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Etude de matériaux solides solgel présentant la proprieté de transmission saturable.Brunel, Marc 09 January 1996 (has links) (PDF)
Le développement rapide des sources lumineuses intenses, accordables en longueur d'onde, représente une menace croissante pour les différents détecteurs existant, et tout particulièrement l'il. Une méthode de protection envisageable est l'utilisation de composes organiques presentant un comportement d'absorption saturable inverse: leur absorption augmente lorsqu'ils sont eclaires par des faisceaux lumineux tres intenses. En utilisant le procede sol-gel, nous avons pu élaborer des materiaux solides compacts dopes avec des molecules de la famille des phtalocyanines. A la longueur d'onde de 532 nanometres, des echantillons de transmission initiale 0,7, ont permis d'induire une densite optique de 1 sous l'effet d'impulsions de forte densite. Avec des echantillons de transmission lineaire 0,4, la densité optique induite est egale a 1,6. Afin de mieux comprendre le processus de saturation de la transmission, nous avons écrit des programmes informatiques permettant de simuler le comportement observe. Ils se sont averes etre d'excellents outils pour mieux cerner les phenomenes mis en jeu. Pour améliorer les performances obtenues, differents types de synthèses ont ete entrepris, et differentes molecules organiques ont ete introduites dans des matrices sol-gel: des tetrabenzoporphyrines, des molécules de fullerènes et de hitci. Pour déterminer les plages spectrales d'efficacité de ces echantillons, des sources impulsionnelles accordables en longueur d'onde ont ete installees. Apres la synthèse de premiers échantillons efficaces dans la partie bleue du spectre visible, il a ete possible d'en elaborer d'autres efficaces dans la partie rouge du spectre. Disposant de materiaux actifs a la longueur d'onde de 620 nanomètres, nous avons alors pu montrer a cette longueur d'onde qu'il s'agit d'un processus ultrarapide qui intervient en moins de cent femtosecondes. Enfin, en utilisant les programmes de simulation developpes, nous avons étudie les performances que nous sommes en droit d'esperer de composes absorbants saturables inverses qui seraient inseres dans un systeme limiteur optique.
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Nouveaux concepts pour des sources laser bleues à base de cristaux dopés NéodymeHérault, Emilie 12 February 2007 (has links) (PDF)
Les sources laser bleues possèdent des applications nombreuses et varies (shows laser, affichage, médecine, spectroscopie, communications sous-marines, stockage de données). Lors de cette thèse, nous avons démontré qu'avec de nouveaux concepts, il est possible de réaliser des sources bleues originales à base de cristaux dopés néodyme. Nous avons dans un premier temps proposé une alternative au laser à Argon en concevant une source basée sur la somme de fréquence de deux raies du néodyme émettant autour de 1060 nm et 910 nm. Afin de choisir le cristal optimal, nous avons mené une étude comparative sur certaines caractéristiques physiques et les performances laser sur la transition 4F3/2-4I9/2 des cristaux de Nd:GdVO4 et Nd:YVO4. Nous avons ensuite conçu et réalisé quatre architectures laser émettant en continu à 491 nm, toutes à base de somme de fréquence intracavité. Les deux premières étaient basées sur des laser bi-longueur d'onde à un seul ou deux cristaux laser. La troisième était composée de deux lasers dont les cavités étaient imbriquées, le cristal non linéaire étant inséré dans la partie commune. Finalement, nous avons réalisé un laser émettant à 1064 nm pompé intracavité à 912 nm. Sur le même principe, nous avons conçu une source en régime déclenché à 491 nm grâce à un nouveau concept d'extraction de puissance par interaction non linéaire. La somme de fréquence a alors lieu intracavité à 912 nm mais extracavité à 1063 nm. Finalement, nous avons étudié et réalisé un laser fonctionnant sur la transition à trois niveaux de l'ion néodyme. Par génération de second harmonique, nous avons ainsi réalisé des sources bleues de longueur d'onde inférieure à 450 nm.
