Development and Detailed Characterization of Innovative, High-Performance Membrane Materials for CO2 Capture Processes

The scope of this dissertation is to study the transport phenomena of small molecules in polymers and membranes for gas separation applications, with particular attention to energy efficiency and environmental sustainability. This work seeks to contribute to the development of new competitive selective materials through the characterization of novel organic polymers such as CANALs and ROMPs, as well as through the combination of selective materials obtaining mixed matrix membranes (MMMs), to make membrane technologies competitive with the traditional ones. Kinetic and thermodynamic aspects of the transport properties were investigated in ideal and non-ideal scenarios, such as mixed-gas experiments. The information we gathered contributed to the development of the fundamental understanding related to phenomenon like CO2-induced plasticization and physical aging. Among the most significant results, ZIF-8/PPO MMMs provided materials whose permeability and selectivity were higher than those of the pure materials for He/CO2 separation. The CANALs featured norbornyl benzocyclobutene backbone and thereby introduced a third typology of ladder polymers in the gas separation field, expanding the structural diversity of microporous materials. CANALs have a completely hydrocarbon-based and non-polar rigid backbone, which makes them an ideal model system to investigate structure-property correlations. ROMPs were synthesized by means of the ring opening metathesis living polymerization, which allowed the formation of bottlebrush polymers. CF3-ROMP reveled to be ultrapermeable to CO2, with unprecedented plasticization resistance properties. Mixed-gas experiments in glassy polymer showed that solubility-selectivity controls the separation efficiency of materials in multicomponent conditions. Finally, it was determined that plasticization pressure in not an intrinsic property of a material and does not represent a state of the system, but rather comes from the contribution of solubility coefficient and diffusivity coefficient in the framework of the solution-diffusion model.

Weekend/weekday differences in concentrations of ozone, nox, and non-methane hydrocarbon in the metropolitan area of São Paulo

Ozone and inhalable particulate matter are the major air pollutants in the Metropolitan Area of São Paulo, Brazil, a region that has more than 19 million inhabitants and approximately 7 million registered vehicles. Proximity of roadways, adjacent land use, and local circulation are just some of the factors that can affect the results of monitoring of pollutant concentrations. The so-called weekend effect (higher ozone concentrations on weekends than on weekdays) might be related to the fact that concentrations of ozone precursors, such as nitrogen oxides (NOx) and Non Methane-Hydrocarbon (NMHC), are relatively lower on weekends. This phenomenon has been reported in some areas of the United States since the 1970s. The differences between the concentrations of ozone in period of weekend and weekday, were obtained from analysis of data hourly average of CETESB for 2004, studied the precursors to the formation of troposphere ozone, the meteorological variables and traffic profile for RMSP. Because of the proximity to sources of emissions from the station Pinheiros showed higher concentrations of NO and NO² and greater variations to the periods weekend and weekday. With fewer vehicles circulating during the weekend, and consequently less emission of pollutants, it has cleaner air and less concentration of NO and NO², there is the ideal setting to the formation of troposphere ozone, despite the lower concentration of NO². The proximity with the source emissions, aided by the increased availability of solar radiation and the presence of ozone precursors, were factors conditions for the occurrence of weekend effect.

The Equilibrium Flux Method for the calculation of flows with non-equilbrium chemical reactions

The Equilibrium Flux Method [1] is a kinetic theory based finite volume method for calculating the flow of a compressible ideal gas. It is shown here that, in effect, the method solves the Euler equations with added pseudo-dissipative terms and that it is a natural upwinding scheme. The method can be easily modified so that the flow of a chemically reacting gas mixture can be calculated. Results from the method for a one-dimensional non-equilibrium reacting flow are shown to agree well with a conventional continuum solution. Results are also presented for the calculation of a plane two-dimensional flow, at hypersonic speed, of a dissociating gas around a blunt-nosed body.

