Social stigma against gender diverse people continues to exist (Rieger & Savin-Williams, 2012), and this extends to gender nonconforming youth (D’Augelli, Grossman, & Starks, 2006). Expression and exploration of fluid gender identity and gender roles are part of typical human development (Institute of Medicine, 2011). Childhood gender nonconformity is defined as variation from norms in gender role behavior (Adelson & The American Academy of Child and Adolescent Psychiatry, 2012). Recommendations for research with gender nonconforming youth include gaining a clearer understanding of safe relationships, which currently lacks in the counseling literature (Institute of Medicine, 2011). Safety occurs when an individual takes psychological and interpersonal risks without fearing negative consequences (Edmondson, 1999). This study explores safety among gender nonconforming youth through the theoretical perspective of constructivism (Lincoln, Lynham, & Guba, 2011) and queer theory (Plummer, 2011) and will utilize the qualitative methods of photo-elicitation (Harper, 2002) and thematic analysis (Boyatiz, 1998). Implications for counseling practitioners, counselor educators, and future research will be discussed.

Les développements récents des techniques de fabrication de matériaux semi-conducteurs de type III-N comme GaN et AlGaN permettent le développement de photo-détecteurs Schottky et métal-semi-conducteur-métal opérant dans le domaine de l'ultraviolet. Alors que les photo-détecteurs à base de GaN et AlGaN ont un faible bruit et un temps de réponse rapide, l'absence de gain interne est un obstacle majeur à leur utilisation dans des applications qui nécessitent des photo-détecteurs à haute sensibilité. Dans ce travail, nous avons conçu et fabriqué des photo-détecteurs à base d'alliage BAlGaN sous forme de monocouches et de super réseaux réalisés par MOVPE et photo-lithographie. Une caractérisation complète de leurs propriétés électriques et électro-optiques a ensuite été réalisée. Nous montrons que ces nouveaux alliages BAlGaN ont un impact majeur sur les performances des photo-détecteurs étudiés. Nous avons pu réaliser des détecteurs présentant un important gain interne (jusqu'à 3x105) donc avec une sensibilité améliorée, un courant d'obscurité faible (jusqu'à 9 ordres de grandeurs plus faible que dans les détecteurs à base de GaN réalisés), une longueur d'onde de coupure ajustable dans la gamme 260-380, et un temps de réponse deux fois plus rapide que dans les détecteurs à base de GaN réalisés. Finalement, nous proposons une interprétation du mécanisme de gain dans ces nouvelles structures reposant sur l'existence de pièges profonds à électrons et à trous / Recent developments in III-N material growth technology such as GaN and AlGaN made possible to fabricate high performance solar-blind Schottky, and metal-semiconductor-metal based photodetectors operating in the ultraviolet range -based photodetectors. While GaN and AlGaN have low noise and fast response times, the lack of high internal gain is a limitation for their use in applications that require high sensitivity photodetectors. In this work, we have designed and fabricated BAlGaN-based photodetectors. For this, several BGaN monolayer and superlattices were grown using MOVPE and lithography processes followed by a full characterization of their electrical and electro-optical properties. We show that these new BAlGaN alloys have tremendous impact on the performance of these photodetectors. We were able to achieve photodetectors with large internal gain (up to 3x105) and thus improved sensitivity, low dark current (up to nine orders of magnitude lower compared to our own GaN-based photodetectors), tunable cut-off wavelength in the 260-380 nm range, and more than two orders of magnitude reduction in the response time compared to our own GaN-based photodetectors. Finally, we propose an interpretation, based on the existence of deep level electron and hole traps, to explain the different mechanisms at the origin of the internal gain in these new structure