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Optical wireless communications with optical power and dynamic range constraintsYu, Zhenhua 22 May 2014 (has links)
Along with the rapidly increasing demand for wireless data while more and more crowded radio frequency (RF) spectrum, optical wireless communications (OWC) become a promising candidate to complement conventional RF communications, especially for indoor short and medium range data transmissions. Orthogonal frequency division multiplexing (OFDM) is considered for OWC due to its ability to boost data rates. However, the average emitted optical power and dynamic range of driving signals of LEDs are two major constraints in OWC. OFDM waveforms exhibits high upper and lower peak-to-average power ratios (PAPRs), which make OFDM signals optical power inefficient and easy to violate the dynamic range of LEDs, resulting clipping and nonlinear distortions. In this dissertation, we analyze and design optical power and dynamic range constrained OWC systems, for which OFDM is our major subject. We first derive distributions of upper PAPR and lower PAPR of OWC-OFDM signals. Then we analyze the clipped OFDM signals in term of error vector magnitude (EVM), signal-to-distortion ratio (SDR), and achievable data rates under both optical power and dynamic range constraints. The next part of this dissertation is the OFDM system design for visible light communications (VLC) considering illumination requirement. We investigate the illumination-to-communication efficiency (ICE) in VLC-OFDM, and design the brightness control and flickering mitigation schemes for VLC-OFDM. In the end, to reduce the complexity of driving circuits of LEDs , we propose using delta-sigma modulators in VLC-OFDM systems to convert continuous magnitude OFDM symbols into two-level LED driver signals without loss of the communication theory advantages of OFDM.
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Analyse qualitative du contenu des signalements retenus à la protection de la jeunesse et leur évaluation pour les enfants de minorités visiblesBousquet Saint-Laurent, Tanya 08 1900 (has links)
Cette recherche propose une analyse qualitative du contenu de signalements retenus à la protection de la jeunesse et leur évaluation pour des enfants de minorités visibles. Les premiers objectifs de cette recherche sont de décrire les deux premières étapes de l’intervention en protection de la jeunesse, soit la réception du signalement et l’évaluation du besoin de protection. Par la suite, elle vise l’élaboration d’une typologie de familles de minorités visibles signalées à la protection de la jeunesse. Une analyse qualitative de contenu est conduite en utilisant une grille d’analyse des dossiers de 48 situations d’enfants signalés à la protection de la jeunesse. Il s’agit d’une analyse secondaire de données d’une étude plus large portant sur l’intervention en protection de la jeunesse auprès de familles de minorités visibles.
Les résultats de la présente étude montrent que les informations consignées aux dossiers par les intervenants respectent les dimensions légales du jugement sur la compromission du développement ou de la sécurité d’un enfant. Toutefois, l’absence d’éléments ethnoculturels dans la majorité des dossiers, ou leur traitement superficiel, sont surprenants. La typologie découlant de cette analyse décrit quatre profils présentant des dynamiques familiales distinctes : les familles traversant une crise, les familles qui abdiquent leur rôle parental, les familles isolées et les familles éclatées.
Ces résultats rendent compte de la diversité des dynamiques familiales et par conséquent, des besoins de ces familles quant aux interventions des services de protection. Enfin, étant donné l’importance de l’évaluation et de ses conclusions dans la trajectoire de ces familles à l’égard de la DPJ, l’intégration des éléments ethnoculturels devrait être systématique afin de leur offrir une réponse adaptée et culturellement sensible. / The first objects of this research are to describe the first two youth protection intervention stages, namely report notification and assessment of the need for protection. Afterwards, the research deals with the development of a typology of visible minority families reported to youth protection services. A qualitative content analysis is conducted using an analysis grid of records dealing with 48 situations of children reported to youth protection services. It is a secondary analysis of data from a broader study dealing with child protection intervention with visible minority families.
The results of the present study show that the information recorded by child-care workers complies with the legal aspects of the judgment on the potential harm to a child’s development or safety. However, the absence of ethnocultural elements in most records or a superficial treatment thereof, are surprising. The typology flowing from this analysis describes four profiles presenting distinct family dynamics: families going through a crisis, families abdicating their parenting responsibilities, isolated families and broken families.
These findings account for the diversity of family dynamics and consequently, those families’ needs in terms of child protection intervention services. Finally, given the importance of the assessment and of these conclusions in the path of those families towards child protection intervention services, the integration of ethnocultural elements should be systematic in order to provide them with an adapted, culturally sensitive response.
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Postsecondary pathways among second-generation immigrants of haitian origin : a Montreal CEGEP case studyCollins, Tya 11 July 2016 (has links)
No description available.