Undergraduate teaching of ideal and real fluid flows: The value of real-world experimental projects

This study describes the pedagogical impact of real-world experimental projects undertaken as part of an advanced undergraduate Fluid Mechanics subject at an Australian university. The projects have been organised to complement traditional lectures and introduce students to the challenges of professional design, physical modelling, data collection and analysis. The physical model studies combine experimental, analytical and numerical work in order to develop students’ abilities to tackle real-world problems. A first study illustrates the differences between ideal and real fluid flow force predictions based upon model tests of buildings in a large size wind tunnel used for research and professional testing. A second study introduces the complexity arising from unsteady non-uniform wave loading on a sheltered pile. The teaching initiative is supported by feedback from undergraduate students. The pedagogy of the course and projects is discussed with reference to experiential, project-based and collaborative learning. The practical work complements traditional lectures and tutorials, and provides opportunities which cannot be learnt in the classroom, real or virtual. Student feedback demonstrates a strong interest for the project phases of the course. This was associated with greater motivation for the course, leading in turn to lower failure rates. In terms of learning outcomes, the primary aim is to enable students to deliver a professional report as the final product, where physical model data are compared to ideal-fluid flow calculations and real-fluid flow analyses. Thus the students are exposed to a professional design approach involving a high level of expertise in fluid mechanics, with sufficient academic guidance to achieve carefully defined learning goals, while retaining sufficient flexibility for students to construct there own learning goals. The overall pedagogy is a blend of problem-based and project-based learning, which reflects academic research and professional practice. The assessment is a mix of peer-assessed oral presentations and written reports that aims to maximise student reflection and development. Student feedback indicated a strong motivation for courses that include a well-designed project component.

An in vitro study of non-axial forces upon the retention of an O-ring attachment

Objective The purpose of this study was to evaluate the retention force of an O-ring attachment system in different inclinations to the ideal path of insertion, using devices to compensate angulations. Material and methods Two implants were inserted into an aluminum base, and ball attachments were screwed to implants. Cylinders with O-rings were placed on ball attachments and connected to the test device using positioners to compensate implant angulations (0 degrees, 7 degrees, and 14 degrees). Plexiglass bases were used to simulate implant angulations. The base and the test device were positioned in a testing apparatus, which simulated insertion/removal of an overdenture. A total of 2900 cycles, simulating 2 years of overdenture use, were performed and 36 O-rings were tested. The force required for each cycle was recorded with computer software. Longitudinal sections of ball attachment-positioner-cylinder with O-rings of each angulation were obtained to analyze the relationship among them, and O-ring sections tested in each angulation were compared with an unused counterpart. A mixed linear model was used to analyze the data, and the comparison was performed by orthogonal contrasts (alpha=0.05). Results At 0 degrees, the retention force decreased significantly over time, and the retention force was significantly different in all comparisons, except from 12 to 18 months. When the implants were positioned at 7 degrees, the retention force was statistically different at 0 and 24 months. At 14 degrees, significant differences were found from 6 and 12 to 24 months. Conclusions Within the limitations of this study, it was concluded that O-rings for implant/attachments perpendicular to the occlusal plane were adequately retentive over the first year and that the retentive capacity of O-ring was affected by implant inclinations despite the proposed positioners. To cite this article:Rodrigues RCS, Faria ACL, Macedo AP, Sartori IAM, de Mattos MGC, Ribeiro RF. An in vitro study of non-axial forces upon the retention of an O-ring attachment.Clin. Oral Impl. Res. 20, 2009; 1314-1319.doi: 10.1111/j.1600-0501.2009.01742.x.

On the analysis of data emerging in non-linear and complex systemscomparison of two X-Ray prony spectra

New arguments proving that successive (repeated) measurements have a memory and actually remember each other are presented. The recognition of this peculiarity can change essentially the existing paradigm associated with conventional observation in behavior of different complex systems and lead towards the application of an intermediate model (IM). This IM can provide a very accurate fit of the measured data in terms of the Prony's decomposition. This decomposition, in turn, contains a small set of the fitting parameters relatively to the number of initial data points and allows comparing the measured data in cases where the “best fit” model based on some specific physical principles is absent. As an example, we consider two X-ray diffractometers (defined in paper as A- (“cheap”) and B- (“expensive”) that are used after their proper calibration for the measuring of the same substance (corundum a-Al2O3). The amplitude-frequency response (AFR) obtained in the frame of the Prony's decomposition can be used for comparison of the spectra recorded from (A) and (B) - X-ray diffractometers (XRDs) for calibration and other practical purposes. We prove also that the Fourier decomposition can be adapted to “ideal” experiment without memory while the Prony's decomposition corresponds to real measurement and can be fitted in the frame of the IM in this case. New statistical parameters describing the properties of experimental equipment (irrespective to their internal “filling”) are found. The suggested approach is rather general and can be used for calibration and comparison of different complex dynamical systems in practical purposes.

Which “place and non-place” do women occupy in social economy organisations?

