Self‐cleaning perovskite type catalysts for the dry reforming of methane

Gas-to-liquid processes are generally used to convert natural gas or other gaseous hydrocarbons into liquid fuels via an intermediate syngas stream. This includes the production of liquid fuels from biomass-derived sources such as biogas. For example, the dry reforming of methane is done by reacting CH4 and CO2, the two main components of natural biogas, into more valuable products, i.e., CO and H2. Nickel containing perovskite type catalysts can promote this reaction, yielding good conversions and selectivities; however, they are prone to coke laydown under certain operating conditions. We investigated the addition of high oxygen mobility dopants such as CeO2, ZrO2, or YSZ to reduce carbon laydown, particularly using reaction conditions that normally result in rapid coking. While doping with YSZ, YDC, GDC, and SDC did not result in any improvement, we show that a Ni perovskite catalyst (Na0.5La0.5Ni0.3Al0.7O2.5) doped with 80.9 ZrO2 15.2 CeO2 gave the lowest amount of carbon formation at 800 °C and activity was maintained over the operating time.

Cloning and Characterization of Two Potent Kunitz Type Protease Inhibitors from Echinococcus granulosus

The tapeworm Echinococcus granulosus is responsible for cystic echinococcosis (CE), a cosmopolitan disease which imposes a significant burden on the health and economy of affected communities. Little is known about the molecular mechanisms whereby E. granulosus is able to survive in the hostile mammalian host environment, avoiding attack by host enzymes and evading immune responses, but protease inhibitors released by the parasite are likely implicated. We identified two nucleotide sequences corresponding to secreted single domain Kunitz type protease inhibitors (EgKIs) in the E. granulosus genome, and their cDNAs were cloned, bacterially expressed and purified. EgKI-1 is highly expressed in the oncosphere (egg) stage and is a potent chymotrypsin and neutrophil elastase inhibitor that binds calcium and reduced neutrophil infiltration in a local inflammation model. EgKI-2 is highly expressed in adult worms and is a potent inhibitor of trypsin. As powerful inhibitors of mammalian intestinal proteases, the EgKIs may play a pivotal protective role in preventing proteolytic enzyme attack thereby ensuring survival of E. granulosus within its mammalian hosts. EgKI-1 may also be involved in the oncosphere in host immune evasion by inhibiting neutrophil elastase and cathepsin G once this stage is exposed to the mammalian blood system. In light of their key roles in protecting E. granulosus from host enzymatic attack, the EgKI proteins represent potential intervention targets to control CE. This is important as new public health measures against CE are required, given the inefficiencies of available drugs and the current difficulties in its treatment and control. In addition, being a small sized highly potent serine protease inhibitor, and an inhibitor of neutrophil chemotaxis, EgKI-1 may have clinical potential as a novel anti-inflammatory therapeutic.

Nucleophilic addition of Nitrones to Electron deficient acetylenes and related studies

Nitrones or azomethine-N-oxides are important precursors for the synthesis of several heterocyclic systems. They belong to the allyl anion type 1,3-dipoles and possess unique structural features which make them extraordinarily useful synthons. They behave as 1,3-dipoles in 1,3-dipolar cycloaddition reactions and as electrophiles in reactions with organometallic reagents. These are the two basic reactions given by nitrones. Nitrones also act as ‘spin traps’ in which they react with short-lived radicals to furnish stable nitroxide radicals which can be detected and identified by electron paramagnetic resonance (EPR) spectroscopy. Recently SmI2 catalysed reductive cross-coupling reactions of nitrones have gained significant interest in which the reactions are initiated by single electron transfer (SET) to nitrones. Apart from these reactions, nitrones are also known to participate in reactions which are initiated by the nucleophilic attack of nitrone-oxygen. In our group, we have also explored the nucleophilic character of nitrones through various reactions. The results obtained enabled us to develop a novel two-step one-pot strategy for quinolines and indoles - the heterocycles renowned for their pharmacological applications, from nitrones and electron deficient acetylenes. Using dibenzoylacetylene and phenylbenzoylacetylene as dipolarophiles, we could introduce a desired functional group at a predetermined position of the quinolines or indoles to be synthesised. In this context, the thesis entitled “NUCLEOPHILIC ADDITION OF NITRONES TO ELECTRON DEFICIENT ACETYLENES AND RELATED STUDIES” portrays our attempt to expand the scope of our x novel synthetic protocol using ester functionalised acetylenes: dimethyl acetylenedicarboxylate (DMAD) and methyl propiolate. The thesis is organised in to five chapters. The first chapter briefly describes the different classes of reactions that nitrone functionality can tolerate. The research problem is defined at the end of this chapter. The second chapter describes the synthesis of different nitrones used for the present study. The optimisation and expansion of scope of the novel strategy towards quinoline synthesis is discussed in the third chapter. The fourth chapter portrays the synthesis of indole-3-carboxylates using the novel strategy. In the fifth chapter, the reaction of N-(2,6-dimethylphenyl) and N-(2,4,6-trimethylphenyl)nitrones are discussed. Here we also discuss the mechanistic reinvestigation of Baldwin’s proposal in the isoxazoline-oxazoline rearrangement. The major outcome of the work is given at the end of the thesis. The structural formulae, schemes, tables and figures are numbered chapter-wise since each chapter of the thesis is organized as an independent unit. All new compounds (except two compounds reported in fourth chapter) are fully characterised on the basis of spectral and analytical data and single crystal X-ray analysis on representative examples. Relevant references are included at the end of individual chapters.

