Tratamento de argila montmorilonítica para a produção de nanocompósitos poliméricos com retardo de propagação de chama

Compared to conventional composites, polymer matrix nanocomposites typically exhibit enhanced properties at a significantly lower filler volume fraction. Studies published in the literature indicate t hat the addition of nanosilicate s can increase the resistance to flame propagation in polymers. In this work, a treatment of montmorillonite (MMT) nano clay and the effect of its ad dition o n flame propagation characteristics of vinyl ester were studied. The resea rch was conducted in two stages. The first stage focused on the purification and activation of the MMT clay collected from a natural deposit to improve compatibility with the polymer matrix . Clay modification with sodium acetate was also studied to improve particle dispersion in the polymer. The second step was focused on the effect of the addition of the treated clay on nanocomposites ’ properties. Nanocomposites with clay con tents of 1, 2, 4 wt. % were processed. T he techniques for the characterization of the clay included X - ray fluorescence (XRF), X - r ay d iffraction (XRD), thermogravimetric a nalysis (TGA), d ifferential scanning c alorimetry (DSC) , s urface area (BET) and Fourier transform infrared spectroscopy (FTIR). For t he characterization of the nanocomposites , the techniques used were thermogravimetric a nalysis (TGA) , differential scanning c alorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) , scanning electron mi croscopy (SEM), transmission electron m icroscopy (TEM), and the determination of tensile strength, modulus of elasticity and resistance to flame propagation. According to the results, the purification and activation treatment with freeze - drying used in thi s work for the montmorillonite clay was efficient to promote compatibility and dispersion in the polymer matrix as evidenced by the characterization of the nanocomposite s . It was also observed that the clay modifica tion using sodium acetate did not produce any significant effect to improve compatibilization of the clay with the polymer. The addition of the treated MMT resulted in a reduction of up to 53% in the polymer flame propagation speed and did not affect the mechanical tensile strength and modulus o f elas ticity of the polymer, indicating compatibility between the clay and polymer. The effectiveness in reducing flame propagation speed peaked for nanocomposites with 2 wt. % clay, indicating that this is the optimum clay concentration for this property. T he clay treatment used in this work enables the production of vinylester matrix nanocomposites with flame - retardancy properties .

Gravidade do olho seco em pacientes internados em unidade de terapia intensiva: análise de conceito e construção de definições

Dry eye syndrome is a multifactorial disease of the tear film, resulting from the instability of the lacrimal functional unit that produces volume change, up or tear distribution. In patients in intensive care the cause is enhanced due to various risk factors, such as mechanical ventilation, sedation, lagophthalmos, low temperatures, among others. The study's purpose is to build an assessment tool of Dry Eye Severity in patients in intensive care units based on the systematization of nursing care and their classification systems. The aim of this study is to build an assessment tool of Dry Eye Severity in hospitalized patients in Care Unit Intensiva.Trata is a methodological study conducted in three stages, namely: context analysis, concept analysis, construction of operational definitions and magnitudes of nursing outcome. For the first step we used the methodological framework for Hinds, Chaves and Cypress (1992). For the second step we used the model of Walker and Avant and an integrative review Whitemore seconds, Knalf (2005). This step enabled the identification of the concept of attributes, background and consequent ground and the construction of the settings for the result of nursing severity of dry eye. For the construction of settings and operational magnitudes, it was used Psicometria proposed by Pasquali (1999). As a result of context analysis, visualized from the reflection that the matter should be discussed and that nursing needs to pay attention to the problem of eye injury, so minimizing strategies are created this event with a high prevalence. With the integrative review were located from the crosses 19 853 titles, selected 215, and from the abstracts 96 articles were read in full. From reading 10 were excluded culminating in the sample of 86 articles that were used to analyze the concept and construction of settings. Selected articles were found in greater numbers in the Scopus database (55.82%), performed in the United States (39.53%), and published mainly in the last five years (48.82). Regarding the concept of analysis were identified as antecedents: age, lagophthalmos, environmental factors, medication use, systemic diseases, mechanical ventilation and ophthalmic surgery. As attributes: TBUT <10s, Schimer I test <5 mm in Schimer II test <10mm, reduced osmolarity. As consequential: the ocular surface damage, ocular discomfort, visual instability. The settings were built and added indicators such as: decreased blink mechanism and eyestrain.