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Espectrofotometria aplicada na análise de nanocarreadores lipídicos contendo ativos para lipodistrofia ginoideBaldissera, Denise Bom 29 April 2014 (has links)
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Previous issue date: 2014-04-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Gynoid lipodystrophy (GLD), also known as cellulite, is a common dermatological condition among women after the puberty, mainly concentrated in the pelvic region, lower limbs and abdomen. It´s a tissue edematous infiltration that promotes unattractive changes, the skin becomes to have a paddled aspect or orange peel , conducing to a low self esteem. The exactly etiology of GLD is unknown, however, its presence and level are related to several factors like genetic, emotional, metabolic and hormonal, besides the age, sex, blood pressure, obesity and habits like smoke, sedentary, tight clothes and poor diet. There are many ways to treat this condition, being the most used and easy accessed the use of cosmetic products having as active principles the vasopressure action, anti-inflammatory, lower microcirculation and lipolytic agents. In the present work, methods for analysis of the lipid nanocarrier containg actives employees for GLD treatment (diidromiricetin, diosgenin and synephrine) were developed and validated. There aren t decrypted monographs in pharmacopeias to analyze these substances in pharmaceutical formulas. In the spectrophotometric method UV-VIS the diosgenin and the dihydromyricetin were quantified in 434 nm and 561 nm, respectively, used as reagents sulfuric acid and ρ- anisaldehyde. Synephrine can be quantified by the derivative ultraviolet spectrophotometry, 239 nm wave-length, in the second order, medium scan, Δλ 10.000 and scale factor of 50, using ethanol as a solvent. The methods showed to be specific, linear, precise, exact and robust to the actives quantification. It can be concluded that the validated methods were of easy execution, fast and with a low cost, to do the quality control analyses. / A lipodistrofia ginoide (LDG), também chamada de celulite, é uma afecção dermatológica comum entre mulheres após a puberdade, concentrando-se preferencialmente na região pélvica, membros inferiores e abdome. Trata-se de uma infiltração edematosa do tecido conjuntivo que promove alterações esteticamente desagradáveis, fazendo com que a pele assuma um aspecto acolchoado ou casca de laranja , levando a uma diminuição da auto-estima. A exata etiologia da LDG é desconhecida, contudo, sua presença e grau de comprometimento estão relacionados a diversos fatores como genéticos, emocionais, metabólicos e hormonais, além da idade, sexo, hipertensão arterial, obesidade e hábitos como fumo, sedentarismo, roupas apertadas e má alimentação. Existem inúmeras formas de se tratar essa condição, sendo a mais utilizada e de fácil acesso o uso de cosméticos contendo princípios ativos com ação vasopressora, anti-inflamatória, estimuladores da microcirculação periférica e agentes lipolíticos. No presente trabalho, métodos para análise de um nanocarreador lipídico contendo ativos empregados para o tratamento da LDG (diidromiricetina, diosgenina e sinefrina) foram desenvolvidos e validados. Não há monografias descritas em farmacopéias para análise desses ativos em formulações farmacêuticas. No método espectrofotométrico UV-VIS a diosgenina e a diidromiricetina foram quantificadas em 434 nm e 561 nm, respectivamente, utilizando como reagentes ácido sulfúrico e ρ-anisaldeido. A sinefrina pode ser quantificada por espectrofotometria ultravioleta derivada, no comprimento de onda de 239 nm, na segunda derivada, velocidade de varredura média, Δλ 10.000 e fator escala de 50, utilizando etanol como solvente. Os métodos demonstraram serem específicos, lineares, precisos, exatos e robustos para a quantificação dos ativos. Sendo assim, pode-se concluir que os métodos validados foram de fácil execução, rápidos e de baixo custo, para a realização das análises de controle de qualidade.
