Transformation of carbon dioxide to diethyl carbonate over ceria and ceria-supported catalysts

Carbon dioxide is regarded, nowadays, as a primary anthropogenic greenhouse gas leading to global warming. Hence, chemical fixation of CO2 has attracted much attention as a possible way to manufacture useful chemicals. One of the most interesting approaches of CO2 transformations is the synthesis of organic carbonates. Since conventional production technologies of these compounds involve poisonous phosgene and carbon monoxide, there is a need to develop novel synthetic methods that would better match the principles of "Green Chemistry" towards protection of the environment and human health. Over the years, synthesis of dimethyl carbonate was under intensive investigation in the academia and industry. Therefore, this study was entirely directed towards equally important homologue of carbonic esters family namely diethyl carbonate (DEC). Novel synthesis method of DEC starting from ethanol and CO2 over heterogeneous catalysts based on ceria (CeO2) was studied in the batch reactor. However, the plausible drawback of the reaction is thermodynamic limitations. The calculated values revealed that the reaction is exothermic (ΔrHØ298K = ─ 16.6 J/ ) and does not occur spontaneously at rooms temperature (ΔrGØ 298K = 35.85 kJ/mol). Moreover, co-produced water easily shifts the reaction equilibrium towards reactants excluding achievement of high yields of the carbonate. Therefore, in-situ dehydration has been applied using butylene oxide as a chemical water trap. A 9-fold enhancement in the amount of DEC was observed upon introduction of butylene oxide to the reaction media in comparison to the synthetic method without any water removal. This result confirms that reaction equilibrium was shifted in favour of the desired product and thermodynamic boundaries of the reaction were suppressed by using butylene oxide as a water scavenger. In order to obtain insight into the reaction network, the kinetic experiments were performed over commercial cerium oxide. On the basis of the selectivity/conversion profile it could be concluded that the one-pot synthesis of diethyl carbonate from ethanol, CO2 and butylene oxide occurs via a consecutive route involving cyclic carbonate as an intermediate. Since commercial cerium oxide suffers from the deactivation problems already after first reaction cycle, in-house CeO2 was prepared applying room temperature precipitation technique. Variation of the synthesis parameters such as synthesis time, calcination temperature and pH of the reaction solution turned to have considerable influence on the physico-chemical and catalytic properties of CeO2. The increase of the synthesis time resulted in high specific surface area of cerium oxide and catalyst prepared within 50 h exhibited the highest amount of basic sites on its surface. Furthermore, synthesis under pH 11 yielded cerium oxide with the highest specific surface area, 139 m2/g, among all prepared catalysts. Moreover, CeO2─pH11 catalyst demonstrated the best catalytic activity and 2 mmol of DEC was produced at 180 oC and 9 MPa of the final reaction pressure. In addition, ceria-supported onto high specific surface area silicas MCM-41, SBA-15 and silica gel were synthesized and tested for the first time as catalysts in the synthesis of DEC. Deposition of cerium oxide on MCM-41 and SiO2 supports resulted in a substantial increase of the alkalinity of the carrier materials. Hexagonal SBA-15 modified with 20 wt % of ceria exhibited the second highest basicity in the series of supported catalysts. Evaluation of the catalytic activity of ceria-supported catalysts showed that reaction carried out over 20 wt % CeO2-SBA-15 generated the highest amount of DEC.

The cytotoxicity of methacryloxylethyl cetyl ammonium chloride, a cationic antibacterial monomer, is related to oxidative stress and the intrinsic mitochondrial apoptotic pathway

Antibacterial monomers incorporated in dentin bonding systems may have toxic effects on the pulp. Thus, the cytotoxicity of antibacterial monomers and its underlying mechanisms must be elucidated to improve the safety of antibacterial monomer application. The influence of an antibacterial monomer, methacryloxylethyl cetyl ammonium chloride (DMAE-CB), on the vitality of L929 mouse fibroblasts was tested using MTT assay. Cell cycle progression was studied using flow cytometry. Production of intracellular reactive oxygen species (ROS) after DMAE-CB treatment was measured using 2,7-dichlorodihydrofluorescein diacetate staining and flow cytometry analysis. Loss of mitochondrial membrane potential, disturbance of Bcl-2 and Bax expression, as well as release of cytochrome C were also measured using flow cytometry analysis or Western blot to explore the possible involvement of the mitochondrial-related apoptotic pathway. DMAE-CB elicited cell death in a dose-dependent manner and more than 50% of cells were killed after treatment with 30 µM of the monomer. Both necrosis and apoptosis were observed. DMAE-CB also induced G1- and G2-phase arrest. Increased levels of intracellular ROS were observed after 1 h and this overproduction was further enhanced by 6-h treatment with the monomer. DMAE-CB may cause apoptosis by disturbing the expression of Bcl-2 and Bax, reducing the mitochondrial potential and inducing release of cytochrome C. Taken together, these findings suggest that the toxicity of the antibacterial monomer DMAE-CB is associated with ROS production, mitochondrial dysfunction, cell cycle disturbance, and cell apoptosis/necrosis.