A Arte de Governar: o exercício do poder pelo saber segundo Michael Foucault

As obras de Michel Foucault exercem influencia em várias áreas das ciências humanas. O mesmo fato se repetiu em teoria das organizações, onde as idéias foucaultianas estão sendo empregadas fundamentalmente para trazer novas luzes para as discussões sobre poder nas organizações. A despeito da influência significativa na área, não há discussões sobre como as obras de Michel Foucault estão sendo utilizadas. A presente dissertação de mestrado tem por objetivo sistematizar os estudos que utilizaram as idéias de Michel Foucault em teoria das organizações, problematizá-los e indicar alguns caminhos para o desenvolvimento desse tipo de análise. De uma forma geral, percebemos que a produção acadêmica em teoria das organizações baseadas nas obras de Michel Foucault tratam majoritariamente das disciplinas e deixam de lado outros aspectos da analítica do poder. Ademais, percebemos que há uma adoção simplificada da analítica do poder e uma junção acriteriosa de conceitos e noções oriundas de diferentes matrizes epistemológicas, além da inadequação da designação “pósmoderno” para classificar as obras de Michel Foucault e suas utilizações em teoria das organizações. Como possíveis desenvolvimentos, indicamos as possibilidades de análise que podem ser abertas na teoria das organizações pelo uso das noções de biopolítica e governamentalidade. / The works of Michel Foucault exert influence in various areas of the humanities. The same thing happened in organization theory, Foucauldian where ideas are being used primarily to bring new light to the discussions about power in organizations. Despite the significant influence in the area, there are discussions about the works of Michel Foucault are being used. This dissertation aims to systematize the studies that used the ideas of Michel Foucault in organization theory, problematize them and indicate some directions for developing this type of analysis. In general, we find that the academic production in the theory of organizations based on the writings of Michel Foucault deal mostly of disciplines and leave out other aspects of analytical power. Moreover, we realize that there is an adoption of simplified analytical power of an indiscriminate and a junction of concepts and notions from different epistemological matrices, besides the inadequacy of the term "postmodern" to classify the works of Michel Foucault and its uses in organizational theory. As possible developments, indicate the possibilities of analysis that can be opened in organization theory by using the notions of biopolitics and governmentality.

Habitudes alimentaires et apports nutritionnels chez les personnes présentant une dystrophie myotonique de type 1

L’objectif de cette étude était de décrire les habitudes alimentaires et les apports nutritionnels des patients atteints de dystrophie myotonique de type 1 (DM1). Au total, 32 femmes et 20 hommes souffrant de DM1 et suivis à la Clinique des maladies neuromusculaires de Jonquière, ont complété un journal alimentaire de 3 jours non consécutifs (2 jours de semaine et 1 jour de fin de semaine). Parmi ces patients, 13,5 % étaient en sous-poids alors que 51,9 % présentaient de l’embonpoint ou de l’obésité. Les apports moyens en lipides et en glucides ne respectaient pas l’étendue des valeurs acceptables pour ces macronutriments. Les apports moyens étaient également insuffisants pour la majorité des micronutriments. Finalement, la consommation d’aliments des quatre groupes du Guide alimentaire canadien était inférieure aux recommandations. Les résultats démontrent qu’une proportion importante des patients avec DM1 présente une alimentation inadéquate.