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ESPECTROFOTOMETRIA APLICADA NA ANÁLISE DE NANOCARREADORES LIPÍDICOS CONTENDO ATIVOS PARA LIPODISTROFIA GINOIDEBaldisserta, Denise Bom 29 April 2014 (has links)
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Previous issue date: 2014-04-29 / Gynoid lipodystrophy (GLD), also known as cellulite, is a common dermatological condition among women after the puberty, mainly concentrated in the pelvic region, lower limbs and abdomen. It´s a tissue edematous infiltration that promotes unattractive changes, the skin becomes to have a paddled aspect or “orange peel”, conducing to a low self esteem. The exactly etiology of GLD is unknown, however, its presence and level are related to several factors like genetic, emotional, metabolic and hormonal, besides the age, sex, blood pressure, obesity and habits like smoke, sedentary, tight clothes and poor diet. There are many ways to treat this condition, being the most used and easy accessed the use of cosmetic products having as active principles the vasopressure action, anti-inflammatory, lower microcirculation and lipolytic agents. In the present work, methods for analysis of the lipid nanocarrier containg actives employees for GLD treatment (diidromiricetin, diosgenin and synephrine) were developed and validated. There aren’t decrypted monographs in pharmacopeias to analyze these substances in pharmaceutical formulas. In the spectrophotometric method UV-VIS the diosgenin and the dihydromyricetin were quantified in 434 nm and 561 nm, respectively, used as reagents sulfuric acid and ρ- anisaldehyde. Synephrine can be quantified by the derivative ultraviolet spectrophotometry, 239 nm wave-length, in the second order, medium scan, Δλ 10.000 and scale factor of 50, using ethanol as a solvent. The methods showed to be specific, linear, precise, exact and robust to the actives quantification. It can be concluded that the validated methods were of easy execution, fast and with a low cost, to do the quality control analyses. / A lipodistrofia ginoide (LDG), também chamada de celulite, é uma afecção dermatológica comum entre mulheres após a puberdade, concentrando-se preferencialmente na região pélvica, membros inferiores e abdome. Trata-se de uma infiltração edematosa do tecido conjuntivo que promove alterações esteticamente desagradáveis, fazendo com que a pele assuma um aspecto acolchoado ou “casca de laranja”, levando a uma diminuição da auto-estima. A exata etiologia da LDG é desconhecida, contudo, sua presença e grau de comprometimento estão relacionados a diversos fatores como genéticos, emocionais, metabólicos e hormonais, além da idade, sexo, hipertensão arterial, obesidade e hábitos como fumo, sedentarismo, roupas apertadas e má alimentação. Existem inúmeras formas de se tratar essa condição, sendo a mais utilizada e de fácil acesso o uso de cosméticos contendo princípios ativos com ação vasopressora, anti-inflamatória, estimuladores da microcirculação periférica e agentes lipolíticos. No presente trabalho, métodos para análise de um nanocarreador lipídico contendo ativos empregados para o tratamento da LDG (diidromiricetina, diosgenina e sinefrina) foram desenvolvidos e validados. Não há monografias descritas em farmacopéias para análise desses ativos em formulações farmacêuticas. No método espectrofotométrico UV-VIS a diosgenina e a diidromiricetina foram quantificadas em 434 nm e 561 nm, respectivamente, utilizando como reagentes ácido sulfúrico e ρ-anisaldeido. A sinefrina pode ser quantificada por espectrofotometria ultravioleta derivada, no comprimento de onda de 239 nm, na segunda derivada, velocidade de varredura média, Δλ 10.000 e fator escala de 50, utilizando etanol como solvente. Os métodos demonstraram serem específicos, lineares, precisos, exatos e robustos para a quantificação dos ativos. Sendo assim, pode-se concluir que os métodos validados foram de fácil execução, rápidos e de baixo custo, para a realização das análises de controle de qualidade.
