039 / bipyridine)tungsten(0). The isolated and purified complex was fully characterized by elemental analysis, IR, UV-Vis, MS, 1H and 13C- NMR spectroscopies. Tetracarbonyl(6-ferrocenyl-2,2&#039 / bipyridine)chromium(0) was also formed by ligand substitution reaction of 6-ferrocenyl-2,2&#039 / -bipyridine with pentacarbonyl(THF)chromium(0) which was prepared by photolytic substitution of CO from hexacarbonyl chromium(0) in THF. However, tetracarbonyl(6-ferrocenyl-2,2&#039 / bipyridine)chromium(0) could not be isolated by column chromatography. Electrochemistry of 6-ferrocenyl-2,2&#039 / -bipyridine and tetracarbonyl(6-ferrocenyl-2,2&#039 / bipyridine)tungsten(0) was studied by cyclic voltammetry and controlled potential electrolysis combined with UV-Vis. The ligand exhibits a reversible reduction and a reversible oxidation belonging to bipyridine and ferrocene moieties, respectively. One reversible reduction, two irreversible oxidation and a reversible oxidation were observed for tetracarbonyl(6-ferrocenyl-2,2&#039 / bipyridine)tungsten(0). The reversible reduction was attributed to bipyridine whereas two irreversible oxidations were assigned to tungsten centers and reversible oxidation to iron center.

Catalysts play a vital role in almost every aspect of our lives and are used in the production of fuels, polymers, chemicals, foods, and pharmaceuticals. One challenge facing the heterogeneous catalysis community is the targeted synthesis of dispersed catalyst ensembles. The Barnes research group has developed a general methodology for the synthesis of nanostructured silicate building block supports and heterogeneous catalysts. This methodology provides researchers with the ability to control the dispersion of surface functionality, the dispersion of metal cation centers, the number of linkages from the metal cation center to the support, the surface area of the support, and the porosity of the support. This dissertation describes work aimed at synthesizing and characterizing nanostructured silicate building block supports and heterogeneous catalysts. Nanostructured silicate building block supports were synthesized by reacting SiCl4py2 with Si8O12(OSnMe3)8. The resulting supports contained spatially isolated Me3Sn groups and the density of Me3Sn groups was targeted by varying the stoichiometric ratio of reactants. The stoichiometric ratio of reactants also controlled the surface area and porosity of the supports. Nanostructured heterogeneous catalysts with isolated tungsten(VI) or zirconium(IV) centers were synthesized by reacting a limiting amount of a metal chloride with either Si8O12(OSnMe3)8 or a premade silicate building block support. Two types of catalysts ensembles were targeted: embedded and surface. Embedded ensembles were successfully targeted using WOCl4 and ZrCl4 while the reaction between WCl6 and the building block did not result in the preparation of the targeted ensemble. However the resulting ensemble was thoroughly characterized even though the targeted ensemble was not produced. In all three cases a single type of catalyst ensembles was synthesized and a high surface area silicate support was generated around the embedded ensembles without disrupting the ensemble itself. Surface ensembles were successfully targeted using ZrCl4. The reaction between the tungsten chlorides (WOCl4 and WCl6) and the premade support did not result in the preparation of the targeted ensembles however the resulting ensembles were thoroughly characterized.