Scientific literature has strengthened the perpetuation of inequality factors in the labour market based on gender, despite the on-going endeavour of various political bodies and legal norms against the vertical and horizontal segregation of women. National and European statistical data shows the relevance and timeless features of theories of market segmentation associated with the labour market dating back to the 70’s of the 20th century. Hence, the European Community considers as a priority in the Europe 2020 strategy, the definition of “policies to promote gender equality […] to increase labour force participation thus adding to growth and social cohesion”. If we consider that on the one hand, social economy is fairly recognised to be equated with market actors and the State for its economic and social role in tackling the current crisis, and on the other hand, that the ideals of the sector, systematised in the “Framework Law of Social Economy” (Law no. 30/2013 8th of May), particularly in article 5 proposing “the respect for the values […] of equality and non-discrimination […], justice and equity […]”, we aim to reflect on indicators that uncover a vertical and horizontal segregation in the labour market. Departing from a mixed methodological approach (extensive and intensive), subject to the topic of "Social Entrepreneurship in Portugal" in social economy organisations, we detect very high rates of employment feminisation, with a ratio of 1 man (23%) for every 3 women (77%). Women are mainly earmarked for technical and operational activities, arising from the privileged intervention areas, namely education, training, health, elderly, families, poverty, ultimately being underrepresented in statutory boards and, as such, far removed from deliberations and strategic resolutions. This is particularly visible in the existing hierarchy of functions and management practices of the responsibility of male members. Thus, it seems easily verified that the sector is travelling away from the ideals of justice and social equity, which can crystallise the "non-place" of women in the definition of a strategic direction of social economy and in the most invisible/private “place” of the organisational setting.

Desarrollo de Algoritmos Numéricos para el Estudio de la Propagación no Lineal de Ondas en Aplicaciones Aeroespaciales y Astrofísicas. Develop to Numerical Algorithms to Study non-Linear Waves Propagation in Aerospace and Astrophysics Applications.

En este proyecto se desarrollarán algoritmos numéricos para sistemas no lineales hiperbólicos-parabólicos de ecuaciones diferenciales en derivadas parciales. Dichos sistemas tienen aplicación en propagación de ondas en ámbitos aeroespaciales y astrofísicos.Objetivos generales: 1)Desarrollo y mejora de algoritmos numéricos con la finalidad de incrementar la calidad en la simulación de propagación e interacción de ondas gasdinámicas y magnetogasdinámicas no lineales. 2)Desarrollo de códigos computacionales con la finalidad de simular flujos gasdinámicos de elevada entalpía incluyendo cambios químicos, efectos dispersivos y difusivos.3)Desarrollo de códigos computacionales con la finalidad de simular flujos magnetogasdinámicos ideales y reales.4)Aplicación de los nuevos algoritmos y códigos computacionales a la solución del flujo aerotermodinámico alrededor de cuerpos que ingresan en la atmósfera terrestre. 5)Aplicación de los nuevos algoritmos y códigos computacionales a la simulación del comportamiento dinámico no lineal de arcos magnéticos en la corona solar. 6)Desarrollo de nuevos modelos para describir el comportamiento no lineal de arcos magnéticos en la corona solar.Este proyecto presenta como objetivo principal la introducción de mejoras en algoritmos numéricos para simular la propagación e interacción de ondas no lineales en dos medios gaseosos: aquellos que no poseen carga eléctrica libre (flujos gasdinámicos) y aquellos que tienen carga eléctrica libre (flujos magnetogasdinámicos). Al mismo tiempo se desarrollarán códigos computacionales que implementen las mejoras de las técnicas numéricas.Los algoritmos numéricos se aplicarán con la finalidad de incrementar el conocimiento en tópicos de interés en la ingeniería aeroespacial como es el cálculo del flujo de calor y fuerzas aerotermodinámicas que soportan objetos que ingresan a la atmósfera terrestre y en temas de astrofísica como la propagación e interacción de ondas, tanto para la transferencia de energía como para la generación de inestabilidades en arcos magnéticos de la corona solar. Estos dos temas poseen en común las técnicas y algoritmos numéricos con los que serán tratados. Las ecuaciones gasdinámicas y magnetogasdinámicas ideales conforman sistemas hiperbólicos de ecuaciones diferenciales y pueden ser solucionados utilizando "Riemann solvers" junto con el método de volúmenes finitos (Toro 1999; Udrea 1999; LeVeque 1992 y 2005). La inclusión de efectos difusivos genera que los sistemas de ecuaciones resulten hiperbólicos-parabólicos. La contribución parabólica puede ser considerada como términos fuentes y tratada adicionalmente tanto en forma explícita como implícita (Udrea 1999; LeVeque 2005).Para analizar el flujo alrededor de cuerpos que ingresan en la atmósfera se utilizarán las ecuaciones de Navier-Stokes químicamente activas, mientras la temperatura no supere los 6000K. Para mayores temperaturas es necesario considerar efectos de ionización (Anderson, 1989). Tanto los efectos difusivos como los cambios químicos serán considerados como términos fuentes en las ecuaciones de Euler. Para tratar la propagación de ondas, transferencia de energía e inestabilidades en arcos magnéticos de la corona solar se utilizarán las ecuaciones de la magnetogasdinámica ideal y real. En este caso será también conveniente implementar términos fuente para el tratamiento de fenómenos de transporte como el flujo de calor y el de radiación. Los códigos utilizarán la técnica de volúmenes finitos, junto con esquemas "Total Variation Disminishing - TVD" sobre mallas estructuradas y no estructuradas.