Qual é a sua tribo? O uso do TAI online no desvelamento de conhecimentos sociais ocultos

The Implicit Association Test (IAT) has succeeded in accessing mental phenomena hardly exposed through self-report and explicit measures well known in the traditional studies on psychology. Although this measurement technique is among the most consistent in international publications, the few articles in Brazil have not deepened on theoretical issues that underlie the practice. This created a gap between the spread of this measure in the country and the production seen in international laboratories, both at quantitative and qualitative terms. In this context, the online labs implemented in several countries, including Brazil, created unique opportunities to overcome these disparities. Our work sought theoretical and conceptual clarification, contextualized to the historical development of the IAT and its online version, displaying affordably an unprecedented presentation of the virtual tool adapted to the Brazilian public. In a second step, we investigated empirically the data obtained by the Brazilian electronic portal "Countries", analyzing the degree of implicit and explicit nationalism of 2271 Brazilian subjects collected from early 2009 to late 2014. Our goal was to determine whether the data results obtained in a time of major sporting confrontation (FIFA World Cup 2010 and 2014) differ from periods when the tournament did not happen. Analyzes showed differences on the eve of the sporting confrontation, when the increase in the implicit nationalism was clearly superior, even with no effect by self-reports. In an independent analysis of a cultural context, there is an oscillation of explicit nationalism over the years, but not for the implicit action. In addition, it was found in women greater degree of implicit and explicit nationalism than in men, with both sexes presenting their preferences towards Brazil. In an end section, we suggest that nationalism may be a by-product of universal mental mechanisms that evolved to identify of the belonging group categorization, corroborating with the group favoritism. We propose that the intensification of the group preference on the eve of the competition has as its ancestral function strengthen the cohesion of the group in preparation to confrontational situations. We pointed out the need for studies on the differences between the sexes in matters relating to group membership belonging. It was expected largest nationalist attitudes in men reflecting the maintenance of cohesive groups in ancient societies. Thus, it appears a singular importance impart the traditional TAI studies with its online version for future investigations of human behavior in various areas of knowledge.

Qual é a sua tribo? O uso do TAI online no desvelamento de conhecimentos sociais ocultos

The Implicit Association Test (IAT) has succeeded in accessing mental phenomena hardly exposed through self-report and explicit measures well known in the traditional studies on psychology. Although this measurement technique is among the most consistent in international publications, the few articles in Brazil have not deepened on theoretical issues that underlie the practice. This created a gap between the spread of this measure in the country and the production seen in international laboratories, both at quantitative and qualitative terms. In this context, the online labs implemented in several countries, including Brazil, created unique opportunities to overcome these disparities. Our work sought theoretical and conceptual clarification, contextualized to the historical development of the IAT and its online version, displaying affordably an unprecedented presentation of the virtual tool adapted to the Brazilian public. In a second step, we investigated empirically the data obtained by the Brazilian electronic portal "Countries", analyzing the degree of implicit and explicit nationalism of 2271 Brazilian subjects collected from early 2009 to late 2014. Our goal was to determine whether the data results obtained in a time of major sporting confrontation (FIFA World Cup 2010 and 2014) differ from periods when the tournament did not happen. Analyzes showed differences on the eve of the sporting confrontation, when the increase in the implicit nationalism was clearly superior, even with no effect by self-reports. In an independent analysis of a cultural context, there is an oscillation of explicit nationalism over the years, but not for the implicit action. In addition, it was found in women greater degree of implicit and explicit nationalism than in men, with both sexes presenting their preferences towards Brazil. In an end section, we suggest that nationalism may be a by-product of universal mental mechanisms that evolved to identify of the belonging group categorization, corroborating with the group favoritism. We propose that the intensification of the group preference on the eve of the competition has as its ancestral function strengthen the cohesion of the group in preparation to confrontational situations. We pointed out the need for studies on the differences between the sexes in matters relating to group membership belonging. It was expected largest nationalist attitudes in men reflecting the maintenance of cohesive groups in ancient societies. Thus, it appears a singular importance impart the traditional TAI studies with its online version for future investigations of human behavior in various areas of knowledge.