Die Anzahl neurodegenerativer Erkrankungen nimmt in unserer Gesellschaft stetig zu. Obwohl inzwischen eine Reihe genetischer Ursachen identifiziert worden sind, wird auch der Einfluss von Umweltfaktoren bei der Pathogenese dieser Erkrankungen zunehmend in Betracht gezogen. Der Beitrag von ultrafeinen Partikeln aus Industrie und Umwelt auf neurodegenerative Erkrankungen steht daher zunehmend im Fokus der Forschung. Die Translokation von ultrafeinen Partikeln bzw. Nanopartikeln ins Gehirn ist bekannt. Die Charakterisierung neuro- und gliotoxischer Wirkungen von Nanopartikeln in einem in vitro System war deshalb Ziel dieser Arbeit. Untersucht wurden Wolframcarbid-Partikel mit und ohne Cobalt, die im Herstellungsprozess von Hartmetallen von Bedeutung sind. Die meisten toxikologischen Daten wurden bisher mit mikrokristallinen WC-Pulvern an Lungenzellen bzw. -gewebe erhoben. Da aber die Verarbeitung von nanoskaligen Partikeln bessere Eigenschaften der Hartmetalle bewirkt, nimmt das Interesse an toxikologischen Studien mit WC-Nanopartikeln zu. Da die Gefahr der Translokation und Akkumulation im Gehirn beim Einatmen von Stäuben am Arbeitsplatz besteht, wurde erstmalig die Toxizität von WC-NP mit und ohne Cobalt auf Zellen des Gehirns untersucht. Für die Durchführung wurden primäre Neuronen, Astrozyten und Mikroglia sowie die Oligodendrozyten-vorläuferzelllinie OLN-93 der Ratte eingesetzt. Alle untersuchten Partikel konnten mittels Elektronenmikroskopie, ICP-Massenspektrometrie und Durchflusszytometrie in den verschiedenen Zelltypen nachgewiesen werden. Untersuchungen mit Cytochalasin D (Inhibitor der Aktinpolymerisation) deuteten auf zell- und partikelspezifische Aufnahmemechanismen hin. Experimente mit Cobaltchlorid und Natriumwolframat konnten beweisen, dass nicht die gelösten Ionen für die Toxizität von WC-Co ursächlich waren, sondern die Partikelform von entscheidender Bedeutung ist. Es zeigte sich jedoch, dass einige der WC-Co verursachten Effekte vermutlich auf dem Cobaltanteil beruhen. Offensichtlich dienen WC-Co-NP als Vehikel, um Cobalt in die Zellen einzuschleusen. Zur toxischen Wirkung trägt auch das Reaktionsvermögen von WC und Cobalt an der beiderseitigen Grenzfläche bei, denn dadurch können in der Zelle vermehrt reaktive Sauerstoffspezies gebildet werden. Im Rahmen der Untersuchungen wurden die zeit- und konzentrationsabhängigen Effekte der Nanopartikelexposition auf die Vitalität, die Proliferation, das Adhäsionsverhalten, das mitochondriale Membranpotential und die Induktion apoptotischer und nekrotischer Zelluntergänge untersucht. Dabei wurden verschiedene Vitalitäts- und Proliferationstests angewendet, um die häufig beobachteten Wechselwirkungen zwischen Reagenzien und Nanopartikeln auszuschließen. Nicht alle untersuchten Nanopartikel erwiesen sich in den durchgeführten Experimenten als akut toxisch. Nur eine Exposition mit WC-Co-NP führte nach 72 h zu einer deutlich verringerten Vitalität und Proliferation bei Astrozyten und OLN-93 Zellen. Eine Exposition mit WC-Co-NP zeigte des Weiteren eine geringe Induktion von Apoptose und Nekrose bei Astrozyten, nicht aber bei OLN-93 Zellen. Neurone wiesen nach einer Exposition mit NP eine wenig verringerte Vitalität auf. Es wurde festgestellt, dass erst die primäre Schädigung von Astrozyten zu einer sekundären Neuronenschädigung führt. Bei der Bewertung der NP-Toxizität müssen daher unbedingt die Wechselwirkungen der Zellen bedacht werden. Die Exposition mit WC- und WC-Co-NP beeinflusste das mitochondriale Membranpotential und das Adhäsionsverhalten der untersuchten Zellen. Neuronen und OLN-93 Zellen zeigten nach NP-Exposition eine verminderte Adhäsion. Auch physiologische Kalziummessungen lieferten einen Hinweis für die veränderte Funktionalität glialer Zellen nach einer NP-Exposition. Des Weiteren wurde die Expression einiger Gene, bedeutend für Adhäsion und extrazelluläre Matrix, mit realtime RT-PCR bei OLN-93-Zellen und Astrozyten überprüft. Es konnte eine Regulation von Mmp9, Timp1, Lama3, Tgfbi, Col8a1 und Hmox1 gezeigt werden. Zusammenfassend lässt sich feststellen, dass die ausgewählten Nanopartikel nicht per se neuro- und gliotoxisch wirkten. Die Partikel können anhand abnehmender Toxizität wie folgt geordnet werden: WC-Co > WC 100na > WC 10n. Auch die Reaktionen der Zellen fielen unterschiedlich aus: die Astrozyten erwiesen sich als die sensitivsten Zellen. Eine Exposition des Gehirns mit WC-Co-NP in hohen Konzentrationen oder über einen längeren Zeitraum könnte also weit reichende Folgen haben, angefangen bei einer gestörten Signalweiterleitung über eine erhöhte Permeabilität der Blut-Hirn-Schranke bis hin zu neurodegenerativen Veränderungen. Diese und weitere Untersuchungen könnten bei der Erstellung von Arbeitsrichtlinien im Umgang mit Hartmetallen, deren Ausgangsmaterial nanoskalige Pulver sind, hilfreich sein und damit einen Beitrag zum Schutz der Arbeiter liefern.