Non-nest mate discrimination and clonal colony structure in the parthenogenetic ant Cerapachys biroi

Understanding the interplay between cooperation and conflict in social groups is a major goal of biology. One important factor is genetic relatedness, and animal societies are usually composed of related but genetically different individuals, setting the stage for conflicts over reproductive allocation. Recently, however, it has been found that several ant species reproduce predominantly asexually. Although this can potentially give rise to clonal societies, in the few well-studied cases, colonies are often chimeric assemblies of different genotypes, due to worker drifting or colony fusion. In the ant Cerapachys biroi, queens are absent and all individuals reproduce via thelytokous parthenogenesis, making this species an ideal study system of asexual reproduction and its consequences for social dynamics. Here, we show that colonies in our study population on Okinawa, Japan, recognize and effectively discriminate against foreign workers, especially those from unrelated asexual lineages. In accord with this finding, colonies never contained more than a single asexual lineage and average pairwise genetic relatedness within colonies was extremely high (r = 0.99). This implies that the scope for social conflict in C. biroi is limited, with unusually high potential for cooperation and altruism.

Imagerie cardiaque non invasive: apport spécifique en clinique des nouvelles modalités (I). Evaluation morphologique [Cardiac imaging: specific clinical role of newly developed non invasive techniques. Part 1: Morphological evaluation].

Echocardiography is the preferred initial test to assess cardiac morphology and ventricular function. Cardiac MRI enables an optimal visualisation of heart muscle without contrast injection, and precise measurement of the ventricular volumes and systolic function. It is therefore an ideal test for patients with poor echocardiographic windows or for the specific evaluation of right heart chambers. Heart CT also remarkably images heart muscle and precisely measures ventricular systolic function after intravenous injection of iodinated contrast. Coronary CT may also, in selected cases, avoid the need for diagnostic coronary angiography. Although very accurate, these imaging modalities are expensive and may be contra-indicated for a particular patient. Their use in clinical practice has to follow the accepted guidelines.

Le coeur des ARN non codants - Un long chemin à découvrir [In the heart of noncoding RNA: a long way to go].

The identification and characterization of long noncoding RNA in a variety of tissues represent major achievements that contribute to our understanding of the molecular mechanisms controlling gene expression. In particular, long noncoding RNA play crucial roles in the epigenetic regulation of the adaptive response to environmental cues via their capacity to target chromatin modifiers to specific locus. In addition, these transcripts have been implicated in controlling splicing, translation and degradation of messenger RNA. Long noncoding RNA have also been shown to act as decoy molecules for microRNA. In the heart, a few long noncoding RNA have been demonstrated to regulate cardiac commitment and differentiation during development. Furthermore, recent findings suggest their involvement as regulators of the pathophysiological response to injury in the adult heart. Their high cellular specificity makes them attractive target molecules for innovative therapies and ideal biomarkers.

Updates in the perioperative and emergency management of non-vitamin K antagonist oral anticoagulants.