Les objectifs de cette thèse sont articulés autour de deux axes principaux : la synthèse et l’étude de cages moléculaires photo-modulables, et la génération de nano-cristaux d’or par photo-catalyse supramoléculaire. Ces deux thématiques sont reliées entre elles par l’exploitation des propriétés photophysiques et photochimiques d’un motif commun, le 9,10-diphénylanthracène (DPA). Dans un premier temps, de nouvelles architectures tridimensionnelles photo-modulables de type cage moléculaire ont été conçues et étudiées. En présence d’oxygène, l’irradiation directe ou sensibilisée du DPA permet de former réversiblement le dérivé endoperoxyde et ainsi moduler les propriétés de complexation de la cage. Les différentes stratégies de synthèse mises en place reposent sur l’exploitation conjuguée de la réactivité de la 2,4,6-trichloro-1,3,5-triazine, et de réactions de chimie « click » (métathèse des oléfines, cycloaddition de Huisgen). L’étude et la modulation des propriétés des reconnaissances ont été effectuées sur des sels de cations alcalins (sodium et césium) et suivies par émission de fluorescence et spectroscopie d’absorption UV-visible. Les résultats obtenus avec deux cages possédant des constantes d'associations élevées (logK = 8,7 pour le cation sodium) montrent une augmentation de la constante d’association d’un facteur 10 et 20 pour respectivement le sodium et le césium entre la forme DPA et la forme endoperoxyde. Dans un second temps, des photocatalyseurs supramoléculaires basés sur le chromophore DPA ont été étudiés en vue de la synthèse de nano-cristaux d’or nus. L’association du chromophore avec des thioéthers permet de former un complexe en phase organique par extraction de sels d’or(III) depuis une phase aqueuse. L’irradiation à 400nm permet la réduction de l’or(III) par transfert d’énergie depuis le 9,10-diphénylanthracène. Les atomes d’or sont ensuite relargués en phase aqueuse pour former des nano-cristaux nus qui ont pu être caractérisés par MET, XPS, AFM et DLS. Par ailleurs, ce procédé est catalytique dans le toluène et un système de réduction en flux continu a été mis au point permettant un turnover moyen de 150. / The goals of this thesis are organized around two major axes: the synthesis and study of photo-gated molecular cages, and the generation of gold nanocrystals by supramolecular photocatalysis. These two themes are connected by the use of the photochemical and photophysical properties of a common chromophore, 9,10-diphenylanthracene (DPA). Three-dimensional photo-gated cage-like architectures were designed and synthesized. Various synthetic strategies based on the combined use of the 2,4,6-trichloro-1,3,5-triazine unit and "click" chemistry reactions (olefin metathesis, Huisgen cycloaddition) were employed for the synthesis. In the presence of oxygen, sensitized or direct irradiation of the DPA chromophore forms the corresponding endoperoxide derivative, thereby modulating the binding properties of the cage. The study and the modulation of the recognition properties were performed on various alkali metal cations and a strong binding of sodium and cesium was evidenced by fluorescence emission and UV-visible absorption spectroscopy. The cages investigated possessed high association constants towards sodium and cesium cations (logK = 8.7 for the sodium cation) which could be reversibly increased by a factor 10 and 20 for sodium and cesium, respectively, upon formation of the endoperoxide. Supramolecular photocatalysis of gold(III) reduction based on the DPA chromophore was also studied for the preparation of uncapped gold nanocrystals. The combination of the DPA chromophore with thioether chains allows the formation of a complex in the organic phase by extraction of gold(III) chloride from an aqueous phase. Irradiation at 400 nm enables the reduction gold(III) by energy transfer from the 9,10-diphenylanthracene followed by oxidation of the solvent. The gold atoms are subsequently released in the aqueous phase to form uncapped nanocrystals characterized using TEM, XPS, AFM, and DLS techniques. Furthermore, the process is catalytic in toluene, where a continuous flow reactor was developed. The latter allowed an average catalytic turnover of 150 to be determined.

