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.

Variable positive end-expiratory pressure can maintain oxygenation in experimental acute respiratory distress syndrome induced by oleic acid in dogs

The use of positive end-expiratory pressure (PEEP) or lung recruitment maneuvers (RM) to improve oxygenation in acute respiratory distress syndrome (ARDS) is used but it may reduce cardiac output (CO). Intermittent PEEP may avoid these complications. Our objective was to determine if variable PEEP compared with constant PEEP is capable of maintaining arterial oxygenation and minimizing hemodynamic alterations with or without RM. Eighteen dogs with ARDS induced by oleic acid were randomized into three equal groups: group 1, low variable PEEP; group 2, high variable PEEP, and group 3, RM + high variable PEEP. All groups were submitted to constant PEEP, followed by variable PEEP (PEEP was increased from 5 to 10 cmH2O in group 1, and from 5 to 18 cmH2O in the other two groups). PaO2 was higher in group 3 (356.2 ± 65.4 mmHg) than in group 1 (92.7 ± 29.7 mmHg) and group 2 (228.5 ± 72.4 mmHg), P < 0.05. PaO2 was maintained during variable PEEP except in group 2 (318.5 ± 82.9 at constant PEEP to 228.5 ± 72.4 at variable PEEP). There was a reduction in CO in group 3 after RM (3.9 ± 1.1 before to 2.7 ± 0.5 L·min-1·(m2)-1 after; P < 0.05), but there was not any difference between constant and variable PEEP periods (2.7 ± 0.5 and 2.4 ± 0.7 L·min-1·(m2)-1; P > 0.05. Variable PEEP is able to maintain PaO2 when performed in combination with RM in dogs with ARDS. After RM, CO was reduced and there was no relevant difference between the variable and constant PEEP periods.

A conjugate of an anti-midkine single-chain variable fragment to doxorubicin inhibits tumor growth

Doxorubicin (DOX) was conjugated to a single-chain variable fragment (scFv) against human midkine (MK), and the conjugate (scFv-DOX) was used to target the chemotherapeutic agent to a mouse solid tumor model in which the tumor cells expressed high levels of human MK. The His-tagged recombinant scFv was expressed in bacteria, purified by metal affinity chromatography, and then conjugated to DOX using oxidative dextran (Dex) as a linker. The molecular formula of this immunoconjugate was scFv(Dex)1.3(DOX)20. In vitro apoptosis assays showed that the scFv-DOX conjugate was more cytotoxic against MK-transfected human adenocarcinoma cells (BGC823-MK) than untransfected cells (55.3 ± 2.4 vs 22.4 ± 3.8%) for three independent experiments. Nude mice bearing BGC823-MK solid tumors received scFv-DOX or equivalent doses of scFv + DOX for 2 weeks and tumor growth was more effectively inhibited by the scFv-DOX conjugate than by scFv + DOX (51.83% inhibition vs 40.81%). Histological analysis of the tumor tissues revealed that the highest levels of DOX accumulated in tumors from mice treated with scFv-DOX and this resulted in more extensive tumor cell death than in animals treated with the equivalent dose of scFv + DOX. These results show that the scFv-DOX conjugate effectively inhibited tumor growth in vivo and suggest that antigen-specific scFv may be competent drug-carriers.

Expression, production, and renaturation of a functional single-chain variable antibody fragment (scFv) against human ICAM-1

Intercellular adhesion molecule-1 (ICAM-1) is an important factor in the progression of inflammatory responses in vivo. To develop a new anti-inflammatory drug to block the biological activity of ICAM-1, we produced a monoclonal antibody (Ka=4.19×10−8 M) against human ICAM-1. The anti-ICAM-1 single-chain variable antibody fragment (scFv) was expressed at a high level as inclusion bodies in Escherichia coli. We refolded the scFv (Ka=2.35×10−7 M) by ion-exchange chromatography, dialysis, and dilution. The results showed that column chromatography refolding by high-performance Q Sepharose had remarkable advantages over conventional dilution and dialysis methods. Furthermore, the anti-ICAM-1 scFv yield of about 60 mg/L was higher with this method. The purity of the final product was greater than 90%, as shown by denaturing gel electrophoresis. Enzyme-linked immunosorbent assay, cell culture, and animal experiments were used to assess the immunological properties and biological activities of the renatured scFv.

