Tesi sul tema "IIIT"

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In this work the synthesis of the heavy lanthanides and yttrium were carried out, using the direct addition of the sodium terephthalate in the respectives metallic chloride solutions. The synthesized compounds were characterized by simultaneous Thermogravimetry and differential scanning calorimetry analysis (TG-DSC), differential scanning calorimetry (DSC), Fourier Transform Infrared Spectroscopy (FTIR), thermogravimetric analyses coupled to Fourier Transform Infrared spectroscopy (TG-FTIR), EDTA complexometry and X ray powder Diffractometry. From the data, it was possible to obtain the general formula of each compound (Ln2(TFta)3.nH2O, where Ln = Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(III), TFta = terephthalate, and n = 4,5 (Tb, Dy and Ho), 4,0 (Er, Tm and Y), 5,0 (Yb) and 6,5 (Lu)), as well as unreported information about the thermal properties, in air atmosphere, thermal stability; molar dehydration enthalpy; main evolved gases from thermal decomposition (H2O, CO2 and CO), the coordination mode between metal and ligand and performing the comparison of the results of X -ray diffraction of the compounds synthesized by the powder method using and the single crystal obtained by hydrothermal synthesis reported in the literature.
A pesquisa na área de compostos de coordenação com ligantes à base de ácidos carboxílicos aromáticos e metais os lantanídeos e ítrio tem sido recorrente devido as suas promissoras aplicabilidades. O presente trabalho tem como objetivo realizar as sínteses dos tereftalatos de lantanídeos pesados e ítrio pelo método direto entre soluções de tereftalato de sódio e os respectivos cloretos metálicos e caracterização dos mesmos por meio das técnicas de análise termogravimétrica e calorimetria exploratória diferencial simultânea (TG-DSC), Calorimetria exploratória diferencial (DSC), Espectroscopia de Infravermelho por Transformada de Fourrier (FTIR), Complexometria por EDTA e Difratometria de raio X pelo método do pó. A partir das informações obtidas desse estudo termoanalítico detalhado, em atmosfera de ar, foi possível obter informações inéditas, como a fórmula geral Ln2(TFta)3.(H2O)2.nH2O, onde Ln corresponde aos Tb(III), Dy(III), Ho(III), Er(III), Tm(III), Yb(III), Lu(III) e Y(III), TFta o tereftalato e n= 2,5 (Tb, Dy e Ho), 2,0 (Er, Tm e Y), 3,0 (Yb) e 4,5 (Lu); estabilidade térmica; grau de hidratação dos compostos; entalpia molar média por molécula de água; indicar os principais produtos gasosos produzidos pela decomposição térmica (H2O, CO2 e CO); sugerir coordenação em ponte entre entre metal e o ligante e realizar a comparação dos resultados de difratometria de raio x dos compostos sintetizados pelo método do pó com os monocristais obtidos por síntese difusão lenta apresentados na literatura.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES
In the last years the interest in the chemistry of coordination compounds of polycarboxylic acids and lanthanides or transition metals has substantially increased, due to their interesting characteristics, such as gas storage (Metal-organic frameworks compounds), luminescence and magnetic properties. A literature survey reveals few studies investigating the properties of lighter lanthanide coordination compounds obtained by soft chemistry routes, and mainly the study of their thermal properties in air atmosphere. In this work the reaction between sodium isophthalate and lighter lanthanides solutions (La – Gd) except Pm, led to the formation of two new coordination compounds, and five already reported in the literature, whose thermal behavior and infrared spectra was investigated. The compounds was characterized by simultaneous Thermogravimetric and differential scanning calorimetry analysis (TG-DSC), differential scanning calorimetry (DSC), Fourier Transform Infrared Spectroscopy (FTIR), thermogravimetric analyses coupled to Fourier Transform Infrared spectroscopy (TG-FTIR) and EDTA complexometry. With the TG-DSC and TG-FTIR data was possible to determinate the general formula of compounds (Ln2(L)3.nH2O, where Ln = La – Gd, except Pm, L = isophthalate, n varies from 2 to 13,5), thermal stability and molar dehydration enthalpy per water molecule, as well as the main evolved gases during thermal decomposition (H2O, CO2 and CO). The FTIR spectra suggest that metal-ligand coordination occurs in the bridging bidentate mode.
Nos últimos anos, tem surgido um grande interesse na química dos compostos de coordenação de ácidos dicarboxílicos com metais de transição ou lantanídeos, devido a sua aplicabilidade em compostos de estrutura molecular porosa (Metal-organic frameworks) e interessantes propriedades luminescentes. Uma revisão na literatura revela a falta de trabalhos estudando de forma sistemática as propriedades térmicas de compostos de coordenação de lantanídeos leves com o ligante isoftalato em atmosfera de ar, principalmente obtidos por meio de vias sintéticas classificadas como brandas. Neste trabalho, foi realizada a síntese dois novos compostos de coordenação, e cinco já reportados pela literatura em diferentes trabalhos, utilizando a metodologia de reação direta entre soluções de ácido isoftálico (ácido 1,3- benzenodicarboxílico) e de lantanídeos (La – Gd) exceto Pm. Os compostos sintetizados foram caracterizados e estudados através das técnicas de análise termogravimétrica e calorimetria exploratória diferencial simultânea (TG-DSC), Calorimetria exploratória diferencial (DSC) e Espectroscopia de Infravermelho por Transformada de Fourrier (FTIR) e Complexometria por EDTA. A partir das curvas TG-DSC e TG-FTIR foi possível a determinar a estequiometria dos compostos, com fórmula geral Ln2(L)3.nH2O (Ln = La a Gd, exceto Pm, L = isoftalato) n variando de 2 a 13,5, bem como estabilidade térmica, grau de hidratação dos compostos e os principais produtos gasosos formados pela decomposição térmica (H2O, CO2 e CO). Através das análises de FTIR pode-se sugerir que o tipo de coordenação entre metal e o ligante é bidentado em ponte.

Thesis (Ph. D.)--Ohio State University, 2003.
Title from first page of PDF file. Document formatted into pages; contains xv, 133 p.: ill. Includes abstract and vita. Advisor: Richard D. Kass, Dept. of Physics. Includes bibliographical references (p. 132-133).

Cette thèse a pour un objectif de mettre à disposition, les données issues de l’un des très rares sites de la Jazireh syrienne, Tell Kashkashok III, qui présente une longue séquence d’occupation, s’étendant du Ve jusqu’au IIIe millénaire av. n. è. Ce site documente plusieurs périodes de l’histoire nord-mésopotamienne (Obeid, Chalcolithique Récent et Jazireh Archaïque) dont chacune a constitué un jalon dans le processus qui déboucha sur l’éclosion de villes dans le Nord syrien. Ces données archéologiques fournissent un nouvel éclairage sur la nature du développement d’une société urbaine dans le Nord de Syrie. En effet, les éléments d’urbanisme apportés par Kashkashok III résident dans la diversité des vestiges architecturaux que le site a produits. Ils permettent d’alimenter la recherche scientifique sur l’évolution des établissements de Mésopotamie du Nord à partir du début du Ve millénaire av. n. è
The purpose of this research is to provide readers new data from one of the very few sites in the syrian Jazireh namely Tell Kashkashok III which contains a long and continuous sequence of occupation spanning three thousand years, extending from the 5th until the third millenniumB.C. The site documents several periods of the history of Northern Mesopotamia (Obeid, Late Chalcolithic and Archaic Jazireh), each of which is a milestone in the process that led to the emergence of cities in Northern Syria. These archaeological data provide new insights into the nature of development of an urban society in northern Syria. The urban planning elements brought by Kashkashok III reside indeed in the diversity of the monumental architectural remains that the site has produced. They allow to feed the scientific researches on the evolution of settlements in Mesopotamia of the North since the beginning of the 5th millennium B.C