L’utilisation de colorants synthétiques se développe depuis de nombreuses années dans des différentes industries. Les procèdes les plus couramment utilises pour le traitement des eaux usées colorées sont les traitements biologiques mais ils ont leurs limites. Les techniques d’oxydation chimique traditionnelle quant a elles conduisent à la coupure de la molécule au niveau du chromophore ne peuvent pas minéraliser totalement des colorants alors que la dépollution complète de ces effluents l’exigerait. Le procède photo-fenton homogène est une technique de traitement qui peut dégrader les effluents colores efficacement. Mais il y a quelques inconvénients majeurs qui limitent l’application industrielle de cette technologie. L’objectif de ce travail de recherche était d’étudier la décoloration et la dégradation des solutions des colorants: acide orange 7 acide orange 8 acide rouge i4 acide rouge 73 et acide bleu 74 par le procède d’oxydation avancée: photo-Fenton heterogene. Dans ce procède la zeolite fe-zsm5 a été utilisée comme un catalyseur heterogene. L’application de ce système nous a permis d une part de diminuer la quantité de boue formée au cours du traitement ainsi que la consommation d’énergie électrique engendrée par l’utilisation d’UV estimée à l aide de la méthode figures-of-merit et d’autre par d’étendre l’application du procède type photo-fenton aux ph plus élevés. La modélisation des procèdes étudies a été faite par deux méthodes à la méthodologie de surface de réponse (RSM) et les réseaux neuronaux artificiels (ANNS) - afin d optimiser la performance de système et également d'évaluer les effets simples et combines des différentes variables sur l’efficacité du traitement. / Large amounts of dyes are annually produced and applied in different industries. The biological methods are widely used for treatment of coloured ef fluents, but they have some limitations. Traditional chemical oxidations that destroy the chromophore of the molecule could not also result the complete mineralisation of the dyes. Homogeneous photo-fenton is a promising technique for treatment of the effluents but there are still some drawbacks that limit the industrial applications of this method. The aim of this work was to study the decolourisation and the degradation of coloured solution containing acid orange 7 acid orange 8 acid red I4 acid red 73 or acid blue 74 by an advanced oxidation process: heterogeneous Photo-fenton. In this study zeolite fe-zsm5 was used as a heterogeneous catalyst. Application of this system not only allowed us to diminish the quantity of sludge formed during the process but also reduced the consummation of electrical energy process keeps its high efficiency even at neutral phs. The modelling of the process was done by two methods - response surface methodology (RSM) and artificial Neural networks (ANNS) in order to optimise the performance of the system and to evaluate the simple and the combined effects of different variables on the process efficiency.

No description available.

The objective of this research was to study the adsorption and photodegradation of crystal violet (CV) dye by using poly(2-hydroxyethylmethacrylate) (PHEMA) hydrogel and nanocomposite TiO2-PHEMA hydrogel. Since the TiO2 nanoparticle has poor solubility, another goal of this study was to make a uniform TiO2 nanocomposite gel. These gels can be used in water treatment and can be easily photodegrade by exposure of sunlight which is similar to exposing to UV-vis. PHEMA was synthesized by free radical polymerization. The nanocomposite gels were characterized by FT-IR and XRD to confirm the presence of TiO2 nanoparticles and CV dye inside the PHEMA hydrogel. The XRD data showed that not only maintaining the crystallinity of the three different phases that had been used, but also the uptake of the dye inside the nanocomposite gels. Moreover, the FT-IR demonstrated the presence of the functional groups of the chemical structure of the gel as well as the nanocomposite gels with the CV dye. The adsorption of CV dye was examined through monitoring UV-Vis absorption. The kinetic study indicated the adsorption of the dye by the nanocomposite gels until reached equilibrium, which is the zero concentration. The photodegradation of CV dye was examined using a medium pressure Hg lamp. It was determined that the composite gels adsorb CV dye from the solution at the beginning while under the photochemical condition. Eventually, the dye in the gel was photodegraded, indicating that in the gel system, the photodegradation process is still effective to dyes. The composite gels containing pure anatase phase titanium are much better photocatalysts and took less time of adsorption than those containing pure rutile and anatase/rutile mixed phases of titania.