Doubly fed wind turbine performance in variable grid conditions

Wind turbines based on doubly fed induction generators (DFIG) become the most popular solution in high power wind generation industry. While this topology provides great performance with the reduced power rating of power converter, it has more complicated structure in comparison with full-rated topologies, and therefore leads to complexity of control algorithms and electromechanical processes in the system. The purpose of presented study is to present a proper vector control scheme for the DFIG and overall control for the WT to investigate its behavior at different wind speeds and in different grid voltage conditions: voltage sags, magnitude and frequency variations. The key principles of variable-speed wind turbine were implemented in simulation model and demonstrated during the study. Then, based on developed control scheme and mathematical model, the set of simulation is made to analyze reactive power capabilities of the DFIG wind turbine. Further, the rating of rotor-side converter is modified to not only generate active rated active power, but also to fulfill Grid Codes. Results of modelling and analyzing of the DFIG WT behavior under different speeds and different voltage conditions are presented in the work.

Variable-speed-drive-based detection methods for problems in fluid handling systems

Fluid handling systems account for a significant share of the global consumption of electrical energy. They also suffer from problems, which reduce their energy efficiency and increase life-cycle costs. Detecting or predicting these problems in time can make fluid handling systems more environmentally and economically sustainable to operate. In this Master’s Thesis, significant problems in fluid systems were studied and possibilities to develop variable-speed-drive-based detection methods for them was discussed. A literature review was conducted to find significant problems occurring in fluid handling systems containing pumps, fans and compressors. To find case examples for evaluating the feasibility of variable-speed-drive-based methods, queries were sent to industrial companies. As a result of this, the possibility to detect heat exchanger fouling with a variable-speed drive was analysed with data from three industrial cases. It was found that a mass flow rate estimate, which can be generated with a variable speed drive, can be used together with temperature measurements to monitor a heat exchanger’s thermal performance. Secondly, it was found that the fouling-related increase in the pressure drop of a heat exchanger can be monitored with a variable speed drive. Lastly, for systems where the flow device is speed controlled with by a pressure measurement, it was concluded that increasing rotational speed can be interpreted as progressing fouling in the heat exchanger.

Premières conséquences de la guerre : transformation mentale des peuples... / Dr Gustave Le Bon

Collection : Bibliothèque de philosophie scientifique

Les 5 milliards sont là ! ! ! sans emprunt ni augmentation des charges publiques par la seule transformation de l'impôt... 2e édition

Comprend : Préambule

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

The essence of a tacit intersection : a heuristic inquiry into nature-based leisure and personal transformation

There are a considerable number of programs and agencies that count on the existence of a unique relationship between nature and human development. In addition, there are significant bodies of literature dedicated to understanding developmentally focused nature-based experiences. This research project was designed to flirther the understanding of this phenomenon. Consequently, the purpose of this research endeavour was to discover the essence ofthe intersection ofpersonal transformation and nature-based leisure, culminating in a rich and detailed account of this otherwise tacit phenomenon. As such, this research built on the assumption of this beneficial intersection of nature and personal transformation and contributes to the understanding ofhow this context is supporting or generating of selfactualization and positive development. Heuristic methods were employed because heuristics is concerned with the quality and essence of an experience, not causal relationships (Moustakas, 1990). Heuristic inquiry begins with the primary researcher and her personal experience and knowledge of the phenomenon. This study also involved four other coresearchers who had also experienced this phenomenon intensely. Co-researchers were found through purposeful and snowball sampling. Rich narrative descriptions of their experiences were gathered through in-depth, semi-structured interviews, and artifact elicitation was employed as a means to get at co-researchers' tacit knowledge. Each coresearcher was interviewed twice (the first interview focused on personal transformation, the second on nature) for approximately four and a half hours in total. Transcripts were read repeatedly to discern patterns that emerged from the study of the narratives and were coded accordingly. Individual narratives were consolidated to create a composite narrative of the experience. Finally, a creative synthesis was developed to represent the essence of this tacit experience. In conclusion the essence of the intersection of nature-based leisure and personal transformation was found to lie in the convergence of the lived experience of authenticity. The physical environment of nature was perceived and experienced to be a space and context of authenticity, leisure experiences were experienced as an engagement of authenticity, and individuals themselves encountered a true or authentic self that emanated from within. The implications of these findings are many, offering suggestions, considerations and implications from reconsidered approaches to environmental education to support for selfdirected human development.