Memoria para optar al título de Químico
En esta Memoria de Título se estudió la extracción y separación de lantano (III), cerio (III), praseodimio (III) y neodimio (III) mediante extracción por solventes utilizando como agentes transportadores los extractantes comerciales D2EHPA, PC88A, LIX 272 y CYANEX 301. El análisis de las curvas de especiación química de los elementos tierras raras (ETR) en fase acuosa en función del pH permiten establecer que en el rango de pH de trabajo los iones de La, Ce y Pr se encuentran principalmente como iones complejados con nitrato. Sin embargo, entre pH 1 y 2 se presenta una competencia con la especie ETR-sulfato. Debido a que el ión nitrato presenta un poder ligante muy débil, en la práctica es posible considerar que los iones ETR se encuentran como especies libres cuando se presenta una competencia frente a un ligante más fuerte, tal como sería en el caso de los extractantes organofosforados, mientras que, la especie ETR-sulfato sería la única especie que podría interferir en la extracción de los iones de ETR. Los experimentos de extracción por solventes realizados entre cada uno de los iones metálicos de ETR con cada uno de los extractantes propuestos, se llevaron a cabo considerando las siguientes variables que afectan al proceso: la concentración de cada uno de los extractantes en la fase orgánica, de cada ión metálico presente en la fase acuosa y el pH de la solución acuosa de alimentación. Un análisis de los resultados obtenidos para la variación en la concentración de extractante indicó que, los valores más altos de extracción se logran cuando se utilizan 40 mM. Los resultados varían dependiendo del ión metálico observándose siempre las mayores extracciones para Pr, y en menor grado consecutivo Nd, Ce y La. Los resultados obtenidos para la variación de pH inicial indicaron que, en general, el porcentaje de extracción se incrementa con el aumento del pH inicial de la solución acuosa de alimentación en todos los experimentos realizados. En el caso de los extractantes D2EHPA y PC88A se alcanzaron extracciones sin una distinción práctica entre cada uno de los iones ETR. Mientras que, en el caso de los extractantes LIX 272 y CYANEX 301 se observó que hay diferenciación clara en el grado de extracción para los distintos ETR. Los resultados obtenidos para la variación en la concentración de ión metálico inicial permitieron aseverar que, en general, el grado de extracción disminuye con el incremento de la concentración de ión metálico en la solución de alimentación inicial para los cuatro extractantes estudiados. Los experimentos de retroextracción de los iones metálicos de ETR presentaron una tendencia moderada a la disminución con el incremento de la concentración de H2SO4 en la fase acuosa para los todos los complejos ETR-extractante estudiados. Sólo se observó que en el caso de los complejos ETR-LIX 272 se lograron porcentajes de retroextracción intermedios que podían ser utilizados en una ruta de separación de los iones ETR. El análisis de los estudios de equilibrio permitió apreciar claramente que la extracción de Pr es la más favorecida en todos los casos, y en menor grado consecutivo Nd, Ce y La. Adicionalmente, se pudo observar que desde el punto de vista de los extractantes el D2EHPA es el que más favorece la reacción de extracción y en menor grado consecutivo PC88A, LIX 272 y CYANEX 301. A partir de un análisis de todos los datos obtenidos se pudo deducir que el extractante LIX 272 cumplió de mejor manera con el requisito de extraer preferentemente alguno de los iones de ETR en ciertas condiciones y, de este modo, poder plantear de esa manera alguna posible ruta de separación. Los estudios cinéticos de extracción indicaron que en general es el Pr el que reacciona más rápidamente, y el La el que reacciona más lentamente, con todos los extractantes. Del mismo modo, se observa que el extractante que reacciona de manera más rápida con los iones metálicos es el D2EHPA y en menor grado consecutivo PC88A, LIX 272 y CYANEX 301. Por otro lado, los experimentos cinéticos de retroextracción indicaron que los complejos ETR-D2EHPA y ETR-PC88A son los que más rápidamente liberan los iones de ETR. Asimismo, el complejo ETR-CYANEX 301 es el que los libera más lentamente. La ruta de separación de iones metálicos en dos etapas propuesta en este estudio utilizando como extractante el LIX 272 cumple en cierta medida con el objetivo planteado. En la primera etapa de extracción se logró incrementar la pureza del La en la fase acuosa hasta un 40%, aproximadamente. Una proyección de este resultado en 8 contactos permitiría obtener un refino constituido exclusivamente por La, alcanzando a aislar cerca del 70% del La inicial. En la segunda etapa de la ruta de separación, que considera la retroextracción de los complejos ETR-LIX 272, se logró aislar cerca del 74% del Ce inicial con una pureza superior al 98%. Una proyección de 3 contactos para esta etapa permitiría obtener una fase acuosa final con un 99,97% de pureza de Ce y con un rendimiento global del proceso de un 54,8%. Esta ruta de separación por equilibrios deja el problema de separación relegado solamente a la dupla Pr y Nd. Por otro lado, la diferencia en un orden de magnitud de las constantes cinéticas de retroextracción para los complejos Pr-LIX 272 y Nd-LIX 272 permitiría proyectar una separación de ambos iones en el tiempo
The extraction and separation of lanthanum (III), cerium (III), praseodymium (III), and neodymium (III) was studied by means of solvent extraction using D2EHPA, PC88A, LIX 272, and CYANEX 301 as extractant. The analysis of the chemical speciation curves of rare earth elements (REE) in aqueous phase as a function of pH allow to establish that in the working pH range the lanthanum, cerium, and praseodymium ions are complexed mainly with nitrate. However, between pH 1 and 2 a competition with REE-sulfate species is observed. Due to the nitrate ion has a very weak binding power, in fact it is possible to consider that REE ions are as free species when there is a competition with a stronger binder, as would be the case of organophosphorus extractants, while REE-sulfate species would be the only species that could interfere in the extraction of REE ions. The solvent extraction experiments, performed between each of the metal ions of REE with each of the proposed extractants, were carried out considering the following variables that affect the process: the concentration of each of the extractants in the organic phase, the concentration of each metal ion present in the aqueous phase and the pH of the aqueous feed solution. An analysis of the obtained results for the variation in the extractant concentration indicated that the highest values of extraction are achieved when using 40 mM. Results vary depending on the metal ion, always showing a preference for the praseodymium and in less consecutive degree for neodymium, cerium, and lanthanum. The obtained results for the variation of initial pH indicated that, in general, the extraction percentage increases with rising initial pH of the aqueous feed solution in all experiments. While in the case of extractants D2EHPA and PC88A no practical distinction between each of the REE ions were achieved, in the case of extractants LIX 272 and CYANEX 301 it was noted that there was clear difference in the degree of extraction for different REE. The results obtained for the variation in initial metal ion concentration allowed to assert that, in general, the extraction degree decreases while increasing metal ion concentration in the initial feed solution for the four extractants studied. Stripping experiments of REE metal ions showed a moderate tendency to decrease with increasing H2SO4 concentration in the aqueous phase for all REE-extractant complexes studied. It was observed that only in the case of REE-LIX 272 complex intermediate stripping percentages were achieved that could be used in a route of the separation of REE ions. The analysis of the equilibrium studies allowed to appreciate clearly that the extraction of praseodymium is the most favored in all cases, and less consecutive neodymium, cerium and lanthanum. Additionally, it was noted that from the point of view of the extractants, D2EHPA is which most favors the extraction reaction and in less consecutive degree for PC88A, LIX 272, and CYANEX 301. From an analysis of all the obtained data it is allowed to conclude that extractant LIX 272 is which better complies with the requirement for removing any REE ions preferably under certain conditions and, thus, can propound some possible separation route. Extraction kinetic studies indicated that in general praseodymium will react faster with all the extractants and also in general, lanthanum reacts more slowly. In the same way, it is noted that the extractant that react faster with the metal ions is D2EHPA and in less consecutive degree for PC88A, LIX 272, and CYANEX 301. Furthermore, stripping kinetic experiments indicated that REE-D2EHPA, and REE-PC88A complexes are the fastest in releasing REE ions. Likewise, REE-CYANEX 301 complex is that which release them more slowly. The separation route of metal ions in two stages proposed in this study using the LIX 272 extractant fulfill in some extent with the stated objective. In the first extraction step it was able to increase the purity of lanthanum in the aqueous phase up to 40%, approximately. A projection of this result for 8 contacts would obtain a refine constituted exclusively of lanthanum, reaching out to isolate about 70% of the original lanthanum. In the second stage of the separation route, that considers the stripping of REE-LIX 272 complexes, about 74% of the initial cerium was isolated with a purity exceeding 98%. A projection of 3 contacts for this stage would provide a final aqueous phase with a purity of 99.97% for cerium and an overall process yield of 54.8%. This equilibrium separation route leaves the separation problem relegated only to the couple praseodymium and neodymium. On the other hand, the difference in an order of magnitude of the stripping kinetic constants for Pr-LIX 272, and Nd-LIX 272 complexes would allow to project a separation of both ions at time