Structure, energetics and reactions of metal cation complexes of dipeptides in the gas phase

Structure, energetics and reactions of ions in the gas phase can be revealed by mass spectrometry techniques coupled to ions activation methods. Ions can gain enough energy for dissociation by absorbing IR light photons introduced by an IR laser to the mass spectrometer. Also collisions with a neutral molecule can increase the internal energy of ions and provide the dissociation threshold energy. Infrared multiple photon dissociation (IRMPD) or sustained off-resonance irradiation collision-induced dissociation (SORI-CID) methods are combined with Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometers where ions can be held at low pressures for a long time. The outcome of ion activation techniques especially when it is compared to the computational methods results is of great importance since it provides useful information about the structure, thermochemistry and reactivity of ions of interest. In this work structure, energetics and reactivity of metal cation complexes with dipeptides are investigated. Effect of metal cation size and charge as well as microsolvation on the structure of these complexes has been studied. Structures of bare and hydrated Na and Ca complexes with isomeric dipeptides AlaGly and GlyAla are characterized by means of IRMPD spectroscopy and computational methods. At the second step unimolecular dissociation reactions of singly charged and doubly charged multimetallic complexes of alkaline earth metal cations with GlyGly are examined by CID method. Also structural features of these complexes are revealed by comparing their IRMPD spectra with calculated IR spectra of possible structures. At last the unimolecular dissociation reactions of Mn complexes are studied. IRMPD spectroscopy along with computational methods is also employed for structural elucidation of Mn complexes. In addition the ion-molecule reactions of Mn complexes with CO and water are explored in the low pressures obtained in the ICR cell.

Biochemical and Structural Studies on PrfA, the Transcriptional Regulator of Virulence in Listeria monocytogenes

Abstract

Listeria monocytogenes is a gram-positive soil saprophytic bacterium that is capable of causing fatal infection in humans. The main virulence regulator PrfA, a member of the Crp/FNR family of transcriptional regulators, activates the expression of essential proteins required for host cell invasion and cell-to-cell spread. The mechanism of PrfA activation and the identity of its small molecule coactivator have remained a mystery for more than 20 years, but it is hypothesized that PrfA shares mechanistic similarity to the E. coli cAMP binding protein, Crp. Crp activates gene expression by binding cAMP, increasing the DNA binding affinity of the protein and causing a significant DNA bend that facilitates RNA polymerase binding and downstream gene activation. Our data suggests PrfA activates virulence protein expression through a mechanism distinct from the canonical Crp activation mechanism that involves a combination of cysteine residue reduction and glutathione (GSH) binding.

Listeria lacking glutathione synthase (ΔgshF) is avirulent in mice; however virulence is rescued when the bacterium expresses the constitutively active PrfA mutant G145S. Interestingly, Listeria expressing a PrfA mutant in which its four cysteines are mutated to alanine (Quad PrfA), demonstrate a 30-fold decrease in virulence. The Quad and ΔgshF double mutant strains are avirulent. DNA-binding affinity, measured through fluorescence polarization assays, indicate reduction of the cysteine side chains is sufficient to allow PrfA to binds its physiological promoters Phly and PactA with low nanomolar affinity. Oxidized PrfA binds the promoters poorly.

Unexpectedly, Quad also binds promoter DNA with nanomolar affinity, suggesting that the cysteines play a role in transcription efficiency in addition to DNA binding. Both PrfA and Quad bind GSH at physiologically relevant and comparable affinities, however GSH did not affect DNA binding in either case. Thermal denaturation assays suggest that Quad and wild-type PrfA differ structurally upon binding GSH, which supports the in vivo difference in infection between the regulator and its mutant.

Structures of PrfA in complex with cognate DNA, determined through X-ray crystallography, further support the disparity between PrfA and Crp activation mechanisms as two structures of reduced PrfA bound to Phly (PrfA-Phly30 and PrfA-Phly24) suggest the DNA adopts a less bent DNA conformation when compared to Crp-cAMP- DNA. The structure of Quad-Phly30 confirms the DNA-binding data as the protein-DNA complex adopts the same overall conformation as PrfA-Phly.

From these results, we hypothesize a two-step activation mechanism wherein PrfA, oxidized upon cell entry and unable to bind DNA, is reduced upon its intracellular release and binds DNA, causing a slight bend in the promoter and small increase in transcription of PrfA-regulated genes. The structures of PrfA-Phly30 and PrfA-Phly24 likely visualize this intermediate complex. Increasing concentrations of GSH shift the protein to a (PrfA-GSH)-DNA complex which is fully active transcriptionally and is hypothesized to resemble closely the transcriptionally active structure of the cAMP-(Crp)-DNA complex. Thermal denaturation results suggest Quad PrfA is deficient in this second step, which explains the decrease in virulence and implicates the cysteine residues as critical for transcription efficiency. Further structural and biochemical studies are on-going to clarify this mechanism of activation.