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Localized modification of conducting and insulating substrates (gold, copper, metal ion-doped sol-gels) by scanning electrochemical microscopy. Application to direct writing / Modification localisée de substrats conducteurs et isolants (or, cuivre, sols-gels dopés avec des ions métalliques), par microscopie électrochimique à balayage. Application à l'écriture directeKandory, Ahmed ismail kareim 19 October 2016 (has links)
De nos jours, la modification de surface fait l'objet d'attentions particulières en raison de sa variété d'applications dans divers domaines. Dans ce contexte, l'objectif de cette thèse a été de traiter de la modification localisée de surfaces dans des conditions douces en utilisant le microscope électrochimique à balayage (SECM). En tant que preuve de concept pour l'écriture directe, différentes stratégies ont été menées pour la modification de surface par gravure de matériaux, greffage de couche organique et modification de la structure chimique surfacique. Des surfaces de verre et d'or ont été les principaux substrats qui ont été modifiés du fait de leur large utilisation notamment dans les nanotechnologies. Cette thèse est présentée sous forme de quatre chapitres et le premier est consacré à la technique SECM ainsi qu'à la modification de surface en général. Les trois autres parties concernent le travail effectué pour valider le concept d'écriture directe. Dans la première partie, une matrice de silice synthétisée par voie sol-gel et dopée avec un ion métallique (cuivre ou or) est utilisée comme matériau d'écriture à l'aide d'une sonde locale (ultramicroéléctrode). Le SECM est utilisé en mode de rétroaction avec des médiateurs tels que viologène de méthyle et le p-benzoquinone. Le diamètre de l'ultramicroélectrode (UME) et la durée d'hydrolyse ont été des facteurs pris en compte pour étudier l'effet sur la taille des plots métalliques électrogénérés. Dans la deuxième partie, la gravure par voie humide localisée de la surface de l'or a été réalisée en utilisant le SECM opérant dans un électrolyte à base de diméthylsulfoxide chargé avec de l'iode. Dans cette méthode, une UME est positionnée (à une distance connue) à proximité de la surface d'or pour générer électrochimiquement l'ion triiodure à la pointe de l'UME de platine, agissant comme oxydant à la surface d'or. La troisième partie comprend deux travaux expérimentaux différents mais complémentaires. Le premier porte sur la réduction électrochimique sur électrode d'or d'un sel de diazonium préparé à partir de l'éthylènediamine, une molécule aliphatique. Pour la première fois, la fonctionnalisation covalente sur or d'un sel de diazonium est démontrée via la diazotation d'un groupe amino de l'éthylènediamine. Dans la seconde partie, un substrat de verre a été greffé par un film à base de 3-aminopropyle silane qui a été réalisée par un procédé sol-gel. Ensuite, la lame de verre modifiée a été fonctionnalisée avec du glutaraldéhyde pour greffer la tyrosinase. Enfin, le mode de réaction du SECM a également été utilisé pour vérifier l’activité catalytique de cette enzyme. La pointe de l’UME est positionnée à proximité de la surface modifiée par l’enzyme afin de réaliser une mesure de courant de l’activité enzymatique à partir d’un balayage horizontal dans le plan x-y. / Nowadays, the modification of surfaces has drawn more attention due to its variety of applications in various domains. Therefore, the purpose of this thesis deals with the localized modification of surfaces in mild condition by using the scanning electrochemical microscope (SECM) instrument. As a proof of concept for direct writing, different strategies have been used for surface modifications through removing surface materials, grafted organic layer and changing the chemical structure of the surface. Gold wafer and glass surfaces were the main substrates which have been modified since these materials are very used especially in nanotechnologies. This dissertation is conducted in four chapters and the first one focuses on SECM technique and surface modifications in general. The three other parts concern the work performed to validate the concept of direct writing. In the first part, metal ion (copper and gold)-doped silica matrices have been prepared by the well-known sol-gel method. Copper and gold metallic particles are produced locally by using the SECM in feedback mode with mediators such as methyl viologen and p-benzoquinone. The diameter of ultramicroelectrode (UME) tip and hydrolysis period were factors taken into account to study the effect on the size of electrogenerated metallic spots. In the second part, the localized wet etching of gold surface has been achieved by using SECM where a dimethylsulfoxide-based electrolyte charged with iodine is used. In this method an UME probe is positioned (at a known distance) close to the gold surface. Friendly environment method was used as etching process to generate electrochemically triiodide ion at the platinum UME tip, acting as an oxidant for gold surface. he third part includes two different experimental works. The first one covers the electrochemical reduction on gold electrode of diazonium salt prepared from ethylenediamine, an aliphatic diamine molecule. For the first time, the covalent functionalization on gold of a diazonium salt is demonstrated, and required diazotization of one amine group from ethylenediamine. In the second work, glass substrate was grafted by 3-aminopropyl silane film which was performed by sol-gel method. Then the modified-glass slide was functionalized by glutaraldehyde solution in order to immobilize tyrosinase molecules. Finally, the feedback mode of SECM has also been used to monitor the catalytic activity of tyrosinase. The tip of ultramicroelectrode was positioned close to the enzyme-modified surface and was scanned horizontally in x-y plane while measuring current from re-generated mediator molecules was carried out.