Das Buch informiert über neueste Methoden und Datengrundlagen eines Flächennutzungsmonitorings sowie kleinräumigen Statistik- und Prognosemethoden. Grundlage sind die Beiträge des 3. Dresdner Flächennutzungssymposiums. Zwei Trends bestimmen die rasante Entwicklung: das stetig verbesserte Datenangebot sowie die Abstimmung von Liegenschafts- und Geotopographie im AAA-Projekt. Diese wird nun endlich die tatsächliche Flächennutzung harmonisieren und neue Perspektiven für ein genaueres Flächennutzungsmonitoring eröffnen. In der Analyse und Visualisierung ist der Trend zu Rasterkarten unübersehbar. Denn administrative Gebietseinheiten werden momentan immer größer und entziehen sich damit einem Monitoring. Sie müssen zwingend um kleinräumigere und zeitlich konstante Analyseeinheiten ergänzt werden; dazu eignen sich insbesondere quadratische geographische Gitterzellen.:Aktuelle Trends der Flächennutzungsentwicklung Flächennutzungsentwicklung in Deutschland – Trendanalysen auf Basis der aktuellen amtlichen Flächenstatistik Gertrude Penn-Bressel............................................................................3 Flächenverbrauch und Landschaftszersiedelung – Wo steht Deutschland im internationalen Vergleich? Stefan Fina............................................................................................11 Aktuelle Ergebnisse des IÖR-Monitors zur Flächennutzung in Deutschland Tobias Krüger........................................................................................23 Methoden des Flächennutzungsmonitorings Fernerkundliche Erhebungen in Kombination mit Geo- und Statistikdaten – Mehrwert durch Datenverknüpfung Wieke Heldens, Hannes Taubenböck, Thomas Esch, Christian Geiß, Michael Wurm, Michael Thiel...................................................................39 Kleinräumige quantitative Abschätzung des deutschen Gebäudebestandes – Ausgangslage und Perspektive Martin Behnisch, Gotthard Meinel..........................................................47 Siedlungsflächenmonitoring in Rasterkarten Markus Dießelmann, Gotthard Meinel, Robert Hecht..............................61 Amtliche Flächenstatistik – ALK – IÖR-Monitor – Ergebnisse eines Vergleichs Gotthard Meinel, Ekkehard Scheffler......................................................71 Visualisierungs- und Bewertungsmethoden Visualisierung von Ergebnissen der Arealstatistik der Schweiz mit Kriging- und Mischrasterkarten Werner Meyer........................................................................................83 Monitoring- und Bewertungsmethoden von Problem- und Stadterneuerungs‑ gebieten – Realisierung im Stadtteilmonitor Dresden Nguyen Xuan Thinh................................................................................93 Raumbeobachtung und Flächenmanagement in der Metropolregion Rhein-Neckar Hans-Peter Hege.................................................................................107 Neue Analyse- und Visualisierungsmöglichkeiten im Monitor der Siedlungs- und Freiraumentwicklung (IÖR-Monitor) Jochen Förster.....................................................................................115 Amtliche Geodaten und -dienste als Grundlage eines Monitorings Das ATKIS Basis-DLM im neuen Gewand – was hat sich geändert Wolfram Kunze....................................................................................125 Das neue Geobasisprodukt 3D-Gebäudestrukturen Stephan Heitmann...............................................................................135 Informationsdienst „GeoDaten Dresden“ – informatorisches Instrument zum Flächensparen? Marcus Dora.........................................................................................141 Indikatoren und Monitoring des Freiraums Indikatoren und Monitoring der biologischen Vielfalt in Deutschland Werner Ackermann, Rainer Dröschmeister, Ulrich Sukopp...................149 Landschaftszerschneidung und Waldfragmentierung – Neue Indikatoren des IÖR-Monitors Ulrich Walz, Tobias Krüger, Ulrich Schumacher.....................................163 Prognosen der Flächeninanspruchnahme Das 30-Hektar-Ziel – Flächensparen auf Kosten sozialer und ökonomischer Belange? Stefan Siedentop.................................................................................173 Modellgestützte Projektion der Flächeninanspruchnahme in den Kreisen Deutschlands bis 2020 Martin Distelkamp, Philip Ulrich............................................................181 Gewerbeflächenprognosen – Methodische Zugänge und Forschungsbedarf Karsten Rusche, Alexander Mayr.........................................................189 Kleinräumige Statistik – Probleme und Lösungen Indikatorensysteme im Spannungsfeld zwischen europäischen Anforderungen und regionalem Informationsbedarf Hans-Dieter Kretschmann....................................................................199 „Äpfel mit Birnen vergleichen, aber nicht mit Zitronen“ – Überlegungen zu einer Erweiterung der regionalstatistischen Analyseeinheiten in der amtlichen Statistik Markus Sigismund................................................................................205 Möglichkeiten und Grenzen der Regionalisierung statistischer Erhebungen am Beispiel des Zensus 2011 Michael Bubik, Karsten Lamla...............................................................213 Das kleinräumige städtische Gliederungssystem AGK als Basis intrakommunaler Informationssysteme Rainer Schönheit..................................................................................219 Strategien der Geoinformationsnutzung Geoinformations-Nutzung durch Geodateninfrastrukturen: Das Beispiel GDI Metropolregion Hamburg Sascha Tegtmeyer...............................................................................229 Planungsraumbezogene Informationsbereitstellung für Monitoring und Analyse – Umsetzungsbaustein der Rahmenstrategie Soziale Stadtentwicklung Berlin Dietrich Bangert...................................................................................235 Kommunale Geodateninfrastrukturen und sozio-technischer Systemwandel: Entwicklungspfade in Deutschland Marc Wolfram.......................................................................................241 Autorenverzeichnis..............................................................................255

This dissertation describes the synthesis and antimicrobial use of a series of half-sandwich Ir(III), Rh(III), Co(III) amino acid and ethylenediamine complexes. This investigation focuses on the formulation (ηn-arene)M(L)X, (L = ethylenediamine or α-amino carboxylate), (M= Ir, Rh, Ru, Co). Arene, Ligand and metal center variations were designed to tailor antimicrobial activity specific for each organism studied (Staphylococcus aureus or Mycobacteria). Each of the D/L-amino acids formed a diasteromeric complex with chiral centers on both the metal center and amino acid ligand. The unique chirality of each center elicits different antimicrobial activity against the Mycobacteria studied. The metal center (M), arene ligand (ηn-arene), and amino acid (aa), were changed independently and studied for the antimicrobial activity. In a similar fashion, each of the complexes modified with ethylenediamine and diamine derivatives were studied for their antimicrobial activity against S.aureus. All complexes were synthesized,characterized by nuclear magnetic resonance (NMR), high-resolution mass spectroscopy (HRMS), single-crystal X-ray diffraction, and elemental analysis. During the course of this work it was found that the amino acid complexes with all metal centers were specific for antimicrobial activity against all types of Mycobacteria, while the diamine derivatives were active against different strains of S.aureus. Acitvity was measured to be as low as 2 ug/mL respectively depending on the complex used. A structure activity relationship was developed to determine what combinations of ligand, metal and arene were necessary to achieve the highest antimicrobial activity. The optimal arene R-chain length for CpR was determined to be R=hexyl for all complexes studied. The most active amino acidcomplex was determined to be that of L-phenylglycine for Mycobacteria, the cis-1,2-diaminocyclohexane complex is the most active ligand against S.aureus. Each metal center had similar activity levels. Toxicological studies were performed to test their viablity to be used in mammalian systems. The complexes with the highest activity were studied against several mammailan cell lines and revealed that mammailan cells were undergoing normal cellular processes at up to 40 times the minimal inhibitory concentration (MIC). A study of the MOA or mechanism of action revealed the ability of the amino acid complexes to affect the peptidyl transferase region on the 23s ribosomal subunit of M.smegmatis. This was accomplished by isolating resistant strains of M.smegmatis towards the most effective complex (Cp*hexyl)Ir(L-phenylglycine)-Cl. Cross drug resistance of these mutants was shown with clarithromycin. The DNA of the 23s ribosomal subunit was sequenced revealing a deletion/insertion mutation within domain V (bases 2057-2058).
Ph. D.

IMpower010 showed significant DFS benefit with atezo after adjuvant chemo in resected NSCLC (Felip Lancet 2021). At the interim DFS analysis, the significance boundary was crossed for the stage II-IIIA PD-L1 TC 1% population (stratified HR, 0.66; 95% CI: 0.50, 0.88), with greatest benefit in the PD-L1 TC 50% subgroup (unstratified HR, 0.43; 95% CI: 0.27, 0.68). Here we present further analyses in PD-L1 TC 50% stage II-IIIA NSCLC pts.