Words on wisdom: perspective transformation in a "learning in retirement institute" /

In this study, 7 men and women with an average age of 77 were interviewed regarding their experience of attending courses at a Learning in Retirement Institute (LRI) in southern Ontario. The purpose was to explore the role of wisdom in the learning of these retirees. Explicit theories of wisdom developed by selected philosophers, psychologists, and religious thinkers were compared to the implicit theories of wisdom that respondents expressed. Further comparisons were drawn between these implicit theories of wisdom and the act of perspective transformation in transformative learning. Some evidence was found that the development of wisdom compares favourably to perspective transformation, especially with regards to the behavioural changes associated with critical self-reflection. Among all the respondents, those 3 LRI stude.its who had also moderated courses indicated that they had experienced the most opportunities for critical self-reflection. These 3 also expressed deep satisfaction in having been able to put their learnings to use as teachers. A recommendation of this study is that opportunities for sharing and acting upon the results of discourse within Learning in Retirement Institutes should be implemented. In the absence of evaluation, opportunities for praxis (such as coop placements) must be developed so that students can measure their success against objective criteria and hence attach meaning to their studies.

The design, synthesis and characterization of new building blocks for the preparation of molecule-based magnetic materials /

Two new families of building blocks have been prepared and fully characterized and their coordination chemistry exploited for the preparation of molecule-based magnetic materials. The first class of compounds were prepared by exploiting the chemistry of 3,3'-diamino-2,2'-bipyridine together with 2-pyridine carbonyl chloride or 2-pyridine aldehyde. Two new ligands, 2,2'-bipyridine-3,3'-[2-pyridinecarboxamide] (Li, 2.3) and N'-6/s(2-pyridylmethyl) [2,2'bipyridine]-3,3'-diimine (L2, 2.7), were prepared and characterized. For ligand L4, two copper(II) coordination compounds were isolated with stoichiometrics [Cu2(Li)(hfac)2] (2.4) and [Cu(Li)Cl2] (2.5). The molecular structures of both complexes were determined by X-ray crystallography. In both complexes the ligand is in the dianionic form and coordinates the divalent Cu(II) ions via one amido and two pyridine nitrogen donor atoms. In (2.4), the coordination geometry around both Cu11 ions is best described as distorted trigonal bipyramidal where the remaining two coordination sites are satisfied by hfac counterions. In (2.5), both Cu(II) ions adopt a (4+1) distorted square pyramidal geometry. One copper forms a longer apical bond to an adjacent carbonyl oxygen atom, whereas the second copper is chelated to a neighboring Cu-Cl chloride ion to afford chloride bridged linear [Cu2(Li)Cl2]2 tetramers that run along the c-axis of the unit cell. The magnetic susceptibility data for (2.4) reveal the occurrence of weak antiferromagnetic interactions between the copper(II) ions. In contrast, variable temperature magnetic susceptibility measurements for (2.5) reveal more complex magnetic properties with the presence of ferromagnetic exchange between the central dimeric pair of copper atoms and weak antiferromagnetic exchange between the outer pairs of copper atoms. The Schiff-base bis-imine ligand (L2, 2.7) was found to be highly reactive; single crystals grown from dry methanol afforded compound (2.14) for which two methanol molecules had added across the imine double bond. The susceptibility of this ligand to nucleophilic attack at its imine functionality assisted via chelation to Lewis acidic metal ions adds an interesting dimension to its coordination chemistry. In this respect, a Co(II) quaterpyridine-type complex was prepared via a one-pot transformation of ligand L2 in the presence of a Lewis acidic metal salt. The rearranged complex was characterized by X-ray crystallography and a reaction mechanism for its formation has been proposed. Three additional rearranged complexes (2.13), (2.17) and (2.19) were also isolated when ligand (L2, 2.7) was reacted with transition metal ions. The molecular structures of all three complexes have been determined by X-ray crystallography. The second class of compounds that are reported in this thesis, are the two diacetyl pyridine derivatives, 4-pyridyl-2,6-diacetylpyridine (5.5) and 2,2'-6,6'-tetraacetyl-4,4'-bipyridine (5.15). Both of these compounds have been designed as intermediates for the metal templated assembly of a Schiff-base N3O2 macrocycle. From compound (5.15), a covalently tethered dimeric Mn(II) macrocyclic compound of general formula {[Mn^C^XJCl-FkO^Cl-lO.SFbO (5.16) was prepared and characterized. The X-ray analysis of (5.16) reveals that the two manganese ions assume a pentagonal-bipyramidal geometry with the macrocycle occupying the pentagonal plane and the axial positions being filled by a halide ion and a H2O molecule. Magnetic susceptibility data reveal the occurrence of antiferromagnetic interactions between covalently tethered Mn(II)-Mn(II) dimeric units. Following this methodology a Co(II) analogue (5.17) has also been prepared which is isostructural with (5.16).