Sparse Sample Detection Using Magnetic Bead Manipulation on a Digital Microfluidic Device

This thesis demonstrates a new way to achieve sparse biological sample detection, which uses magnetic bead manipulation on a digital microfluidic device. Sparse sample detection was made possible through two steps: sparse sample capture and fluorescent signal detection. For the first step, the immunological reaction between antibody and antigen enables the binding between target cells and antibody-­‐‑ coated magnetic beads, hence achieving sample capture. For the second step, fluorescent detection is achieved via fluorescent signal measurement and magnetic bead manipulation. In those two steps, a total of three functions need to work together, namely magnetic beads manipulation, fluorescent signal measurement and immunological binding. The first function is magnetic bead manipulation, and it uses the structure of current-­‐‑carrying wires embedded in the actuation electrode of an electrowetting-­‐‑on-­‐‑dielectric (EWD) device. The current wire structure serves as a microelectromagnet, which is capable of segregating and separating magnetic beads. The device can achieve high segregation efficiency when the wire spacing is 50µμm, and it is also capable of separating two kinds of magnetic beads within a 65µμm distance. The device ensures that the magnetic bead manipulation and the EWD function can be operated simultaneously without introducing additional steps in the fabrication process. Half circle shaped current wires were designed in later devices to concentrate magnetic beads in order to increase the SNR of sample detection. The second function is immunological binding. Immunological reaction kits were selected in order to ensure the compatibility of target cells, magnetic bead function and EWD function. The magnetic bead choice ensures the binding efficiency and survivability of target cells. The magnetic bead selection and binding mechanism used in this work can be applied to a wide variety of samples with a simple switch of the type of antibody. The last function is fluorescent measurement. Fluorescent measurement of sparse samples is made possible of using fluorescent stains and a method to increase SNR. The improved SNR is achieved by target cell concentration and reduced sensing area. Theoretical limitations of the entire sparse sample detection system is as low as 1 Colony Forming Unit/mL (CFU/mL).

Perceived risk of death in older primary care patients

There is a large gap between life expectancy and healthy life years at age 65. To reduce this gap, it is necessary that people with medical concerns perceived at higher risk of adverse outcomes are readily identified and treated. The same goes for the need to implement prevention plans. The main objectives of this study are to, in a first step, (a) estimate the percentage of medical concerns, (b) identify factors associated with this concern; in a second step, (c) estimate the perceived risk of death, and (d) evaluate the ability of medical concerns to predict this risk. Results show that the existence and severity of medical concerns are crucial in the prediction of perceived risk of death. Early identification of severity of medical concerns and the availability and adequacy of informal caregiving should allow healthcare professionals to promptly initiate an appropriate assessment and treatment of older patients.

Effective end wall profiling rules for a highly loaded compressor cascade

This paper presents a numerical study of a linear compressor cascade to investigate the effective end wall profiling rules for highly-loaded axial compressors. The first step in the research applies a correlation analysis for the different flow field parameters by a data mining over 600 profiling samples to quantify how variations of loss, secondary flow and passage vortex interact with each other under the influence of a profiled end wall. The result identifies the dominant role of corner separation for control of total pressure loss, providing a principle that only in the flow field with serious corner separation does the does the profiled end wall change total pressure loss, secondary flow and passage vortex in the same direction. Then in the second step, a multi-objective optimization of a profiled end wall is performed to reduce loss at design point and near stall point. The development of effective end wall profiling rules is based on the manner of secondary flow control rather than the geometry features of the end wall. Using the optimum end wall cases from the Pareto front, a quantitative tool for analyzing secondary flow control is employed. The driving force induced by a profiled end wall on different regions of end wall flow are subjected to a detailed analysis and identified for their positive/negative influences in relieving corner separation, from which the effective profiling rules are further confirmed. It is found that the profiling rules on a cascade show distinct differences at design point and near stall point, thus loss control of different operating points is generally independent.