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Att förstå sitt lärande : En pilotstudie av högstadieelevers uppfattningar om metakognitiva frågor i ämnena bild och svenska / To understand One's Learning : A pilot study about senior-level students' apprehensions of metacognitive questions in the subjects Art and SwedishVossman Strömberg, Anneli January 2018 (has links)
Syftet med pilotstudien är att pröva hur rekommenderade metoder för att uppmuntra elevers metakognitiva tänkande kan användas. Metakognition handlar om ”att lära att lära” och är relaterat till begrepp såsom återkoppling, självreglering och formativ bedömning. Forskning visar att elever som får träning i metakognition ökar sina prestationer. Ett av skolans mål enligt läroplanen för grundskolan, förskoleklassen och fritidshemmet 2011/2017 är att eleverna ska utveckla förmågan att bedöma sina resultat. Jag har undersökt hur elever i årskurs sju besvarar och uppfattar metakognitiva frågor i ämnena bild och svenska. Eleverna svarade på metakognitiva frågor vid tre olika tillfällen: vid planeringen, under genomförande samt vid utvärderingen av arbetsuppgiften. I samband med frågorna svarade de även på en enkät om hur de uppfattade de metakognitiva frågorna. Avsikten är att använda pilotstudiens resultat för att bereda mark för en större studie. I studien har en kvalitativ forskningsmetod använts. Resultatet visar att det är väsentligt att lärarna tar reda på elevernas olika förförståelse för de metakognitiva frågorna. Majoriteten av elever upplever de metakognitiva frågorna som oanvändbara, men av olika skäl. Om eleverna inte förstår frågorna tycker de att frågorna blir något utöver arbetsuppgiften. Om eleverna har en hög metakognitiv förförståelse kommer de att anse att frågorna är överflödiga. De flesta eleverna upplevde att de metakognitiva frågorna tog tid från den uppgift de skulle genomföra. Några elever uttryckte stort missnöje, stor frustration och irritation över frågorna. För att metakognitivt tänkande ska kunna tränas metodiskt med avsedd effekt, måste eleverna vara motiverade. En nyckelfaktor är att eleverna förstår vad träningen ska leda till. Detta behöver läraren arbeta med på olika sätt med olika grupper av elever. / This pilot study aims to test how recommended methods to promote students’ metacognitive thinking can be used. Metacognition is about “learning how to learn” and is related to conceptions like feedback, self-regulation and formative assessment. Research shows that students that get training in metacognition increase their performances. One of the goals according to the Swedish Curriculum for the compulsory school, preschool class and the recreation centre 2011/2017 is that students shall develop the ability to assess their results. I have examined how students in grade seven answer and apprehend metacognitive questions in the compulsory subjects Art and Swedish. The students answered metacognitive questions at three different times: when planning, when carrying through and when evaluating the task. In connection to answering the questions they also answered a questionnaire about their conception of the metacognitive questions. The intention is to use the result of the pilot study to prepare for a larger study. A qualitative research method has been used in this study. The result show that it’s substantial that the teachers find out about the students different preunderstanding of the metacognitive questions. The majority of the students find the metacognitive question useless, but for different reasons. If the students don’t understand the questions they think that the questions are something in addition to the task. If the students have a high metacognitive preunderstanding they will consider the questions as redundant. Most students thought that the metacognitive questions took time from the task they were supposed to do. Some students expressed great dissatisfaction, big frustration and irritation over the questions. To be able to train metacognitive thinking methodically with desired effect the students have to be motivated. A key factor is that the students understand what the training is supposed to leading. The teacher has to work in different ways with different groups of students with this.
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Inactivation of Microorganisms by PhotocatalysisSontakke Sharad, M January 2012 (has links) (PDF)
Photocatalysis is an advanced oxidation process, which has shown to possess an enhanced capability to remove a wide range of contaminants. It involves the use of a semiconductor photocatalyst and a photon source. Photocatalysis has several advantages such as mild reaction conditions like ambient temperature and pressure, good control over the reaction and faster reaction kinetics. Semiconductor photocatalysts such as TiO2, ZnO, Fe2O3, CdS, ZnS, etc. absorbs light of energy greater than or equal to its band gap and the electron in the valence band gets excited to conduction band leaving behind the hole in valence band. These charge carrier pair results in the formation of various reactive oxygen species such as hydroxyl and superoxide radicals which results in the degradation of chemical contaminants and inactivation of microorganisms.