Gadamer's transformation of hermeneutics : from Dilthey to Heidegger

Abstract: The purpose of this paper is to show how Gadamer's hermeneutics synthesizes the insights of both Heidegger and Dilthey in order to introduce a new hermeneutics. Gadamer's hermeneutics is based not only on the priority of ontology, as Heidegger insists, and neither is it only a product of life which can be objectively understood through study and rigorous method, as Dilthey suggests. For Gadamer, hermeneutics is the bringing together of ontology in terms of history. By this synthesis Gadamer not only places himself within the context of a Lebensphilosophie, but also shows that it is within language that Being can be disclosed according to a lived context. Throughout this paper the philosophies ofDilthey and Heidegger are explicated within a historical context as to bring out how, and why, Gadamer sees the need to surpass these philosophies. Through Gadamer's philosophy of play and the game, language, the dialogical model, application, and the fusion of horizons we can see how Gadamer's critique and questioning of these two philosophy leads to his new hermeneutics. Special attention is paid to the role in which these two contrasting philosophies were used to complement each other in the product of Gadamer' s philosophical hermeneutics as it is presented in his major work Truth andMethod. For Gadamer, the task of understanding is never complete. Therefore, his hermeneutics remains a dynamic structure with which we can always question the past and our traditions. This paper seeks to show his philosophical movements within these questions

Paradigms and prisons: a narrative of translation and transformation : my hero's journey from "at-risk" youth to teacher/learner in a jail setting /

All life is suffering. Life is the pursuit ofhappiness. These are two foundational Buddhist dictums that, in their simplicity, I have entirely misunderstood regarding their depth, misreading them as contradictory. Indeed, my superficial interpretations led me to Thoreau's life ofquiet desperation and deep depression. We come to know and bring understanding to our lives by storying them. My own Hero's Journey, the path from my egoic selftoward the universal Self, can be understood as the resultant translations and transformations. Inevitably each of us is involved in such a story, though most are unaware of the stages along our own Hero's journey. ' Narrative honours writing as a means of knowing. The contemplative reflection allows insight into our imprisoning paradigms, beliefs, behaviours, and blind spots. My research revisits and explores nodal experiences along my Hero's Journey through 4 categories: self, society, soil, and Self. While the value of this process of narrative inquiry lay in its ability to come to know and understand one's self, perhaps its greater value is of a more universal nature. My inquiry, while adding to the body of academic educational narrative literature, may also illuminate a path to educators, students, and all interested, encouraging a response to the call of their own Hero's journey. I am a teacher/learner in a jail setting, working with youth between the ages of 12 and 18 who have committed crimes such as armed robbery, assault, rape, and murder. As this thesis follows my continual development from egoic self/teacher/learner to universal Self/Teacher/Learner, it also enables me to both consciously and unconsciously open the ways in which I expand my care, compassion, and love to work with at-risk youth.

Organizational change: implications of culture and leadership in the transformation to a total quality management paradigm

The study was undertaken to investigate organizational readiness for change to a total quality management (TQM) paradigm as the corporate-wide strategy within a long-term care facility. The focus of the study was on leadership values and organizational cultural characteristics that could either accelerate or impede the change process at The Public Hospital. structurally, the ~tudy included 'three distinct components. The first component examined the management philosophy outlined by Deming (1986) and his contemporary Juran (1989) in order to determine what leadership values best support the new Total Quality Management paradigm. Secondly, this information was compared to present leadership values at The Public Hospital with the purpose of identifying opportunities for improvement within the organization's current culture as the hospital moves toward the desired TQM culture. The final component, a roadmap, was developed to reflect the most appropriate direction for organizational change at The Public Hospital.