Decision Making for Teams of Mobile Robots

In the past years, we could observe a significant amount of new robotic systems in science, industry, and everyday life. To reduce the complexity of these systems, the industry constructs robots that are designated for the execution of a specific task such as vacuum cleaning, autonomous driving, observation, or transportation operations. As a result, such robotic systems need to combine their capabilities to accomplish complex tasks that exceed the abilities of individual robots. However, to achieve emergent cooperative behavior, multi-robot systems require a decision process that copes with the communication challenges of the application domain. This work investigates a distributed multi-robot decision process, which addresses unreliable and transient communication. This process composed by five steps, which we embedded into the ALICA multi-agent coordination language guided by the PROViDE negotiation middleware. The first step encompasses the specification of the decision problem, which is an integral part of the ALICA implementation. In our decision process, we describe multi-robot problems by continuous nonlinear constraint satisfaction problems. The second step addresses the calculation of solution proposals for this problem specification. Here, we propose an efficient solution algorithm that integrates incomplete local search and interval propagation techniques into a satisfiability solver, which forms a satisfiability modulo theories (SMT) solver. In the third decision step, the PROViDE middleware replicates the solution proposals among the robots. This replication process is parameterized with a distribution method, which determines the consistency properties of the proposals. In a fourth step, we investigate the conflict resolution. Therefore, an acceptance method ensures that each robot supports one of the replicated proposals. As we integrated the conflict resolution into the replication process, a sound selection of the distribution and acceptance methods leads to an eventual convergence of the robot proposals. In order to avoid the execution of conflicting proposals, the last step comprises a decision method, which selects a proposal for implementation in case the conflict resolution fails. The evaluation of our work shows that the usage of incomplete solution techniques of the constraint satisfaction solver outperforms the runtime of other state-of-the-art approaches for many typical robotic problems. We further show by experimental setups and practical application in the RoboCup environment that our decision process is suitable for making quick decisions in the presence of packet loss and delay. Moreover, PROViDE requires less memory and bandwidth compared to other state-of-the-art middleware approaches.

Un poison même à petite dose : étude de la structure latente et des facteurs développementaux du sadisme sexuel

Les délinquants sexuels sadiques sont généralement décrits comme une entité clinique particulière commettant des délits graves. Or, la notion même de sadisme sexuel pose un nombre important de problèmes. Parmi ceux-ci, on retrouve des problèmes de validité et de fidélité. Perçu comme une maladie dont on est atteint ou pas, le sadisme a été étudié comme si les sadiques étaient fondamentalement différents. À l’heure actuelle, plusieurs travaux laissent croire que la majorité des troubles psychologiques se présentent comme une différence d'intensité (dimension) plutôt qu’une différence de nature (taxon). Même si la conception médicale prévaut encore en ce qui concerne le sadisme sexuel, plusieurs évoquent l’idée qu’il pourrait être mieux conceptualisé à l’aide d’une approche dimensionnelle. En parallèle, nos connaissances sur les facteurs contributifs au développement du sadisme sexuel sont limitées et reposent sur de faibles appuis empiriques. Jusqu'à présent, très peu d'études se sont intéressées aux facteurs menant au développement du sadisme sexuel et encore moins ont tenté de valider leurs théories. En outre, nos connaissances proviennent majoritairement d'études de cas portant sur les meurtriers sexuels, un sous-groupe très particulier de délinquants fréquemment motivé par des intérêts sexuels sadiques. À notre connaissance, aucune étude n'a proposé jusqu'à présent de modèle développemental portant spécifiquement sur le sadisme sexuel. Pourtant, l'identification de facteurs liés au développement du sadisme sexuel est essentielle dans notre compréhension ainsi que dans l'élaboration de stratégie d'intervention efficace. La présente thèse s'inscrit dans un contexte visant à clarifier le concept de sadisme sexuel. Plus spécialement, nous nous intéressons à sa structure latente, à sa mesure et à ses origines développementales. À partir d'un échantillon de 514 délinquants sexuels évalué au Massachusetts Treatment Center, la viabilité d’une conception dimensionnelle du sadisme sexuel sera mise à l’épreuve à l'aide d'analyses taxométriques permettant d'étudier la structure latente d'un construit. Dans une seconde étape, à l'aide d'analyses de Rasch et d'analyses appartenant aux théories de la réponse à l'item à deux paramètres, nous développerons la MTC Sadism Scale (MTCSS), une mesure dimensionnelle du sadisme sexuel. Dans une troisième et dernière étape, un modèle développemental sera élaboré à l'aide d'équations structurales. La présente thèse permettra de contribuer à la clarification du concept de sadisme sexuel. Une clarification de la structure latente et des facteurs développementaux permettra de saisir les devis de recherche les plus à même de capturer les aspects essentiels. En outre, ceci permettra d'identifier les facteurs pour lesquels une intervention est la plus appropriée pour réduire la récidive, ou la gravité de celle-ci.