The Redox Potentials of n-type Colloidal Semiconductor Nanocrystals

Thesis (Ph.D.)--University of Washington, 2016-08

Karl-Josef Pazzini / Marianne Schuller / Michael Wimmer (Hrsg.): Lehren bildet? Vom Rätsel unserer Lehranstalten Bielefeld: transcript 2010 [Rezension]

Rezension von: Karl-Josef Pazzini / Marianne Schuller / Michael Wimmer (Hrsg.): Lehren bildet? Vom Rätsel unserer Lehranstalten Bielefeld: transcript 2010 (338 S.; ISBN 978-3-8376-1176-2)

Klaus Fröhlich-Gildhoff / Stefanie Pietsch / Michael Wünsche / Maike Rönnau-Böse (Hrsg.): Zusammenarbeit mit Eltern, Ein Curriculum für die Aus- und Weiterbildung, (Materialien zur Frühpädagogik Bd. 7) plus CD, Freiburg: Verlag FEL 2011(264 S. [...] [Sammelrezension]

Sammelrezension von: 1. Klaus Fröhlich-Gildhoff / Stefanie Pietsch / Michael Wünsche / Maike Rönnau-Böse (Hrsg.): Zusammenarbeit mit Eltern, Ein Curriculum für die Aus- und Weiterbildung, (Materialien zur Frühpädagogik Bd. 7) plus CD, Freiburg: Verlag FEL 2011 (264 S.; ISBN 978-3-932650-43-3) 2. Susanne Viernickel / Iris Nentwig-Gesemann / Henriette Harms / Sandra Richter / Stefanie Schwarz: Profis für Krippen, Curriculare Bausteine für die Aus- und Weiterbildung frühpädagogischer Fachkräfte, (Materialien zur Frühpädagogik Bd. 8) plus CD, Freiburg: Verlag FEL 2011 (210 S.; ISBN 978-3-932650-44-)

Katrin Ulrike Zaborowski / Michael Meier / Georg Breidenstein: Leistungsbewertung und Unterricht, Ethnographische Studien zur Bewertungspraxis in Gymnasium und Sekundarschule. Wiesbaden: VS Verlag für Sozialwissenschaften 2011 [Rezension]

Rezension von: Katrin Ulrike Zaborowski / Michael Meier / Georg Breidenstein: Leistungsbewertung und Unterricht, Ethnographische Studien zur Bewertungspraxis in Gymnasium und Sekundarschule, Wiesbaden: VS Verlag für Sozialwissenschaften 2011 (376 S.; ISBN 978-3-531-16808-1)

Michael Schratz / Johanna F. Schwarz / Tanja Westfall-Greiter: Lernen als bildende Erfahrung, Vignetten in der Praxisforschung, Mit einem Vorwort von Käte Meyer-Drawe und Beiträgen von Horst Rumpf, Carol Ann Tomlinson, Mike Rose u.a. Innsbruck: Studienverlag 2012 [Rezension]

Rezension von: Michael Schratz / Johanna F. Schwarz / Tanja Westfall-Greiter: Lernen als bildende Erfahrung, Vignetten in der Praxisforschung, Mit einem Vorwort von Käte Meyer-Drawe und Beiträgen von Horst Rumpf, Carol Ann Tomlinson, Mike Rose u.a., Innsbruck: Studienverlag 2012 (161 S.; ISBN 978-3706551182)

Large eddy simulation of shock boundary layer interaction control using micro-vortex generators