This thesis investigates the electrochromic NixW1-x oxide thin film system, where 0 < x < 1. The thin films were deposited by reactive DC magnetron co-sputtering from one Ni and one W metal target. In addition, Ni oxide was deposited with water vapor added to the sputtering gas. The different compositions were structurally characterized by X-ray diffraction, X-ray photoelectron-, Rutherford backscattering- and Raman spectroscopy. Possible nanostructures were studied by ellipsometry together with effective medium theory. Optical and electrochemical properties were investigated by spectrophotometry and cyclic voltammetry in 1 M lithium perchlorate in propylene carbonate (Li-PC). Li-PC electrolyte was used as it is being compatible with both W and Ni oxides. Few studies have previously been made on Ni oxides in Li-PC. Films with high Ni content, 0.85 < x < 1, were polycrystalline and all other films were amorphous. W-rich films, x < 0.5, consisted of a mixture of W oxide and NiWO4 -phases, and the Ni-rich samples, x > 0.5, probably consisted of hydrated Ni oxide and NiWO4 -phases. Films with 0 < x < 0.3 showed electrochromic properties similar to W oxide, and films with 0.7 < x < 1 behaved as Ni oxide. For 0.4 < x < 0.7 no optical change was seen. At the border of cathodic electrochromic and non-electrochromic behavior, i.e. x ~ 0.4, the sample behaved as an optically passive intercalation material. The transmittance change was 0.45 and 0.15 for the W-rich and Ni-rich films, respectively. Ni addition to W oxide improved the coloration efficiency. For the Ni-rich films the charge insertion/extraction and optical modulation was low and an aging effect resulted in strong bleaching of the samples. The advantage of W addition to Ni oxide was that the transparency at the bleached state was enhanced. Moreover, it was found that the hydrous character of the Ni oxide had a large impact on the electrochromic performance, both when electrochemically cycled in KOH and in the non-aqueous Li-PC.

Thesis (M.S.)--University of Texas at El Paso, 2008. / Title from title screen. Vita. CD-ROM. Includes bibliographical references. Also available online.

Thesis (Ph. D.)--University of Texas at Austin, 2004. / Supervisor: Michael D. Bryant. Vita. Includes bibliographical references.

Thesis (Ph. D.)--Ohio State University, 2007. / Title from first page of PDF file. Includes bibliographical references (p. 208-222).