Impacts des dépositions atmosphériques de fer sur les assemblages phytoplanctoniques et la production de diméthylsulfure dans le Pacifique Nord-Est contemporain et dans le contexte de l’acidification des océans

La croissance du phytoplancton est limitée par les faibles concentrations de fer (Fe) dans près de 40% de l’océan mondial. Le Pacifique subarctique Nord-Est représente une de ces zones limitées en fer et désignées High Nutrient - Low Chlorophyll (HNLC). Cet écosystème, dominé par des cellules de petite taille telles les prymnésiophytes, est caractérisé par de très faibles concentrations estivales de chlorophylle a et de fortes concentrations de macronutriments. Il a été maintes fois démontré que les ajouts de fer, sous différentes formes chimiques (habituellement FeSO4), dans les zones HNLC, stimulent la croissance et modifient la structure des communautés planctoniques en favorisant la croissance des cellules de grande taille, notamment les diatomées. Ces effets sur la communauté planctonique ont le potentiel d’influencer les grands mécanismes régulateurs du climat, tels la pompe biologique de carbone et la production de diméthylsulfure (DMS). Les poussières provenant des déserts du nord de la Chine sont reconnues depuis longtemps comme une source sporadique importante de fer pour le Pacifique Nord-Est. Malgré leur importance potentielle, l’influence directe exercée par ces poussières sur l’écosystème planctonique de cette zone HNLC n’a jamais été étudiée. Il s’agit d’une lacune importante puisque le fer associé aux poussières est peu soluble dans l’eau de mer, que la proportion biodisponible n’est pas connue et que les poussières peuvent avoir un effet inhibiteur chez le phytoplancton. Cette thèse propose donc, dans un premier temps, de mesurer pour la première fois l’effet de la fertilisation de la communauté planctonique du Pacifique Nord-Est par un gradient de concentrations de poussières désertiques naturelles. Cette première expérimentation a démontré que le fer contenu dans les poussières asiatiques est biodisponible et qu’une déposition équivalente à celles prenant place au printemps dans le Pacifique Nord-Est peut résulter en une stimulation significative de la prise de nutriments et de la croissance du phytoplancton. Mes travaux ont également montré que l’ajout de 0,5 mg L-1 de poussières peut résulter en la production d’autant de biomasse algale que l’ajout de FeSO4, l’espèce chimique utilisée lors des expériences d’enrichissement en fer à grande échelle. Cependant, les ajouts de FeSO4 favorisent davantage les cellules de petite taille que les ajouts de poussières, observation démontrant que le FeSO4 n’est pas un proxy parfait des poussières asiatiques. Dans un deuxième temps, je me suis intéressée à une source alternative de fer atmosphérique, les cendres volcaniques. Mon intérêt pour cette source de fer a été attisé par les observations d’une floraison spectaculaire dans le Pacifique Nord-Est, ma région d’étude, associée à l’éruption de 2008 du volcan Kasatochi dans les îles Aléoutiennes. Forte de mon expérience sur les poussières, j’ai quantifié l’effet direct de ces cendres volcaniques sur la communauté planctonique du Pacifique Nord-Est. Mes résultats ont montré que le fer contenu dans les cendres volcaniques est également biodisponible pour le phytoplancton. Ils ont également montré que cette source de fer peut être aussi importante que les poussières désertiques dans la régulation de la croissance du phytoplancton dans cette partie de l’océan global à l’échelle millénaire. Dans un troisième temps, j’ai estimé comment l’acidification des océans modulera les réponses des communautés planctoniques aux dépositions naturelles de fer mises en évidence lors de mes expériences précédentes. Pour ce faire, j’ai effectué des enrichissements de poussière dans de l’eau de mer au pH actuel de 8.0 et dans l’eau de mer acidifiée à un pH de 7.8. Mes résultats ont montré une diminution du taux de croissance du phytoplancton dans le milieu acidifié mais pas de changement notable dans la structure de la communauté. Les ajouts de poussières et de cendres, de même que les variations de pH, n’ont pas eu d’effet significatif sur la production de DMS et de son précurseur le diméthylsulfoniopropionate (DMSP), probablement en raison de la courte durée (4 jours) des expériences. L’ensemble des résultats de cette thèse montre que le fer contenu dans diverses sources atmosphériques naturelles est biodisponible pour le phytoplancton du Pacifique Nord-Est et que des taux de déposition réalistes peuvent stimuler la croissance de manière notable dans les premiers jours suivant une tempête désertique ou une éruption volcanique. Finalement, les résultats de mes expériences à stresseurs multiples Fer/acidification suggèrent une certaine résistance des communautés phytoplanctoniques à la diminution du pH prédite d’ici la fin du siècle pour les eaux de surface des océans.