III-V materials such as indium arsenide (InAs) and gallium arsenide (GaAs) are increasingly used in electronic and photovoltaic devices. The extensive application of these materials may lead to release of III-V ionic species during semiconductor manufacturing or disposal of decommissioned devices into the environment. Although arsenic is recognized as an important contaminant due to its high toxicity, there is a lack of information about the toxic effects of indium and gallium ions. In this study, acute toxicity of As(III), As(V), In(III) and Ga(III) species was evaluated using two microbial assays testing for methanogenic activity and 02 uptake, as well as two bioassays targeting aquatic organisms, including the marine bacterium Aliivibrio fischeri (bioluminescence inhibition) and the crustacean Daphnia magna (mortality). The most noteworthy finding was that the toxicity is mostly impacted by the element tested. Secondarily, the toxicity of these species also depended on the bioassay target. In(III) and Ga(III) were not or only mildly toxic in the experiments. D. magna was the most sensitive organism for In(III) and Ga(III) with 50% lethal concentrations of 0.5 and 3.4 mM, respectively. On the other hand, As(III) and As(V) caused clear inhibitory effects, particularly in the methanogenic toxicity bioassay. The 50% inhibitory concentrations of both arsenic species towards methanogens were about 0.02 mM, which is lower than the regulated maximum allowable daily effluent discharge concentration (2.09 mg/L or 0.03 mM) for facilities manufacturing electronic components in the US. Overall, the results indicate that the ecotoxicity of In (III) and Ga(III) is much lower than that of the As species tested. This finding is important in filling the knowledge gap regarding the ecotoxicology of In and Ga.

Thesis (MSc)--University of Stellenbosch, 2003.
ENGLISH ABSTRACT: Ruthenium, as one of the platinum group metals, was investigated to determine the aquation rate constant of [RuCl6]3- and the anation rate constant of [RuCl5(H2O)]2-. This two reactions represent the equilibrium reaction [RuCl6]3- + H2O ⇄ [RuCl5(H2O)]2- + Cl-. The reactions were followed, using stopped-flow injection and UV/Visible spectroscopy, at different temperatures. The aquation and anation rate constants were determined with good precision and thermodynamic values for the reactions were calculated. The pseudo first order aquation rate constant, k65, was determined by calculation from the regression line as k65 = 52.1 (±3.7) x10-3 s-1 at 25°C. The activation energy, Ea, is 90.1 (±1.2) kJ.mol-1 and the enthalpy and entropy of activation is 87.7 (±1.2) kJ.mol-1 and 24.7 (±4.3) J.K-1.mol-1, respectively. The aquation rate constant was found to be dependent on the hydrochloric acid concentration, decreasing with increasing hydrochloric acid concentration. From the regression line at 25°C the second order anation rate constant, k56, was calculated as 1.62 (±0.11) x10-3 M-1s-1. The activation energy is 88.0 (±1.4) kJ.mol-1, with the enthalpy and entropy of activation 85.6 (±1.4) kJ.mol-1 and –11.2 (±4.7) J.K-1.mol-1, respectively. The influence of the hydrochloric acid concentration of the solution on the anation rate constant was not investigated. The equilibrium constant for the reaction studied was calculated from the rate constants for the aquation and anation reactions. The equilibrium constant, K6, was calculated as 0.0311 M-1 at 25°C. The equilibrium constant, when compared to literature, was found to be dependent on the hydrochloric acid concentration. It was then used, in conjunction with data from the literature, to construct two distribution diagrams. Distribution diagrams for the Ru(III) aquachloro species show between 79.9% to 72.3% [RuCl6]3- present in 12M HCl. The two distribution diagrams were very similar and it is not possible to resolve the issue of a final distribution diagram for the aqua-chloro Ru(III) system without further investigation into the all the other rate constants of the Ru(III) aqua-chloro species. The rate constants and thermodynamic values for the Ru(III) reaction were compared to corresponding data (from literature) for Rh(III) and Ir(III) because several comparisons between these platinum group metals have been noted. It was found that for both the aquation and anation rate constants, the following trend was observed: Ru(III) > Rh(III) > Ir(III). These differences are in certain cases exploited in the refining of these platinum group metals. Crystals of diethylenetriamine hexachlororuthenate(III) was prepared and characterised by x-ray crystallography and CHN analysis. The average Cl-Ru bond length for the crystal was 2.371 Å. The crystal structure was compared to hexaaquaaluminium hexachlororuthenate(III) tetrahydrate and diethylenetriamine hexachlororhodate(III). The metal-chloride bond lengths of all the crystals were found to be similar (2.350 Å – 2.375 Å). The diethylenetriamine crystal structures compared well. The conclusion was that the crystals prepared were diethylenetriamine hexachlororuthenate(III).
AFRIKAANSE OPSOMMING: Ruthenium(III), een van die platinum groep metaal-ione, is in hierdie studie ondersoek om die akwasie tempo konstante van [RuCl6]3- en die anasie tempo konstante van [RuCl5(H2O)]2- te bepaal. Dié twee reaksies verteenwoordig die ewewigsreaksie [RuCl6]3- + H2O ⇄ [RuCl5(H2O)]2- + Cl-. Die verloop van die reaksies is met behulp van UV/Sigbare spektroskopie by verskillende temperature gevolg. Die akwasie en anasie tempo konstantes is bepaal met goeie presisie en die termodinamiese konstantes van die reaksies is bereken. Die pseudo-eerste orde akwasie tempo konstante, k65, is bepaal deur middel van regressie, as 52.1 (±3.7) x10-3 s-1 by 25°C. Die aktiverings energie, Ea, is bereken as 90.1 (±1.2) kJ.mol-1 en die entalpie en entropie van aktivering is onderskeidelik 87.7 (±1.2) kJ.mol-1 en 24.7 (±4.3) J.K-1.mol-1. Daar is gevind dat die akwasie reaksie konstante afhanklik was van die soutsuur konsentrasie: dit neem af soos die soutsuur konsentrasie toeneem. Met behulp van die regressie lyn is die anasie tempo konstante bepaal by 25°C as 1.62 (±0.11) x10-3 M-1s-1. Die aktiveringsenergie is bepaal as 88.0 (±1.4) kJ.mol-1 en die entalpie en entropie van aktivering, onderskeidelik as 85.6 (±1.4) kJ.mol-1 en –11.2 (±4.7) J.K-1.mol-1. Die invloed van die soutsuur konsentrasie op die anasie tempo konstante is nie bepaal nie. Die ewewigskonstante vir die reaksie wat ondersoek is, is bereken met die tempo konstantes vir die akwasie en anasie reaksies. Die ewewigskonstante, K6, is bereken as 0.0311 M-1 by 25°C. Toe die ewewigskonstante vergelyk is met die literatuur waardes, is gevind dat die ewewigskonstante afhanklik is van die soutsuur konsentrasie. Saam met die waardes wat in die literatuur gevind is, is die ewewigskonstante gebruik om twee distribusie diagramme te bereken. Die distribusie diagramme vir die Ru(III) spesies toon onderskeidelik 79.9% en 72.3% [RuCl6]3- in 12M HCl. Die twee distribusie diagramme is baie eenders en dit is nie moontlik om ‘n finale distribusie diagram op te trek totdat die uitstaande tempo konstantes tussen die akwachloro Ru(III) spesies bepaal word nie. Die tempo konstantes en termodinamiese waardes wat bepaal is vir die Ru(III) reaksie is vergelyk met gelyksoortige waardes in die literatuur van Rh(III) en Ir(III) omdat daar ooreenkomste tussen die platinum groep metale opgemerk is. Daar is bevind dat die akwasie én anasie reaksies die volgende patroon volg: Ru(III) > Rh(III) > Ir(III). Die verskille word in sekere gevalle benut in die raffinering van hierdie metale. Kristalle van dietileentriamien heksachlororuthenaat(III) is berei en gekarakteriseer met behulp van CHN analise en x-straal kristallografie. Die gemiddelde Cl-Ru bindingsafstand vir die kristal was 2.371 Å. Die kristalstruktuur is vergelyk met dié van heksaäkwaäluminium hexachlororuthenaat(III) tetrahidraat en diëtileentriamien heksachlororhodaat(III). Die chloried-metaal bindingsafstand vir die kristalle was soortgelyk (2.350 Å – 2.375 Å). Die diëtileentriamien kristalstrukture stem goed ooreen. Die gevolgtrekking was dat die kristalle wat voorberei is wel diëtileentriamien heksachlororuthenaat(III) was.