Perioperative management of patients treated with the non-vitamin K antagonist oral anticoagulants is an ongoing challenge. Due to the lack of good clinical studies involving adequate monitoring and reversal therapies, management requires knowledge and understanding of pharmacokinetics, renal function, drug interactions, and evaluation of the surgical bleeding risk. Consideration of the benefit of reversal of anticoagulation is important and, for some low risk bleeding procedures, it may be in the patient's interest to continue anticoagulation. In case of major intra-operative bleeding in patients likely to have therapeutic or supra-therapeutic levels of anticoagulation, specific reversal agents/antidotes would be of value but are currently lacking. As a consequence, a multimodal approach should be taken which includes the administration of 25 to 50 U/kg 4-factor prothrombin complex concentrates or 30 to 50 U/kg activated prothrombin complex concentrate (FEIBA®) in some life-threatening situations. Finally, further studies are needed to clarify the ideal therapeutic intervention.

Arterial Therapies of Non-Colorectal Liver Metastases.

BACKGROUND: The unique situation of the liver with arterial and venous blood supply and the dependency of the tumor on the arterial blood flow make this organ an ideal target for intrahepatic catheter-based therapies. Main forms of treatment are classical bland embolization (TAE) cutting the blood flow to the tumors, chemoembolization (TACE) inducing high chemotherapy concentration in tumors, and radioembolization (TARE) without embolizing effect but very high local radiation. These different forms of therapies are used in different centers with different protocols. This overview summarizes the different forms of treatment, their indications and protocols, possible side effects, and available data in patients with non-colorectal liver tumors. METHODS: A research in PubMed was performed. Mainly clinical controlled trials were reviewed. The search terms were 'embolization liver', 'TAE', 'chemoembolization liver', 'TACE', 'radioembolization liver', and 'TARE' as well as 'chemosaturation' and 'TACP' in the indications 'breast cancer', 'neuroendocrine', and 'melanoma'. All reported studies were analyzed for impact and reported according to their clinical relevance. RESULTS: The main search criteria revealed the following results: 'embolization liver + breast cancer', 122 results, subgroup clinical trials 16; 'chemoembolization liver + breast cancer', 62 results, subgroup clinical trials 11; 'radioembolization liver + breast cancer', 37 results, subgroup clinical trials 3; 'embolization liver + neuroendocrine', 283 results, subgroup clinical trials 20; 'chemoembolization liver + neuroendocrine', 202 results, subgroup clinical trials 9; 'radioembolization liver + neuroendocrine', 64 results, subgroup clinical trials 9; 'embolization liver + melanoma', 79 results, subgroup clinical trials 15; 'chemoembolization liver + melanoma', 60 results, subgroup clinical trials 14; 'radioembolization liver + melanoma', 18 results, subgroup clinical trials 3. The term 'chemosaturation liver' was tested without indication since only few publications exist and provided us with five results and only one clinical trial. CONCLUSION: Despite many years of clinical use and documented efficacy on intra-arterial treatments of the liver, there are still only a few prospective multicenter trials with many different protocols. To guarantee the future use of these efficacious therapies, especially in the light of many systemic or surgical therapies in the treatment of non-colorectal liver metastases, further large randomized trials and transparent guidelines need to be established.

La multiculturalité, la communauté et les femmes non-conventionnelles dans The Diviners de Margaret Laurence et O Pioneers! de Willa Cather

Résumé Ce mémoire traite des enjeux multiculturels du tournant du vingtième siècle en Amérique du Nord, des problématiques de la communauté de face-à-face ainsi que de la non-conventionalité des protagonistes féminins présents dans The Diviners (1974) de Margaret Laurence et O Pioneers! (1913) de Willa Cather. Cette étude a pour objectif de faire des liens entre ces deux œuvres qui ont été écrites par des auteures féminines, qui mettent en scène des femmes fortes et émancipées dans des petites communautés multiculturelles de l’Ouest. Cette étude traitera également des différences entre les deux romans, soit l’époque et le contexte. Cette étude s’intéressera, en premier lieu, aux différents enjeux de la multiculturalité et analysera les deux romans à la lumière de concepts tels le Melting pot, l’assimilation et l’interculturalité. Cette étude s’intéressera ensuite aux problématiques de la communauté de face-à-face. Elle aura pour objectif de déconstruire l’idéal type de la communauté de face-à-face et de démontrer comment frictions et rejets font partie du quotidien des personnages des deux romans. En dernier lieu, cette étude s’intéressera à la non-conventionalité des personnages féminins principaux. En effet, chacune à leur manière, les protagonistes fracassent les stéréotypes féminins de leur milieu et de leur époque afin de s’émanciper.