The performance of supersonic engine inlets and external aerodynamic surfaces can be critically affected by shock wave / boundary layer interactions (SBLIs), whose severe adverse pressure gradients can cause boundary layer separation. Currently such problems are avoided primarily through the use of boundary layer bleed/suction which can be a source of significant performance degradation. This study investigates a novel type of flow control device called micro-vortex generators (µVGs) which may offer similar control benefits without the bleed penalties. µVGs have the ability to alter the near-wall structure of compressible turbulent boundary layers to provide increased mixing of high speed fluid which improves the boundary layer health when subjected to flow disturbance. Due to their small size,µVGs are embedded in the boundary layer which provide reduced drag compared to the traditional vortex generators while they are cost-effective, physically robust and do not require a power source. To examine the potential of µVGs, a detailed experimental and computational study of micro-ramps in a supersonic boundary layer at Mach 3 subjected to an oblique shock was undertaken. The experiments employed a flat plate boundary layer with an impinging oblique shock with downstream total pressure measurements. The moderate Reynolds number of 3,800 based on displacement thickness allowed the computations to use Large Eddy Simulations without the subgrid stress model (LES-nSGS). The LES predictions indicated that the shock changes the structure of the turbulent eddies and the primary vortices generated from the micro-ramp. Furthermore, they generally reproduced the experimentally obtained mean velocity profiles, unlike similarly-resolved RANS computations. The experiments and the LES results indicate that the micro-ramps, whose height is h≈0.5δ, can significantly reduce boundary layer thickness and improve downstream boundary layer health as measured by the incompressible shape factor, H. Regions directly behind the ramp centerline tended to have increased boundary layer thickness indicating the significant three-dimensionality of the flow field. Compared to baseline sizes, smaller micro-ramps yielded improved total pressure recovery. Moving the smaller ramps closer to the shock interaction also reduced the displacement thickness and the separated area. This effect is attributed to decreased wave drag and the closer proximity of the vortex pairs to the wall. In the second part of the study, various types of µVGs are investigated including micro-ramps and micro-vanes. The results showed that vortices generated from µVGs can partially eliminate shock induced flow separation and can continue to entrain high momentum flux for boundary layer recovery downstream. The micro-ramps resulted in thinner downstream displacement thickness in comparison to the micro-vanes. However, the strength of the streamwise vorticity for the micro-ramps decayed faster due to dissipation especially after the shock interaction. In addition, the close spanwise distance between each vortex for the ramp geometry causes the vortex cores to move upwards from the wall due to induced upwash effects. Micro-vanes, on the other hand, yielded an increased spanwise spacing of the streamwise vortices at the point of formation. This resulted in streamwise vortices staying closer to the wall with less circulation decay, and the reduction in overall flow separation is attributed to these effects. Two hybrid concepts, named “thick-vane” and “split-ramp”, were also studied where the former is a vane with side supports and the latter has a uniform spacing along the centerline of the baseline ramp. These geometries behaved similar to the micro-vanes in terms of the streamwise vorticity and the ability to reduce flow separation, but are more physically robust than the thin vanes. Next, Mach number effect on flow past the micro-ramps (h~0.5δ) are examined in a supersonic boundary layer at M=1.4, 2.2 and 3.0, but with no shock waves present. The LES results indicate that micro-ramps have a greater impact at lower Mach number near the device but its influence decays faster than that for the higher Mach number cases. This may be due to the additional dissipation caused by the primary vortices with smaller effective diameter at the lower Mach number such that their coherency is easily lost causing the streamwise vorticity and the turbulent kinetic energy to decay quickly. The normal distance between the vortex core and the wall had similar growth indicating weak correlation with the Mach number; however, the spanwise distance between the two counter-rotating cores further increases with lower Mach number. Finally, various µVGs which include micro-ramp, split-ramp and a new hybrid concept “ramped-vane” are investigated under normal shock conditions at Mach number of 1.3. In particular, the ramped-vane was studied extensively by varying its size, interior spacing of the device and streamwise position respect to the shock. The ramped-vane provided increased vorticity compared to the micro-ramp and the split-ramp. This significantly reduced the separation length downstream of the device centerline where a larger ramped-vane with increased trailing edge gap yielded a fully attached flow at the centerline of separation region. The results from coarse-resolution LES studies show that the larger ramped-vane provided the most reductions in the turbulent kinetic energy and pressure fluctuation compared to other devices downstream of the shock. Additional benefits include negligible drag while the reductions in displacement thickness and shape factor were seen compared to other devices. Increased wall shear stress and pressure recovery were found with the larger ramped-vane in the baseline resolution LES studies which also gave decreased amplitudes of the pressure fluctuations downstream of the shock.

Using a voxel-based krogh cylinder array to simulate microvascular contrast enhancement

The goal of this study is to better simulate microscopic and voxel-based dynamic contrast enhancement in magnetic resonance imaging. Specifically, errors imposed by the traditional two-compartment model are reduced by introducing a novel Krogh cylinder network. The two-compartment model was developed for macroscopic pharmacokinetic analysis of dynamic contrast enhancement and generalizing it to voxel dimensions, due to the significant decrease in scale, imposes physiologically unrealistic assumptions. In the project, a system of microscopic exchange between plasma and extravascular-extracellular space is built while numerically simulating the local contrast agent flow between and inside image elements. To do this, tissue parameter maps were created, contrast agent was introduced to the tissue via a flow lattice, and various data sets were simulated. The effects of sources, tissue heterogeneity, and the contribution of individual tissue parameters to an image are modeled. Further, the study attempts to demonstrate the effects of a priori flow maps on image contrast, indicating that flow data is as important as permeability data when analyzing tumor contrast enhancement. In addition, the simulations indicate that it may be possible to obtain tumor-type diagnostic information by acquiring both flow and permeability data.