Memoria para optar al título de Químico
En esta Memoria de Titulo se estudió la transferencia del lantano (III), cerio (III), praseodimio (III) y neodimio (III), desde una fase acuosa de alimentación hacia una fase acuosa de retroextracción, por medio del transportador órgano fosforado CYANEX 272 contenido en una membrana liquida emulsificada. En primera instancia se estudió el comportamiento ácido base de cuatro extractantes (D2EHPA, PC-88A, CYANEX 272, CYANEX 301) permitiendo conocer sus pKa aparentes y su disponibilidad para reaccionar con los iones Tierras Raras (TR) a ciertos pH. A partir de este conocimiento y las reacciones de extracción propiamente tales fue posible proponer la utilización de una fase acuosa de alimentación tamponada con el ácido 3-cloropropiónico a pH 4. A través de los experimentos de extracción por solvente de cada uno de los iones TR con los cuatro extractantes en estudio, se determinó que el extractante más adecuado para el proceso fue el CYANEX 272, debido a su alta capacidad de extracción y mayor selectividad con los cuatro iones TR. Si bien en un principio todos los experimentos se realizaron con alimentaciones monometálicas, después fue preciso probar el grado de competencia que se generaría al realizar la extracción de los iones lantánidos desde una alimentación polimetálica. Los resultados fueron coincidentes con los experimentos de extracción individuales de los iones TR, en donde el lantano es el ión que menos se extrajo en comparación con los otro tres. Por otro lado, los experimentos de retroextracción revelaron que ion cerio presentaba el menor grado de transferencia hacia la fase acuosa interna. Todos estos conocimientos generados revelaron que la dupla Nd-Pr era difícil de separar con las condiciones ya establecidas. Por esta razón se agregó EDTA como agente quelante a una alimentación que contenía estos dos iones en iguales concentraciones (2mM), lográndose un coeficiente de selectividad máximo (SPr/Nd) de 1,7. Los experimentos de extracción por solvente (SX) generaron el conocimiento base para los experimentos de transporte de los cuatro iones lantánidos con CYANEX 272 a través de las Membranas Líquidas Emulsificadas (MLE). Previo al inicio de los experimentos de transferencia fue necesario lograr una doble emulsión de estabilidad adecuada en función de las concentraciones variables de sus componentes: transportador CYANEX 272, tensoactivo SPAN 80, Ln+3 (lantánidos) total y HCl en la fase acuosa de retroextracción. A partir del estudio de estabilidad, se observó que la concentración del tensoactivo SPAN 80 presentó el efecto más crítico, donde una cantidad insuficiente produjo pérdida de la fase acuosa interna, disminuyendo el rendimiento de extracción. Por otro lado, una cantidad excesiva de SPAN 80 provocó el hinchamiento de la emulsión primaria. Como consecuencia de esto la fase acuosa interna que contiene al ion de interés se diluye o pierde pureza. En términos generales, para conservar el volumen de 75 mL de emulsión primaria, formada por 25 mL de fase acuosa interna más 50 mL de fase orgánica, es necesario utilizar alrededor de 1,2% p/v de SPAN 80, cuando la concentración en la alimentación de cada uno de los ETR es 0,5 mM. Para concentraciones mayores se necesita aproximadamente entre 2-2,1% p/v de tensoactivo. Con los experimentos preliminares de transferencia de los iones TR en estudio, se pudo determinar que los elementos lantano, cerio, praseodimio y neodimio fueron extraídos eficientemente en el orden del 90% desde la alimentación, mientras que fueron transportados a través de la membrana hacia la fase acuosa interna en un rango entre 40-60%. Posteriormente, un estudio cinético de la extracción de cada uno de los ETR, permitió observar que durante los primeros 5 min los iones cerio, praseodimio y neodimio experimentaron un rápido decaimiento en su concentración en la fase acuosa externa, mientras que para el ion lantano se requirió al menos de 10 min. Finalmente, para lograr un enriquecimiento de cada uno de los iones metálicos mediante MLE desde una solución polimetálica, se realizaron dos diseños experimentales, uno de tipo screening y otro de optimización. Los resultados del primer diseño indicaron que el factor tiempo fue el único que presentó un efecto significativo sobre los porcentajes de extracción y transferencia de los ETR a través de la doble emulsión. En el segundo diseño los resultados indicaron que la presencia de EDTA en la fase acuosa externa tuvo un efecto negativo sobre el grado de transferencia de los iones TR hacia la fase orgánica.
In this work the transference of lanthanum (III), cerium (III), praseodymium (III) and neodymium (III) were studied, from a feed aqueous phase toward a backextraction aqueous phase by means of the organophosphorous CYANEX 272 carrier contained into an emulsified liquid membrane. In the first instance the acid-base behavior of the four extractants (D2EHPA, PC-88A, CYANEX 272 and CYANEX 301) were studied allowing to know their apparent pKa and through it the availability to react with the rare earth ions (RE) at certain pH. From this knowledge and the actual such extraction reactions it was possible to propose the use of a buffered feed aqueous phase with 3-cloropropionic acid at pH 4. Through the solvent extraction experiments for each one of the RE with the considered four extractants, it was determined that the most appropriated extractant for the process was CYANEX 272, owing to its high extraction capacity and better selectivity for the four RE ions. Although at first all experiments were performed with monometallic feeds, afterward it was necessary to test the degree of competition that would be generated to perform the extraction of lanthanide ions from a polymetallic feed solution. The results were consistent with the individual extraction experiments of the RE ions, wherein lanthanum is the lesser extracted ion compared with the other three ones. On the other hand, the backextraction experiments showed that the cerium ion had the lowest degree of transference toward the internal aqueous phase. All this generated knowledge revealed that the pair Nd-Pr was difficult to separate at the established conditions. For this reason, EDTA as a chelating agent was added to the feed solution that contained these two ions at identical concentrations (2 mM), achieving a maximum selectivity coefficient (SPr/Nd) of 1.7. The solvent extraction (SX) experiments generated the base knowledge for the transport experiments of the four lanthanide ions with CYANEX 272 through Emulsified Liquid Membranes (ELM). Before starting the transfer experiments it was necessary to achieve a satisfactory stability of the double emulsion as a function of the variation of the component concentrations: carrier CYANEX 272, surfactant SPAN 80, total Ln3+ (lanthanides) and HCl in the backextraction aqueous phase. From this stability study it was observed that the concentration of SPAN 80 surfactant showed the most significant effect, where an insufficient amount caused the loss of the internal aqueous phase, decreasing the efficiency of extraction. On the other side, an excessive amount of SPAN 80 caused a swelling degree of the primary emulsion. As a consequence the internal aqueous phase that contains the ion of interest is diluted or lost its purity. In general terms, for keeping the volume of 75 mL of the primary emulsion, consisting of 25 mL of internal aqueous solution plus 50 mL of the organic solution, it is necessary to use about 1.2% w/v of the SPAN 80, when the concentration of each the REE in the feeding is 0.5 mM. For higher concentrations of the total REE about 2 to 2.1% w/v of surfactant are needed, approximately. From the preliminary experiments related with the transfer study of the RE ions, it was determined that the lanthanum, cerium, praseodymium and neodymium elements are removed efficiently in the order of 90% from the feed solution, while they were transported across the membrane toward the internal aqueous phase in the range of 40-60%. Afterward, a kinetic study of the extraction of each one of the REE, allowed to note that during the first 5 min of the carrying out tests the cerium, praseodymium and neodymium ions experimented a fast decline in the concentration in the external aqueous phase, whereas for the ion lanthanum at least 10 min was required. Finally, to achieve an enrichment of each one of the metal ions from a polymetallic solution by means MLE, two experimental designs were conducted, a screening one and another one related with the optimization type. The results of the first design indicated that the time factor was the unique significant effect on the extraction and transfer rates of the REE through the double emulsion. In the second design the results indicated that the presence of EDTA in the external aqueous phase has a negative effect on the transfer degree of the RE ions towards the organic phase.
Fondecyt

This work examines possible safety risks associated with the operation of IIoT technologies in industrial production. The content of this document is an analysis of used IIoT technologies, their purpose and method of implementation into production processes and the company's technology strategy. The outcome of this analysis will serve to develop possible risk scenarios and their associated impacts. Finally, I recommend possible changes that either eliminate these risks completely or at least minimize them.