Neste trabalho foram estudadas as características elétricas e ópticas de filmes de carbono tipo diamante (DLC Diamond-Like Carbon) depositados em um sistema de sputtering RF magnetron reativo em substratos de silício e vidro. Foram depositadas amostras em condições de processo distintas em cada tipo de substrato, sendo duas condições de pressão (5 mTorr e 10 mTorr) e para cada uma, quatro condições de potência de RF (100 W, 150 W, 200 W e 250 W). Os filmes depositados foram submetidos às seguintes técnicas de caracterização: perfilometria, para obtenção da espessura dos filmes e com isso a taxa de deposição; elipsometria, para obtenção do índice de refração; obtenção de curvas I-V, para obtenção da resistividade elétrica e cálculo do ganho de foto corrente, e da curva C-V de alta frequência, para cálculo da constante dielétrica dos filmes; transmitância óptica, para o cálculo do gap óptico através do método de Tauc; fotoluminescência, para determinar a emissão característica deste gap e espectroscopia de infravermelho por transformada de Fourier (FTIR), para se observar os tipos de ligações presentes no filme e calcular a relação entre hibridizações sp3 e sp2 entre átomos de carbono e hidrogênio no filme. As variações de algumas características dos filmes de DLC com os parâmetros de processo são apresentadas e comparadas. De acordo com as características dos filmes obtidos neste trabalho, com a variação dos parâmetros de processo, é possível sua aplicação como dielétrico de campo, por apresentarem baixa constante dielétrica, sendo o valor mais baixo obtido igual a 3,4; como material dielétrico de porta considerando os filmes com alta constante dielétrica, chegando a 6,7; como material para cobertura, devido à alta uniformidade (até 95%); e, o que foi mais explorado neste trabalho, para aplicações como sensores foto sensíveis, sendo que o maior ganho de foto corrente obtido foi 67 vezes. A possibilidade de produção de filmes de DLC com diferentes propriedades através da variação das condições de processo mostra sua versatilidade para uso em diferentes aplicações. / In this work it was studied electrical and optical characteristics of diamond-like carbon (DLC) films deposited in a reactive RF magnetron sputtering system on silicon and glass substrates. Samples were deposited at different process conditions in each type of substrate at two pressure conditions (5 mTorr and 10 mTorr) and four conditions of RF power (100 W, 150 W, 200 W and 250 W). The DLC films were characterized by the following techniques: high step meter analysis, to obtain the thickness of the films and thus the deposition rate; Ellipsometry to obtain the refractive index; electrical characterization by the I-V curve, to obtain the resistivity and calculate the photo current gain, and high-frequency C-V curve, to calculate the dielectric constant of the films; optical transmittance, to calculate the optical gap by the Tauc method; photoluminescence analysis, to determine the characteristic emission of this gap; Fourier transform infrared spectroscopy (FTIR), to observe the different carbon-hydrogen bonds and calculate its sp3/sp2 hybridizations ratio. The way some characteristics of DLC films vary with the process parameters are presented and compared in this work. According to the characteristics of the DLC films obtained in this work, with the variation of the process parameters it is possible their application as low k dielectric insulators, because of its low dielectric constant, being the lowest obtained value 3.4; as dielectric gate material, reaching 6.7 in the films deposited in this work, as coating material due to its high uniformity (95%), and which was further explored in this work, for applications like photo-sensitive sensors, since it was obtained samples with photo current gain up to 65. The possibility of producing DLC films with different properties by varying process parameters shows its versatility for using in different applications.

Nossa trajetória no fotojornalismo, marcada por treze anos de trabalho como repórter-fotográfico e editor de fotografia na Empresa Folha da Manhã S.A. nos permitiu conhecer minuciosamente, na prática, o processo de construção de uma imagem fotojornalística. Apesar da produção internacional relativamente abundante e de trabalhos brasileiros de renomados profissionais da área, a produção teórica sobre os aspectos da fotografia no contemporâneo é ainda incipiente no Brasil, principalmente no que diz respeito às inovações tecnológicas e seu impacto no fotojornalismo. Entre as questões mais instigantes da pesquisa e da teoria da imagem estão as tensões entre realidade e ficção e ética e ideologia. Segundo os parâmetros aceitos nas redações, uma boa fotografia é aquela que consegue aliar a precisão da informação com uma contundente beleza plástica. No fotojornalismo, mais que em qualquer outra modalidade de uso da fotografia, o registro fotográfico tem a necessidade de ser entendido, em sua gênese, como um documento, como um atestado comprobatório não apenas de que o fato aconteceu, mas que o mesmo ocorreu tal qual podemos observar na fotografia publicada no veículo. Como pensar então em informação precisa ou em verdade se sabemos de antemão que quando o fotógrafo documenta um acontecimento no espaço-tempo ele está invariavelmente, no ato fotográfico, descolando aquele recorte do real de seu contexto, interpretando o fato de acordo com sua cultura e sua ideologia? No fotojornalismo, essas tensões se revelam sobretudo na busca do