Transformation in teaching : listening to every voice

Action research is a methodology that supports practitioner research. This study is an exploration of one researcher's practice using the living-theory approach to action research. Initially, my focus was to improve my practice by asking how I can facilitate transformative learning experiences with the teachers with whom I work. As part of this search, I examined the contradictions between my espoused and implicit values. In keeping with the evolving nature of my inquiry, I unveiled the telos that constituted the impetus for my search, which began as a tension about the quality of my interactions and ended as a quest to find my voice among the others'. I used personal narratives, journal entries, a videotaping session, interactions with critical friends and interviews with colleagues and administrators to engage in a process of continuing self- and interactive reflection. Throughout my study, I explored how theoretical concepts intertwine with personal experiences. In the final chapter, I share the possible connections between my living educational theory and a more general theory of transformative learning. I conclude my study with a look at the transformation process I underwent as a result of the study and the new questions I formulated as I began the action research spiral again.

The role of the Ruah YHWH in creative transformation : a process theology perspective applied to Judges 14

La Ruah YHWH joue un rôle important dans la transformation créative de l’univers et des entités actuelles; cependant, une réflexion concernant les modalités de ce rôle reste à développer. La théologie processuelle offre une plateforme à partir de laquelle sont examinées diverses facettes des rôles que peut jouer la Ruah YHWH dans un monde où le chaos semble dominer. L’objectif de ce mémoire est justement d’explorer la Ruah YHWH dans son rôle de transformation créative au service, ultimement de l’ordre, de la paix et de l’harmonie dans le monde, les communautés, la vie des entités actuelles, etc. Le Chapitre 1 passe en revue des notions clés de la théologie processuelle. Le concept des “entités actuelles” est d’abord défini. Sont ensuite examinées les différentes phases du devenir d’une entité actuelle. Finalement, les concepts de “créativité” et de “transformation”, dans une perspective de la Ruah YHWH font l’objet d’observations attentives avant d’aborder « trois natures » de Dieu, à savoir primordiale, conséquente, et superjective. Le Chapitre 2 s’intéresse à la péricope centrale de ce mémoire : Juges 13:24-14:20. Le découpage de la structure de cette péricope est basé sur des critères de critique textuelle et d’analyse syntaxique. La première analyse s’attarde aux difficultés que le texte hébreu présente, alors que la deuxième met l’accent sur l’organisation structurelle des propositions grammaticales des versets. Les deux analyses me permettent ensuite de proposer une traduction du péricope. Le Chapitre 3 se veut une application de ce qui a été élaboré au Chapitre 1 sur la péricope analysée au Chapitre 2. Ce troisième chapitre permet de mettre en pratique une approche processuelle originale développée par Robert David dans son livre Déli_l’ ÉCRITURE. Dans la foulée des chapitres qui le précèdent, le Chapitre 4 propose quelques principes herméneutiques contemporains pouvant éclairer le rôle de la Ruah YHWH dans l’avancée créative du monde : vie, amour, et paix.

Evidence for a reference frame transformation of vestibular contributions to voluntary reaching movements

Les estimations des mouvements de soi provenant des signaux vestibulaires contribuent à la planification et l’exécution des mouvements volontaires du bras lorsque le corps se déplace. Cependant, comme les senseurs vestibulaires sont fixés à la tête alors que le bras est fixé au corps, les signaux vestibulaires doivent être transformés d’un système de référence centré sur la tête à un système centré sur le corps pour pouvoir contribuer de façon appropriée au contrôle moteur du bras. Le but premier de ce travail était d’étudier l’évidence d’une telle transformation. La stimulation galvanique vestibulaire (SGV) a été utilisée pour activer les afférences vestibulaires et simuler une rotation autour d’un axe naso-occipital fixe pendant que des sujets humains faisaient des mouvements du bras dans le plan horizontal, avec la tête dans différentes orientations. Une transformation des signaux vestibulaires implique que la SVG devrait simuler une rotation autour d’un axe horizontal lorsque la tête est droite et autour d’un axe vertical lorsque la tête est en flexion antérieure. La SGV devrait ainsi perturber les mouvements du bras en fonction de l’orientation de la tête. Nos résultats démontrent que les signaux vestibulaires contribuant aux mouvements d’atteinte sont effectivement transformés en un système de référence centrée sur le corps. Le deuxième but de ce travail était d’explorer les mécanismes utilisant ces signaux vestibulaires transformés. En comparant les effets de la SGV appliquée avant ou pendant les mouvements d’atteinte nous avons montré que les signaux vestibulaires transformés contribuent à des mécanismes de compensation distincts durant la planification des mouvements d’atteinte comparativement à l’exécution.