The selective oxidation of organic compounds represents a leading technology for chemical industries. They are used in chemical synthesis in the pharmaceutical and petrochemicals industries, and possible the decontamination of harmful substances. However, oxidations reaction are among the most challenging processes to control. Many stoichiometric oxidants with heavy metals are expensive, or toxic maybe both, and therefore unfeasible to be utilized. The ideal processes for catalytic oxidation would use molecular oxygen or hydrogen peroxide as the primary oxygen source, with transition metal catalysts to mimic the predominant oxidation catalysts in Nature, the cytochrome P450 enzymes. This study focuses on the synthesis of porphyrin and corrole macrocyclic ligands and the corresponding iron(III) complexes which are fully characterized by UV-vis, GC/MS, and NMR spectroscopies. In this work, the potential of catalytic oxidation reactions towards organic sulfides by these metal complexes were studied. The iron(III) porphyrin and iron(III) corrole catalysts have shown excellent activity and selectivity for sulfoxidation reactions. Various reaction conditions and environmental effects were investigated including solvent, axial ligands, water, amounts of oxygen source, and substrate scope. The optimal conditions were determined for iron(III) porphyrin/ corrole-catalyzed sulfoxidations with PhI(OAc)2 as the mild oxygen source. Competitive catalytic oxidation of substituted thioanisoles versus thioanisole by iron(III) corrole with PhI(OAc)2 were studied. The spectral studies of iron(III) corrole with PhI(OAc)2 in the presence of organic sulfide showed that a well-known diiron(IV)-μ-oxo biscorrole was formed with a second-order rate constant of k2= (3.5 ± 0.3)×103 M-1·s-1. A catalytic cycle was proposed on the basis of the mechanistic study, suggesting a highly reactive iron(V)-oxo corrole as the active oxidizing intermediate.

The Wechsler Memory Scale –iii is the newest version of a six-decade old neuropsychological inventory. Since its conception, the Wechsler Memory Scale has been highly utilized by practitioners to accurately assess various memory functions in adult subjects. Revisions made within this inventory include the Faces I subtest, a facial recognition scale, which was added in order to strengthen the instrument’s accuracy at measuring episodic memory. Facial recognition, both cross-race and within-race, has been researched extensively and consistent biases have been found between race of test taker and cross-racial identification. Theories of exposure/contextual interaction (environment) and biological foundations have been the subject of study in the past in order to determine from where these racial identification deficits stem. The current study focuses on revealing bias in the Faces I subtest, regarding to an unequal distribution of racially representative faces in the testing materials. Eighty-eight college students were recruited to view forty-eight pictured faces from the Faces I subtest and determine the racial category to which the pictured face belonged. The subjects’ categorical responses were the basis for calculating a percent agreement score for racial category of each face. It was determined, using the results of subjects’ responses, that the Faces I subtest contained an unequal distribution of racially representative faces in both the Target and Interference testing material. This confirmed the presence of an inherent bias within the subscale. The implications of memory accuracy for the WMS-iii are discussed as it relates to different fields of study, but none more directly than the criminal justice system. Eyewitness testimony is a pivotal evidentiary tool in the criminal justice system, and ramifications of cross-racial identification deficits and biases in the tools to accurately assess memory are increasingly bringing this once heavily relied upon tool into question.

Ces travaux de thèse ont pour objectif la séparation actinides (III) / lanthanides (III) par un procédé de nanofiltration assistée par complexation. Ainsi, un pilote de filtration membranaire tangentielle a été conçu et implanté dans une boîte à gants d'un laboratoire de l'installation ATALANTE du CEA-Marcoule. Une caractérisation physico-chimique de la membrane Desal GH (OSMONICS), retenue pour réaliser la séparation An(III)/Ln(III), a été effectuée pour déterminer notamment le potentiel zêta de la couche active et sa tenue aux rayonnements ionisants. En outre, une étude paramétrique a également été réalisée pour optimiser la sélectivité de complexation, et les conditions opératoires de rétention des complexes. Enfin, la séparation de traces d'Am(III) contenues dans un mélange de Ln(III), simulant la charge réelle issue d'un cycle de retraitement, a été évaluée avec plusieurs complexants de type acide polyaminocarboxylique en fonction de pH de la solution et de la quantité de ligand

Ruthenium(III) acetylacetonate was employed for the first time as homogeneous catalyst in the hydrolysis of sodium borohydride. Ruthenium(III) acetylacetonate was not reduced by sodium borohydride under the experimental conditions and remains unchanged after the catalysis, as shown by FT-IR and UV-Vis spectroscopic characterization. Poisoning experiments with mercury, carbon disulfide or trimethylphosphite provide compelling evidence that ruthenium(III) acetylacetonate is indeed a homogenous catalyst in the hydrolysis of sodium borohydride. Kinetics of the ruthenium(III) acetylacetonate catalyzed hydrolysis of sodium borohydride was studied depending on the catalyst concentration, substrate concentration and temperature. The hydrogen generation was found to be first order with respect to both the substrate concentration and catalyst concentration. The activation parameters of this reaction were also determined from the evaluation of the kinetic data: activation energy
Ea = 25.6 &
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1.3 kJ.mol-1, the enthalpy of activation
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S# = -170 ±
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K-1. Ruthenium(III) acetylacetonate provides the lowest activation energy ever found for the hydrolysis of sodium borohydride. Ruthenium(III) acetylacetonate was found to be highly active catalyst providing 1183 total turnovers in the hydrolysis of sodium borohydride over 180 min before they are deactivated. The recorded turnover frequency (TOF) is 6.55 min-1.

Denna studie behandlar det historiska datorspelet Europa Universalis III utifrån en bildanalys. Vår avsikt med arbetet var att undersöka genuskonstruktioner samt se vilken typ av historiebruk som kommer till uttryck genom den västerländska historiekulturen i spelet. I vår bildanalys har vi använt oss av Eva Blomberg och Knut Kjeldstadli. Det vi har kommit fram till är att Europa Universalis III till största del använder sig av historiska markörer och igenkänningsprincipen samt att spelet är ett uttryck för det kommersiella historiebruket. Vidare har vi funnit att datorspelsskaparna genom det kommersiella historiebruket dragit nytta av den västerländska historiekulturen för att göra ekonomiska vinster och locka spelare. Spelet har även en stark postkolonial syn.Europa Universalis III befäster stereotyper. De män som framställs har typiska manliga roller och den vita mannen hamnar högst upp i hierarkin. Kvinnan synliggörs endast en gång i spelet och då i form av drottning Elisabeth I. Vi tror, eftersom kvinnan inte finns representerad på fler ställen i spelet, att detta grundar sig i att hennes plats ansågs vara i hemmet och inte i det offentliga rummet förr. Dessutom så tror vi att Europa Universalis III: s målgrupp riktar sig till manliga spelare, som bär på en västerländsk historiekultur.

Theater
M.F.A.
Richard III is regarded as one of Shakespeare's longest and most complex plays, with a complicated plot, and a character that is a Machiavellian villain. After a workshop of Act I as an MFA Directing Project, I was granted by Temple University to stage a full production of Richard III as my thesis. Approaching the play proved difficult for me due to my lack of experience with Shakespearean text. However, by analyzing Shakespeare's text, and approaching the adaptation with the goal to make the story as clear as possible, I desired to create a production that embodied the idea of "now." The designed team and I created a world that was a-historic pulling from classic and modern forms that provided the necessary landscape for the play to occur. Through a series of seven chapters I explain my process from conception to production. I also evaluate my growth as a director during this artistic achievement. A Director's Script, Actor's Lexicon, Program Note, Design Renderings and Production Photos support my journey to opening night of Richard III.
Temple University--Theses

The Congenital Dyserythropoietic Anemias (CDA) are rare hereditary hemolytic disorders with large bi- to multi-nucleated erythroblasts in the bone marrow. Hemolysis is negative in a direct antiglobulin test (DAT). Based on morphology and clinical picture, three major forms of CDAs, type I, II, and III have been defined. CDA III, dominantly inherited, constitutes the rarest type with a majority of cases belonging to a family in Västerbotten, Sweden. The genetic background of CDA I and CDA II has been linked to mutations in CDAN1 and SEC23B respectively. The mutation of CDA III has been linked to 15q22 in earlier studies. In this project we have defined the causative genetic lesion in two families with CDA III. The novel mutation KIF23 c.2747C>G (p.P916R) was shown to segregate with CDA III in the Swedish and American CDA III families and was absent in 356 healthy controls. KIF23 encodes mitotic kinesin-like protein 1 (MKLP1), which plays a central role in the last step of cytokinesis. RNAi-based knock-down and rescue experiments demonstrated that the p.P916R mutation causes cytokinesis failure in HeLa cells, resulting in increasing number of bi-nuclear cells, consistent with appearance of large multinucleated erythroblasts in CDA III patients. We conclude that CDA III is caused by a mutation in KIF23, encoding MKLP1, a conserved mitotic kinesin crucial for cytokinesis. Flow cytometry with eosin-5´-maleimide (EMA), anti-CD55 and anti-CD59 is commonly used when investigating non-autoimmune hemolytic anemias. Reduced fluorescence of EMA, typically detected in hereditary spherocytosis, is also seen in CDA II, while reduction of CD55 and CD59 characterizes paroxysmal nocturnal hemoglobinuria (PNH). We studied the flow cytometric profile of EMA, CD55, and CD59 on erythrocytes in CDA III. We found no abnormality of the erythrocyte membrane in CDA III and concluded that standard flow cytometry cannot be used to discriminate between CDA III and normal controls. In CDA I and CDA II a majority of patients, including those who are not transfusion dependent, suffer from iron overload, which, according to earlier studies, is not the case in CDA III. We found that individuals of the Västerbotten CDA III family carry mutations in the hemochromatosis (HFE) gene. Three CDA III patients with heterozygous or compound HFE mutations need treatment with phlebotomy due to iron overload. One of them carries heterozygous H63D mutation, which is not reported to lead to iron overload by itself in otherwise healthy individuals. We propose that molecular genetic testing of the HFE gene is indicated in all patients with CDA, including CDA III.