The physical classroom environment : roles, conceptions, and preferences

The problem addressed in this thesis is that a considerable proportion of students around the world attend school in inadequate facilities, which is detrimental for the students’ learning outcome. The overall objective in this thesis is to develop a methodology, with a novel approach to involve teachers, to generate a valuable basis for decisions regarding design and improvement of physical school environment, based on the expressed needs for a specific school, municipality, or district as well as evidence from existing research. Three studies have been conducted to fulfil the objective: (1) a systematic literature review and development of a theoretical model for analysing the role of the physical environment in schools; (2) semi structured interviews with teachers to get their conceptions of the physical school environment; (3) a stated preference study with experimental design as an online survey. Wordings from the transcripts from the interview study were used when designing the survey form. The aim of the stated preference study was to examine the usability of the method when applied in this new context of physical school environment. The result is the methodology with a mixed method chain where the first step involves a broad investigation of the specific circumstances and conceptions for the specific school, municipality, or district. The second step is to use the developed theoretical model and results from the literature study to analyse the results from the first step and transform them in to a format that fits the design of a stated preference study. The final step is a refined version of the procedure of the performed stated preference study.

Catalizzatori polifunzionali per la sintesi di Metil Isobutil Chetone

In this work, we have examined the activity and selectivity of new catalysts for the single-stage production of methyl isobutyl ketone (MIBK, 4- methyl-2-pentanone) from acetone (both in liquid and gas phase), using a fixed bed reactor operated in the temperature range between 373 and 473 K. The main reaction pathways for the synthesis of MIBK from acetone are given in Fig.1. The first step is the self condensation of acetone to diacetone alcohol (DAA, 4-hydroxy-4-methyl-2-pentanone); the second step is the dehydration of DAA to mesityl oxide (MO, 4-methyl-3-penten-2-one); the final step is the selective hydrogenation of the carbon–carbon double bond of MO to form MIBK. The most commonly observed side reactions are over-condensations and unselective hydrogenations (also shown in Fig.1). Two types of catalysts were studied: i)Pd supported on MgO-SiO2 mixed oxides with ratio of Mg to Si, synthetized using Ohnishi’s method and ii)Pd supported on alumina doped with 5% or 10% of MgO. The different Mg-Si and Mg-Al catalysts were characterized by different techniques (XRD, BET, SEM, NH3-TPD and CO2-TPD) and tested under different conditions in the condensation of acetone to diacetone alcohol and its dehydration to mesityl oxide to enhance the activity. Palladium was chosen as metal component, and its hydrogenation activity was studied. A low hydrogenation activity negatively affects the acetone conversion and promotes the production of mesityl oxide. Hydrogenation conditions being too severe may favor the unwanted hydrogenation of acetone to 2-propanol and of MIBK to methyl isobutyl carbinol (MIBC, 4-methyl-2-pentanol) but this effect is less detrimental to the MIBK selectivity than an unsufficient hydrogenation activity.

Conservation narratives in Peru: envisioning biodiversity in sustainable development

In the mega-diverse country Peru, a resource intensive development model collides with the interest of conserving biodiversity. Peruvian biodiversity experts have developed different lines of argumentation as to how to integrate conservation into the sustainable development of their country. Applying grounded theory, I define five groups of conservation narratives based on the analysis of 72 qualitative interviews with experts working in areas of biodiversity conservation. I have labeled them: biodiversity protectionists, biodiversity traditionalists, biodiversity localists, biodiversity pragmatists, and biodiversity capitalists. These groups are each discussed in connection with what they have to say about biodiversity in relation to human life, valuation and knowledge systems, participation and leadership, substitutability of natural capital, and its predominant political strategy. In a second step, a comparative analysis of the dominant and diverging political perspectives is made. I argue that by deconstructing underlying premises and ideologies, common ground and possible opportunities for collaboration can be identified. Moreover, although the presented results can serve as a discussion scaffold to organize conservation debates in Peru, this example demonstrates how the terms biodiversity and sustainability are operationalized in conservation narratives.