Frank-Michael Kuhlemann: Modernisierung und Disziplinierung. Sozialgeschichte des preußischen Volksschulwesens 1794-1872. (Kritische Studien zur Geschichtswissenschaft. Bd. 96.) Göttingen: Vandenhoeck & Ruprecht 1992 [Rezension]

Rezension von: Frank-Michael Kuhlemann: Modernisierung und Disziplinierung. Sozialgeschichte des preußischen Volksschulwesens 1794-1872. (Kritische Studien zur Geschichtswissenschaft. Bd. 96.) Göttingen: Vandenhoeck & Ruprecht 1992. 468 S.

Diet, microbes and gut immune responses in the pathogenesis of experimental type 1 diabetes

Type 1diabetes (T1D) is an autoimmune disease, which is influenced by a variety of environmental factors including diet and microbes. These factors affect the homeostasis and the immune system of the gut. This thesis explored the altered regulation of the immune system and the development of diabetes in non-obese diabetic (NOD) mice. Inflammation in the entire intestine of diabetes-prone NOD mice was studied using a novel ex-vivo imaging system of reactive oxygen and nitrogen species (RONS), in relation to two feeding regimens. In parallel, gut barrier integrity and intestinal T-cell activation were assessed. Extra-intestinal manifestations of inflammation and decreased barrier integrity were sought for by studying peritoneal leukocytes. In addition, the role of pectin and xylan as dietary factors involved in diabetes development in NOD mice was explored. NOD mice showed expression of RONS especially in the distal small intestine, which coincided with T-cell activation and increased permeability to macromolecules. The introduction of a casein hydrolysate (hydrolysed milk protein) diet reduced these phenomena, altered the gut microbiota and reduced the incidence of T1D. Extra-intestinally, macrophages appeared in large numbers in the peritoneum of NOD mice after weaning. Peritoneal macrophages (PM) expressed high levels of interleukin-1 receptor associated kinase M (IRAK-M), which was indicative of exposure to ligands of toll-like receptor 4 (TLR-4) such as bacterial lipopolysaccharide (LPS). Intraperitoneal LPS injections activated T cells in the pancreatic lymph nodes (PaLN) and thus, therefore potentially could activate islet-specific T cells. Addition of pectin and xylan to an otherwise diabetes-retarding semisynthetic diet affected microbial colonization of newly-weaned NOD mice, disturbed gut homeostasis and promoted diabetes development. These results help us to understand how diet and microbiota impact the regulation of the gut immune system in a way that might promote T1D in NOD mice.

Soziale Ungleichheiten beim Übergang von der Grundschule in die Sekundarstufe I. Theorie, Forschungsstand, Interventions- und Fördermöglichkeiten

Auf der Basis eines theoretischen Modells zum Übergangsprozess, in dem primäre und sekundäre Herkunftseffekte nach Boudon unterschieden werden, fasst der vorliegende Beitrag den empirischen Kenntnisstand zum Einfluss der familiären Herkunft auf den Übergang von der Grundschule in die Sekundarstufe I zusammen. Dabei wird neben den primären Effekten zwischen verschiedenen Arten von sekundären Herkunftseffekten unterschieden: sekundäre Effekte der Leistungsbeurteilung, der Schullaufbahnempfehlung und des Übergangsverhaltens. Die Befunde sprechen für die Existenz primärer und sekundärer Herkunftseffekte im deutschen Schulsystem: Kinder aus sozial schwachen Familien haben schlechtere Schulleistungen, erhalten jedoch selbst bei gleichen Testleistungen noch schlechtere Beurteilungen durch die Lehrkräfte (Noten und Schullaufbahnempfehlungen) und gehen bei gleichen Testleistungen und Schulnoten und gleicher Empfehlung häufiger auf niedrigere Schulformen über. Weiterhin werden Ergebnisse aus Studien zur Quantifizierung und Neutralisation von primären und sekundären Herkunftseffekten vorgestellt und diskutiert sowie mögliche Interventions- und Fördermöglichkeiten zur Verringerung der Herkunftseffekte beim Übergang aufgezeigt.