Ce travail comporte trois parties. La première concerne l'étude magnétique de sites actifs de métallobiomolécules en utilisant un susceptomètre à SQUID. De par sa haute sensibilité, cet instrument permet de mesurer le signal paramagnétique de métalloprotéines en solution. Nous avons développé une méthodologie de ces mesures. Nous avons appliqué cette technique à des protéines fer-soufre comme la protéine Sulfite Réductase ou la protéine Ferrédoxine II et des protéines au fer à pont oxo comme la protéine Utéroferrine. Nous confrontons nos résultats à ceux obtenus par d'autres méthodes. Dans la deuxième partie de ce travail, nous exposons les propriétés magnétiques de complexes homo et hétérobinucléaires présentant le motif suivant [M(III)(μ - O)(μ -CH3CO2)2M'(III)]2+ avec M,M'=Fe,Fe; Fe,Mn ; Fe,Cr; Mn,Mn; V,V. Nous envisageons ensuite la relation entre les phénomènes d'échange et la liaison métal-métal en nous appuyant sur notre étude expérimentale d'un composé dinucléaire du Mn(IV) où les ions sont pontés par trois ligands μ-oxo. Enfin, dans la dernière partie, nous examinons la spectroscopie de systèmes polynucléaires à valence mixte au Mn(III) et Mn(IV) et élaborons différents modèles pour interpréter le spectre RPE multiligne observé pour l'état S2 du site de dégagement d'oxygène des plantes
This work is constituted of three parts. The first part involves magnetization studies of biomolecule metallic active sites using a SQUID susceptometer. Due to the high sensitivity of those new susceptometer, the paramagnetic signal of metallic centers of metalloproteins in solution can now be measured accurately. We developed new methods to achieve those measurements. We applied this technique to iron-sulfur proteins like Sulfite Reductase or Ferredoxine II and proteins containing two iron atoms bridged by an oxo group like Uteroferrin. We compare our results with those obtained by other methods. In the second part of this work, we present magnetic properties of homo and heterodinuclear compounds exhibiting the core [M(III)(μ - O)(μ -CH3CO2)2M'(III)]2+with M,M' = Fe,Fe; Fe,Mn; Fe,Cr; Mn,Mn; V,V. Then, we explore the relationship between exchange phenomena and metal­metal bonding using our experimental study of a Mn(IV) dinuclear compound where the two manganese atoms are bridged by three oxo groups. In the last part, we examine EPR spectroscopy of polynuclear Mn(III) and Mn(IV) compounds and build up various madel in order to interpret the multiline EPR spectra of the 82 state of the Oxygen Evolving Center of the Photosystem II of plants

Trettio kognitivt friska testpersoner (ålder M=31,9 år, utbildning M=16,3 år) testades med både WAIS-III (”Wechsler Adult Intelligence Scale - third edition”) och WAIS-III NI (”WAIS-III som neuropsykologiskt instrument”) för att undersöka eventuella skillnader i resultat mellan testen. Testpersonerna fick en signifikant ökning vid testning med WAIS-III NI jämfört med testning med WAIS-III på HIK (11,1), VIK (14,7), PIK (3,9), VF (11,4), POI (5,5), AMI (8,8), BK (1,6), LI (3,3), BL (0,6), AR (3,1), SR (1,1), IN (1,5) och FÖ (2,8). Det fanns en signifikant positiv korrelation mellan ålder och hur stor diskrepansen var mellan de olika versionerna för BL (r=0,379, p=0,039) och MA (r=0,413, p=0,023) samt en negativ korrelation mellan ålder och diskrepansen på FÖ (r=-0,422, p=0,020). Det fanns en signifikant negativ korrelation mellan utbildningsnivå och hur stor diskrepansen var mellan de olika versionerna av AR (r=-0,399, p=0,029).

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Neste trabalho foi realizado a síntese, caracterização e estudos termoanalíticos dos compostos de adição dos cloroacetatos de lantanídeos (III) com a 2-piperidinona. Os complexos obtidos foram analisados por titulação complexométrica com EDTA e análise elementar de carbono, hidrogênio e nitrogênio e foram caracterizados por condutividade eletrolítica molar, espectroscopia de absorção na região do infravermelho, espectroscopia de absorção na região do visível para o complexo de neodímio em solução de dimetilformamida e estudos de análise térmica: Análise Termogravimétrica (TG e DTG) e Calorimetria Exploratória Diferencial (DSC). Os compostos são sólidos, ligeiramente higroscópicos, solúveis em água e dimetilformamida (DMF). Os valores de condutância eletrolítica molar, medidas à 25ºC e em solução de DMF, indicaram comportamento não-eletrólitos, em solução de dimetilformamida. Nos espectros de absorção na região do infravermelho dos compostos de adição analisados, a frequência de estiramento do ligante (νCO) e a frequência de estiramento assimétrica do carboxilato (νassCOO) se deslocaram para frequências de menores energias, indicando que a coordenação do ligante ocorreu através do oxigênio do grupo carbonila. No espectro de absorção na região do visível, para o complexo de neodímio, foi determinada a força do oscilador (P), a qual indicou uma pouca influência do solvente nas transições hipersensitivas 4I9/2→ 2G7/2, 2G5/2 e na região da transição 4I9/2→ 2P1/2 do íon Nd3+. Os valores obtidos a partir das curvas termogravimétricas (TG/DTG) informaram que os complexos quando aquecidos, sofrem fusão sem decomposição, exceto para o complexo de neodímio, que apresenta decomposição durante a sua fusão. As curvas DSC, apresentaram picos com características endotérmicas e exotérmicas, ligadas respectivamente à fusão e decomposição dos complexos.

Santrauka Šio tyrimo tikslas – įvertinti WAIS-III psichometrines charakteristikas. Tyrime iš viso dalyvavo 75 tiriamieji, kuriems kvalifikuoti tyrėjai pateikė WAIS-III užduotis. Atrenkant tyrimo dalyvius, buvo vykdoma tikslinė atranka, remiantis šiais kriterijais: amžiumi, gyvenamąja vieta ir išsilavinimu. Šiame tyrime dalyvavo 36 vyrai ir 39 moterys. Tiriamųjų amžius nuo 16 iki 79 metų. Vertinant WAIS-III psichometrines charakteristikas, buvo įvertintas atskirų subtestų užduočių tinkamumas, naujų užduočių tinkamumas, verbalinių ir neverbalinių subtestų patikimumas dalijimo pusiau metodu ir testo konstrukto validumas. Buvo vertintas verbalinių ir neverbalinių subtestų užduočių tinkamumas, remiantis užduoties sunkumo bei diferencinės galios indeksais, koreguotos koreliacijos koeficientu. Labiausiai pakito Žodyno subtestas, kuriame buvo paliktas 21 originalios versijos žodis ir pridėta 12 naujų žodžių. Panašumų subteste buvo palikta 19 originalios versijos užduočių ir pridėtos 3 naujos. Informacijos subteste buvo palikti 24 originalios versijos klausimai ir pridėta 4 nauji. Supratingumo subteste buvo palikta 18 originalios versijos užduočių ir pridėtos 2 naujos. Visų verbalinių subtestų užduotys buvo išdėliotos nauja tvarka, išskyrus Skaičių eilė ir Raidžių – skaičių eilės. Paveikslėlių užbaigimo, Kubelių kompozicijos, Matricų ir Paveikslėlių užbaigimo užduotys buvo išdėliotos nauja tvarka. Objektų surinkimo subtestas buvo paliktas toks, koks pateikiamas originalioje versijoje... [toliau žr. visą tekstą]
Summary The purpose of this research is to evaluate WAIS-III psychometric characteristics. In total 75 subjects participated in the research; they were provided with WAIS-III tasks by the qualified researchers. When selecting the participants for the research, a target selection was carried out based on the following criteria: age, place of residence and education. 36 men and 39 women participated in this research. The age of the participants was from 16 to 79 years. While evaluating WAIS-III psychometric characteristics suitability of separate tasks of the subtests was estimated, as well as availability of new tasks, reliability of verbal and non-verbal subtests by the odd/even method and also the validity of the construct of the test. Suitability of the tasks of the verbal and non-verbal subtests was evaluated based on the indexes of the complexity of the task and the differential power, coefficient of the adjusted correlation. The Vocabulary subtest was transformed the most, in it 21 words from the original version were maintained and 12 new words added. In the Similarities subtest 19 tasks from the original version were maintained and 3 new tasks added. In the Information subtest 24 questions from the original version were maintained and 4 new questions added. In the Comprehension subtests 18 tasks were maintained from the original version and 2 new tasks were added. All the tasks of verbal subtests were set out in a new order, except for the Digit Span and Letter –... [to full text]