TiO2 is the most widely used catalyst in photocatalytic studies because of its high photocatalytic activity, non-toxicity and wide availability. Anatase phase TiO2 has been reported to possess higher photocatalytic activity than the rutile phase. Although there are several methods to synthesize TiO2, solution combustion synthesis is a single step process to produce pure anatase phase TiO2. The catalyst produced by this method has been shown to be superior to the commercially available Degussa P-25 catalyst for the degradation of various chemical contaminants. The present investigation focuses on the use of combustion synthesized catalyst for the inactivation of microorganisms. The photocatalytic activity was compared with commercial Degussa P-25 catalyst.
The various aspects of photocatalytic inactivation reactions studied in this dissertation are: i) photocatalytic inactivation of microorganisms in presence of UV light, ii) effect of various parameters on the inactivation, iii) photocatalytic inactivation in presence of visible light, iv) use of immobilized catalyst for the photocatalytic inactivation, v) understanding of mechanism and kinetics of inactivation.
Combustion synthesized TiO2 (CS-TiO2), combustion synthesized 1% Ag substituted TiO2 (Ag/TiO2 (Sub)) and 1% Ag impregnated CS-TiO2 (Ag/TiO2 (Imp)) were used as photocatalysts. The catalysts were characterized by powder XRD, TEM, BET surface area, UV-Vis spectroscopy, TGA and photoluminescence spectroscopy. The photocatalytic inactivation experiments were carried out using E. coli (K-12 MG 1655), a bacterial strain and P. pastoris (X-33), a yeast strain, as model microorganisms.
The results demonstrate higher photocatalytic activity of all the combustion synthesized catalysts than commercial Degussa P-25 catalyst. The optimum catalyst concentration was 0.25 g/L and the maximum inactivation was observed in the presence of Ag/TiO2 (Imp) catalyst. Rapid and complete inactivation of the microorganisms was observed at lower initial cell concentrations. A reduced photocatalytic inactivation was observed in presence of various anions (HCO3¯ , SO4 2¯ , Cl¯ and NO3¯ ) and cations (Na, K, Caand Mg). Even a small addition of H2O2 was observed to improve the photocatalytic inactivation. At higher dosage of H2O2, a 2 min exposure was sufficient to result in a complete inactivation. Changing the initial pH of the solution was observed to have no significant effect on the photocatalytic inactivation.
All the combustion synthesized catalysts showed higher activity as compared to those obtained with commercial Degussa P-25 TiO2 in presence of visible light. The higher photocatalytic activity of combustion synthesized TiO2 can be attributed to the lesser crystallite size, higher surface area, large amount of hydroxyl groups and decreased band-gap energy of the catalyst.
The present study demonstrates the potential use of catalyst immobilized thin films for the photocatalytic inactivation of E. coli in the presence of UV light. The CS-TiO2 catalyst was immobilized on glass substrate by LbL deposition technique. The performance of immobilized CS-TiO2 was compared to commercial Degussa Aeroxide TiO2 P-25 (Aeroxide) catalyst. The effect of various operating parameters like catalyst loading, surface area and number of bilayers on inactivation has been investigated. It was observed that increasing the number of bilayers and the concentration did not influence the inactivation but increased surface area led to an increase in inactivation. It was observed that the catalyst immobilized on glass slides can be used for repeated experimental cycles with the same efficiency. It was observed that the inactivation process can be studied in continuous mode by using catalyst immobilized on glass beads.
The work also focused attention towards understanding the microorganism inactivation mechanism and kinetic aspects. Various microscopy techniques such as optical microscopy, scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to study the inactivation mechanism. From the images obtained, it was suggested that the inactivation is caused due to rupture of cell wall. The mechanism was also examined by carrying out degradation experiments on cell component such as protein and media component such as dextrose. UV alone was
observed to degrade protein and the presence of catalyst showed no additional effect. On the other hand, dextrose does not respond to photocatalytic degradation even at a lower concentration. The photocatalytic degradation of Orange G dye was reduced by addition of dextrose sugar or protein which shows a possibility of competitive degradation.
The kinetics of inactivation was studied by various models available in literature such as the power-law model, Chick-Watson model, modified Hom model, GInaFIT tool and a Langmuir-Hinshelwood type model. It was observed that power-law based kinetic model showed good agreement with the experimental data. A mechanistic Langmuir-Hinshelwood type model was also observed to model the inactivation reactions with certain assumptions.
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