Made available in DSpace on 2014-10-09T12:44:30Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:57:21Z (GMT). No. of bitstreams: 1 06907.pdf: 7394695 bytes, checksum: bde9c680792583e55f4754af5867fe98 (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Neste trabalho foram obtidos filmes de óxido de tungstênio pelo método sol-gel modificado, tendo como precursor o tungstato de sódio dihidratado (Na2WO4.2H2O) e como agente estruturante o surfactante cloreto de dodeciltrimetilamônio (DTAC). O comportamento dos sistemas em meio aquoso foi avaliado por medidas de pH, condutividade e viscosidade. Foram avaliadas duas metodologias de obtenção dos filmes de óxido de tungstênio: a primeira consistiu na obtenção de filmes de tungstato de sódio, através de sistemas contendo 10 mmol.L-1 de Na2WO4.2H2O em diferentes concentrações de DTAC, por casting, e conversão do tungstato de sódio a óxido de tungstênio pela acidificação dos filmes; a segunda metodologia consistiu na conversão dos sistemas aquosos contendo 20 mmol.L-1 de Na2WO4.2H2O, em diferentes concentrações de DTAC, em ácido tungstico, obtenção dos filmes por spin coating e, calcinação em presença de ar. Os filmes foram obtidos em substratos de silício (100) recobertos com dióxido de silício e avaliados por Difração de Raios-X, Espectrometria de retroespalhamento Rutherford, Espectroscopia Raman, Microscopia Eletrônica de Varredura e ensaios fotocatalíticos. As alterações na concentração precursor e agente estruturante não afetaram significativamente o pH e a viscosidade dos sistemas precursores. A determinação da concentração micelar crítica (cmc) do DTAC, obtida através da condutividade, foi de 13 mmol.L-1 e 9,88 mmol.L-1 para os sistemas contendo 10 e 20 mmol.L-1 de Na2WO4.2H2O, respectivamente. Em ambas metodologias o produto final foi o óxido de tungstênio em forma de disco e placas. As espessuras dos filmes obtidos na primeira metodologia variaram de 4 a 5 μm e as estruturas tiveram diâmetros médios de 4,37 μm e 114 nm. Na segunda metodologia as espessuras foram de 0,5-1,0 μm e as estruturas obtidas tiveram diâmetros médios em torno de 95-103 nm. Os filmes obtidos apresentaram atividade fotocatalítica, uma vez que duplicaram a velocidade da reação de degradação do corante alaranjado de metila em relação ao sistema sem o filme. / In this work tungsten oxide films have been obtained bymodified sol-gel method, with sodium tungstate dehydrate (Na2WO4.2H2O) as the precursor and the cationic surfactant dodecyltrimethylammonium chloride (DTAC) as structuring agent.The behavior in aqueous media of precursor/structuring agent systems was characterized by pH, conductivity and viscosity measurements. Two methods for obtaining tungsten oxide films were evaluated: the first consisted in obtaining sodium tungstate films from the systems containing 10 mmol.L-1 of Na2WO4.2H2O at different DTAC concentrations, by casting, converting the sodium tungstate to tungsten oxide; the second method consisted in the conversion of the aqueous systems containing 20 mmol.L-1 of Na2WO4.2H2O at different DTAC concentrations to tungstic acid, obtaining the films by spin coating and, posteriorly, calcination in the presence of air. The films were obtained on silicon substrate (100) with a 50 nm layer of silicon dioxide and were characterized by X-ray diffraction, Rutherford backscattering spectrometry, Raman spectroscopy, Scanning Electron Microscopy and photocatalytic tests. The precursor concentration and structuring agent do not affect significantly the pH and the viscosity of the precursor systems in aqueous media.The values of critical micelle concentration (CMC) of DTAC, obtained by the conductivity, were of13 mmol.L-1 and 9,88 mmol.L-1, for the systems containing 10 and 20 mmol.L-1 de Na2WO4.2H2O, respectively.In both adopted methods the final product is the tungsten oxide, with nano and micrometric structures in the form of discs and plates. The thickness of the films obtained in the first method varied from 4 to 5 μm and the structures presented an average diameter around 4,37 μm and 114 nm. The thickness of the films obtained with the second methodvariedfrom0,5to 1 μm and the structures presented an average diameter from 95 to103 nm.The obtained tungsten oxide films presented photocatalytic activity, since doubled the reaction rate of methyl orange dye degradation with respect to the system without the film.

Mesoporous WO3 powders were prepared via sol-gel processing synthesis using nonionic surfactant Pluronic (P-123) as the template. The influences of heating temperature on the pore structure and properties of WO3 powders were investigated. Three kinds of modifications were compared and evaluated after finding out the best heating condition. Different amount of lanthanum was doped into mesoporous WO3 to improve its Oxygen Reduction Reaction (ORR) activity. Several factors contributing to the increase of catalytic performance were discussed. Vulcan carbon powder was also used as a support to increase the catalysts’ electrical conductivity as well as dispersity. The component, microstructure and specific surface area of samples were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM) and N2 adsorption-desorption analysis. A three-electrode system with a rotating disk electrode (RDE) was used to detect samples’ electrochemical performance towards ORR in alkaline solutions. The as-prepared mesoporous La/WO3 powder with a ratio of La: W = 1: 10, calcined at 550℃ and supported by 25 wt% Vulcan carbon powder, exhibited highest ORR catalytic activity.