Publicación a texto completo no autorizada por el autor
Una deformidad se define como una forma o postura anormal de una parte del cuerpo debido a fuerzas mecánicas no disruptivas; surge con mayor frecuencia durante la vida fetal tardía debido a fuerzas mecánicas, afectando a menudo el sistema músculo-esquelético. Las deformidades dentofaciales pueden presentarse en forma aislada y afectar sólo la mandíbula, o bien, extenderse a múltiples estructuras craneofaciales, ser unilaterales o bilaterales, o expresarse en el plano facial vertical, horizontal o transversal. El caso clínico que se muestra, presenta a un paciente de sexo masculino con una deformidad dentofacial clase III producto de una proyección horizontal de la mandíbula, tratado en el servicio de cirugía oral y maxilofacial del HNAL y servicio de ortodoncia de la Clínica de Post Grado de la UNMSM, se realiza una revisión teórica de la patología, fase pr quirúrgica, fase post quirúrgica y seguimiento de 1 año post quirúrgico. El objetivo de este trabajo es describir las características clínicas de una deformidad dentofacial clase III y presentar el manejo ortodóntico quirúrgico de acuerdo al protocolo establecido de las instituciones participantes.

Music Composition
Ph.D.
ABSTRACT Marimba Rossa is a three-movement concert piece for marimba and symphony orchestra. The 14-minute piece is written in the spirit of the Italian Baroque concertos of Antonio Vivaldi (the "Red Priest" for whom the piece is named), using a harmonic and rhythm language that is heavily influenced by the concert and pop music of the late twentieth-century. Marimba Rossa was composed with the concept of Ars Combinatoria in mind. First espoused by George Rochberg in 1973, Ars Combinatoria is concert music that uses musical gestures drawn from any musical tradition. The accompanying monograph provides a detailed history of the modern concert marimba and an account of the evolution of its concert and popular music repertoire. Specific information about the marimba's origins in Asia, its place in the Bible, the development of the European strohfiedel xylophone, the refinement of the instrument in America, and a discussion of the Guatemalan, Mexican, and Japanese marimba tradition is included to provide a context and rationale for the composing of Marimba Rossa. The contributions of John Calhoun Deagan, Ulysses G. Leedy, George Hamilton Green, Harry Breuer, Clair Omar Musser, and others are chronicled. Other topics include: the use of the xylophone in the symphony orchestra; polytonality; modal writing; and the folk music of Calabria, Italy. The monograph also describes the juxtaposition of the marimba and various instrumental consorts and the metaphoric class struggle these pairings represent in Marimba Rossa.
Temple University--Theses

Avant 1941, dans les villes grandes et moyennes, on trouvait, pour tenir les comptes, recouvrer les recettes et payer les dépenses locales, des receveurs municipaux qui étaient choisis par la ville elle-même et soumis à l’autorité du maire. Ils avaient hérité d’un passé remontant aux origines mêmes du fait urbain, au moment où le regroupement des hommes et des richesses avait permis l’émergence de fiscalités et d’administrations autonomes. Avec la loi du 5 avril 1884, ils furent chargés de conforter les institutions républicaines au sein d’une nouvelle configuration dans laquelle le local servait d’assise à la politique nationale. Leur pérennité manifestait la force d’un pouvoir municipal qui résistait à toutes les velléités de contrôle des comptes, jusqu’au moment où, en 1930, ils changèrent soudain de camp, demandant à entrer dans les cadres du ministère des Finances. Instruments de deux pouvoirs revendiquant chacun une forte légitimité, ils nous conduisent au plus profond des liens financiers noués entre les communes et l’État, ainsi que dans les failles de l’articulation générale entre centralisation et décentralisation. Les hommes étaient à l’image du rôle qu’on leur faisait jouer. Fortement impliqués dans la vie de la cité, ils n’étaient pas des techniciens mais des notables ou des militants. Émanations de la ville qu’ils allaient servir, ils ne pouvaient remplir la mission de contrôle comptable qui leur avait été assignée mais finirent par intérioriser la contrainte normative qui pesait sur eux. L’étude de ces personnages méconnus agit comme un révélateur des pratiques et des représentations en matière de comptabilité, de finances et de gouvernement local
Avant 1941, dans les villes grandes et moyennes, on trouvait, pour tenir les comptes, recouvrer les recettes et payer les dépenses locales, des receveurs municipaux qui étaient choisis par la ville elle-même et soumis à l’autorité du maire. Ils avaient hérité d’un passé remontant aux origines mêmes du fait urbain, au moment où le regroupement des hommes et des richesses avait permis l’émergence de fiscalités et d’administrations autonomes. Avec la loi du 5 avril 1884, ils furent chargés de conforter les institutions républicaines au sein d’une nouvelle configuration dans laquelle le local servait d’assise à la politique nationale. Leur pérennité manifestait la force d’un pouvoir municipal qui résistait à toutes les velléités de contrôle des comptes, jusqu’au moment où, en 1930, ils changèrent soudain de camp, demandant à entrer dans les cadres du ministère des Finances. Instruments de deux pouvoirs revendiquant chacun une forte légitimité, ils nous conduisent au plus profond des liens financiers noués entre les communes et l’État, ainsi que dans les failles de l’articulation générale entre centralisation et décentralisation. Les hommes étaient à l’image du rôle qu’on leur faisait jouer. Fortement impliqués dans la vie de la cité, ils n’étaient pas des techniciens mais des notables ou des militants. Émanations de la ville qu’ils allaient servir, ils ne pouvaient remplir la mission de contrôle comptable qui leur avait été assignée mais finirent par intérioriser la contrainte normative qui pesait sur eux. L’étude de ces personnages méconnus agit comme un révélateur des pratiques et des représentations en matière de comptabilité, de finances et de gouvernement local

La révolte qui suivit l'assassinat de Ptolémée de Maurétanie ne put empêcher l'annexion du pays et la création de deux provinces romaines. Volubilis, ville phare de cette province de l'extrême occident africain, rejoint ainsi toutes ces cités qui ont contribué au rayonnement de la civilisation romano-africaine. La ville, qui n'était pas restée à l'écart de la koiné culturelle méditerranéenne adopte, à l'instar des autres cités africaines, les cultes introduits par les nouveaux maîtres et met en place la religion impériale, gage de loyauté des populations. Pourtant, derrière cette apparente conformité, l'examen des documents laisse apparaître des particularités propres à cette cité où certaines des grandes divinités africaines n'ont rencontré que peu d'écho quand elles ne sont pas absentes. Faut-il, malgré l'ignorance où nous sommes de la vie religieuse à Volubilis durant l'époque préromaine, chercher dans l'existence de cultes antérieurs, l'explication de cette adhésion sélective ? Rome a, certes, toléré l'expression de particularismes dans la vie religieuse mais elle n'en a pas moins imposé ces dieux
The rebellion which followed the murder of Ptolemy of Mauritania could not prevent the annexation of the country and the founding of two Roman provinces. Volubilis, the leading city of this farthest African West, thus joins all the cities that have contributed to the worldwide influence of the afro-roman civilisation. The city, which had already been influenced by the Mediterranean cultural koine, adopts, alike the other African cities, the cults introduced by the new masters and sets the Emperor's cult as a token of the populations' loyalty. However, beyond this apparent conformity the analysis of the documents reveals some original characteristics about this city where a number of great African gods have met tedious welcome if not none at all. In Spite of our ignorance of religious life in Volubilis during the pre-roman period, shall this selective adhesion be explained by the existence of former cults ? Rome has actually tolerated that specificities be expressed in religious life but it has nonetheless imposed its gods