Unusual surface and edge morphologies, sp2 to sp3 hybridized transformation and electronic damage after Ar+ ion irradiation of few-layer graphene surfaces

Roughness and defects induced on few-layer graphene (FLG) irradiated by Ar+ ions at different energies were investigated using X-ray photoemission spectroscopy (XPS) and atomic force microscopy techniques. The results provide direct experimental evidence of ripple formation, sp2 to sp3 hybridized carbon transformation, electronic damage, Ar+ implantation, unusual defects and edge reconstructions in FLG, which depend on the irradiation energy. In addition, shadowing effects similar to those found in oblique-angle growth of thin films were seen. Reliable quantification of the transition from the sp2-bonding to sp3-hybridized state as a result of Ar+ ion irradiation is achieved from the deconvolution of the XPS C (1s) peak. Although the ion irradiation effect is demonstrated through the shape of the derivative of the Auger transition C KVV spectra, we show that the D parameter values obtained from these spectra which are normally used in the literature fail to account for the sp2 to sp3 hybridization transition. In contrast to what is known, it is revealed that using ion irradiation at large FLG sample tilt angles can lead to edge reconstructions. Furthermore, FLG irradiation by low energy of 0.25 keV can be a plausible way of peeling graphene layers without the need of Joule heating reported previously

Hegemony, Private Actors, and International Institutions: Transnational Corporations as the agents of transformation of the trade regime from GATT to the WTO

Diese Dissertation hat das Ziel, zum einen die Transformation des Handelssystems von der GATT zur Welthandelsorganisation (WTO) im Kontext einer veränderten Weltordnung und zum anderen die Rollen von transnationalen Unternehmen im Rahmen dieser Transformation zu untersuchen und zu verstehen. Die Arbeit wird theoretisch vom Neogramscianismus angeleitet, da die etablierten Ansätzen in den Internationalen Beziehungen und der International Politischen Ökonomie nur unzureichend die intersubjektive Natur von Regimen und nicht-staatlichen Akteuren darstellen. Für Anhänger des Neogramscianismus sind internationale Regime intersubjektive Einheiten, deren Zusammenspiel von Ideen und Machtkonfigurationen historische Strukturen prägen. Die Hegemonie ist ein Konzept, das soziale Einflüsse als Agenten historischen Wandels in international Regimen und der Weltordnung zusammenbindet. Mit dem Konzept der Hegemonie wird eine Machtsituation beschrieben, in der politische Macht in legitime Autorität übersetzt wird, indem die Zustimmung subalterner Akteure eingeholt wird. Hegemonie beinhaltet die konsensuellen Aspekte von Machtausübung in einer jeweiligen Weltordnung. Diese Dissertation argumentiert vor allem, dass die Transformation des Handelssystems als hegemonisch bezeichnet werden kann, da sie parallel mit der Transformation der Weltordnung von einer von den USA dominierten Nachkriegszeit zu einer neoliberalen Hegemonie stattfand. Mit der Transformation zur Welthandlungsorganisation wird der legale Rahmen des Handelssystems neu strukturiert und ihre normative Grundlagen neu definiert, wodurch der ethische Rahmen des Neoliberalismus reflektiert wird. Diese Änderungen werden in der neuartigen Anerkennung der legitimen Autorität des Marktes gegenüber Nationalstaaten und der Anerkennung von der Notwendigkeit von bindenden Disziplinen, die Regierungen übergeordnet sind, reflektiert. Diese Dissertation analysiert zwei Fälle, um die Rolle von transnationalen Unternehmen innerhalb diese Transformationsprozesses zu erklären. Dabei wird der Fokus vor allem auf die Aktivitäten und Fähigkeiten der Unternehmen gerichtet, die Ausrichtung des Handelsregimes zu bestimmen. Die erste Studie untersucht die Eingliederung von Dienstleistungen in das GATT Regime vor und während der Uruguay-Runde (1986 – 1994) und argumentiert, dass diese Eingliederung zu einer Neudefinierung von Liberalisierung und Normen der Nichtdiskriminierung führte. Die zweite Studie analysiert den gescheiterten Versuch, ausländische Direktinvestitionen noch bevor und während der 2001 begonnenen Doha Runde in die Welthandelsorganisation zu integrieren. Letztendlich wird in dieser Dissertation argumentiert, dass transnationale Unternehmen, die in den Vereinigten Staaten ansässig sind, hegemonische Agenten der Regimetransformation waren und eine wichtige Rolle dabei gespielt haben, Dienstleistungen in das GATT einzubinden. Und zwar gelang ihnen dies durch eine in den späten 1970er Jahren begonnenen Kampagne. Auf der einen Seite war die Kampagne darin erfolgreich, etablierte Denkstrukturen zu Handelsthemen systematisch im Sinne des Neoliberalismus zu verändern – und zwar sowohl hinsichtlich der normativen Inhalte als auch der intersubjektiven Bedeutungen des Regimes. Auf der anderen Seite deutet der Fall des Investitionsabkommens die Grenzen der hegemonischen Ideen, Institutionen, und Strömungen seit den frühen 90er Jahren an. Transnationale Unternehmen, die in Europa ansässig waren, sind mit ihren Bemühungen gescheitert, das Regime weiter zu transformieren und das Thema Investitionen in die legalen und normativen Rahmenbedingungen der WTO zu integrieren. Die Prioritäten und Strategien der transnationalen Unternehmen, die Agenda der WTO zu beeinflussen, waren beschränkt und wurden im Kontext einer angefochtenen neoliberalen Hegemonie geformt, die wiederum von dem Widerstand und anti-hegemonischen Kampagnen der Zivilgesellschaft beeinflusst wurden. Die Analyse in dieser Dissertation wurde durch eine qualitative Diskursanalyse von Sekundär- und Primärquellen durchgeführt: Regierungsvorschläge, Verhandlungstexte, Konferenzzusammenfassungen und Statements von Unternehmen.

Lean Enterprise Transformation: Measuring and Accelerating the transition to lean.

PowerPoint presentation that showcases: • Research Objectives • Strategic Value of the Lean Enterprise • Multi-Stakeholder Value Optimization • Lean Enterprise Self-Assessment Tool (LESAT) • Leading and Lagging Indicators of Lean Enterprise Transformation • Empirical Results in the Aerospace Industry • Accelerating the Lean Transformation - Linking LESAT to Strategic Objectives • Summary and Questions

Adaptation to climate change : from resilience to transformation.

Es un análisis exhaustivo de las dimensiones sociales del cambio climático, pues se considera una prioridad para el desarrollo humano aprender a vivir con sus efectos. Se presentan una serie de opciones que puede afrontar la humanidad en esta tarea estrictamente defensiva de adaptación a los riesgos del calentamiento global de la Tierra. Es una obra de referencia para los estudiantes de pregrado y postgrado interesados en los estudios sobre cambio climático, geografía y desarrollo.

Solvent-induced dynamic single-crystal-to-single-crystal transformation of a synthetic peptide-based cyclic compound

Solvent induced single-crystal-to-single-crystal transformation has been demonstrated indicating the dynamic behavior of one dimensional arrays obtained from a self-assembled new synthetic cyclic peptide.

Flavanol monomer-induced changes to the human faecal microflora

We have investigated the bacterial-dependent metabolism of (-)-epicatechin and (+)-catechin using a pH-controlled, stirred, batch-culture fermentation system reflective of the distal region of the human large intestine. Incubation of (-)-epicatechin or (+)-catechin (150mg/l or 1000mg/l) with faecal bacteria, led to the generation of 5-(3,4'-dihydroxyphenyl)-gamma-valerolactone, 5-phenyl-gamma-valerolactone and phenylpropionic acid. However, the formation of these metabolites from (+)-catechin required its initial conversion to (+)-epicatechin. The metabolism of both flavanols occurred in the presence of favourable carbon sources, notably sucrose and the prebiotic fructo-oligosaccharides, indicating that bacterial utilisation of flavanols also occurs when preferential energy sources are available. (+)-Catechin incubation affected the growth of select microflora, resulting in a statistically significant increase in the growth of the Clostridium coccoides-Eubacterium rectale group, Bifidobacterium spp. and Escherichia coli, as well as a significant inhibitory effect on the growth of the C. histolyticum group. In contrast, the effect of (-)-epicatechin was less profound, only significantly increasing the growth of the C. coccoides-Eubacterium rectale group. These potential prebiotic effects for both (+)-catechin and (-)-epicatechin were most notable at the lower concentration of 150 mg/l. As both (-)-epicatechin and (+)-catechin were converted to the same metabolites, the more dramatic change in the growth of distinct microfloral populations produced by (+)-catechin incubation may be linked to the bacterial conversion of (+)-catechin to (+)-epicatechin. Together these data suggest that the consumption of flavanol-rich foods may support gut health through their ability to exert prebiotic actions.

A catemer-to-dimer structural transformation in cyheptamide

A catemeric crystal structure of cyheptamide undergoes a transformation in the solid-state upon heating to produce a dimer-based form whose structure has been determined from laboratory X-ray powder diffraction ( XRPD) data, thereby providing the first conclusive evidence of a carbamazepine analogue crystallising in both hydrogen bonded motifs.