equilíbrio possível entre informação e plasticidade, entre a sua natureza noticiosa que o obriga a se manter fortemente conectado a um referente e sua necessidade de conquistar a atenção do olhar do leitor contemporâneo, numa árdua batalha travada nas páginas de jornais e revistas com as imagens idealizadas e tecnicamente perfeitas da publicidade. Neste sentido, esta dissertação, que surge a partir da experiência de quem conheceu os mecanismos que regem o surgimento e a efetuação de uma pauta fotográfica na grande imprensa, pretende contribuir para ampliar o espaço desta reflexão na produção brasileira. Além disso, visamos analisar, ao cruzar a nossa experiência com a bibliografia contemporânea acerca da representação dos fatos na mídia impressa, as possíveis transformações ocorridas no conceito de documento fotográfico no período que vai da implantação da cor na impressão dos jornais diários brasileiros até o momento atual, passando pelo ingresso das câmeras digitais nas redações dos jornais. E, por fim, objetivamos também mostrar, por meio de imagens de violência recolhidas na mídia impressa, como esse processo pode corroborar para que os fotojornalistas e suas empresas façam, inconscientemente ou não, o uso da fotografia como uma ferramenta de criação, propagação e perpetuação de estigmas e preconceitos na sociedade. Sistematizar teórica e criticamente nossa experiência profissional obtida ao longo do trabalho como jornalista, repórter-fotográfico e editor de fotografia e, dessa forma, contribuir para a discussão acerca da profissão por nós escolhida, é um dos principais motivos que nos levaram a propor como objeto desta pesquisa uma análise do fotojornalismo a partir da sua produção desde diferentes perspectivas. / Our trajectory in photojournalism, marked by thirteen years of work as a reporter and photographic editor of the company Empresa Folha da Manhã S.A. allowed us to know, in practice, the process of creation an photojournalistic image. Despite the international production relatively abundant and the work of renowned Brazilian professionals in the area, the production on the theoretical aspects of photography in contemporary is still incipient in Brazil, especially with regard to technological innovations and their impact on photojournalism. Among the most instigatings issues of research and theory of the image are the tensions between reality and fiction and ethics and ideology. According to the editors accepted parameters, a good photograph is one that can combine the accuracy of the information with a convincingly plastic beauty. In photojournalism, more than any other mode of use of the photograph, the photographic record needs to be understood in its genesis, as a document such as a real certificate not only that the fact happened, but that it happened just the we see in the photograph published in the vehicle. Since then, how can we think on accurate information or true if we know in advance that when the photographer documents an event in space-time it is invariably, in the photographic act, unstick that cut of reality of its context, interpreting the fact based on his culture and his ideology? In photojournalism, these tensions are revealed especially in the search of the possible balance between information and plasticity, and its nature that requires that the news remains strongly connected to a referential and their need to win the attention of the readers contemporary look, in a tough battle fought on the pages of newspapers and magazines with the idealized and technically perfect images of advertising. Therefore, this dissertation, which arises from the experience of those who knew the mechanisms that govern the appearance and the execution of a photographic pauta, seeks to expand the space for discussion in the Brazilian production. Also, aim to analyze, by crossing our experience with the contemporary literature about the representation of the facts in press, the possible changes in the concept of photographic as a document, from the period of deployment of colors in printing the brazilianss newspaper untill today, and the advent of digital cameras in editors of newspapers. Finally, we also intend to show, throughout images of violence gathered in press, how this process can corroborate to the photojournalists and their enterprises to do, unconsciously or not, the use of photography as a tool for the creation, propagation and perpetuation of stigmas and prejudices in society. To systematize theoretical and critically our experience obtained during our career as a journalist, editor-reporter of photography and thus contribute to the discussion about the profession we have chosen, is one of the main reasons that led us to propose as the subject of this research an analysis of photojournalism from its production from different perspectives.

A pesquisa inicialmente intitulada: \"Retratos da Serra da Canastra\", teve como proposta a realização de um ensaio fotográfico autoral. Com o intuito de promover a reflexão sobre a construção do livro de autor e sobre os processos de edição da produção artística em suas finalidades específicas, o resultado previsto foi a criação de um livro e a realização de uma exposição. / Originally titled as \"Portraits of the Serra da Canastra\", the research looked to do a photographic essay. Aiming to promote reflection on the construction of an artist\'s book and about edition processes of artistic production in their specific purposes, the expected result was the creation of a book and perform an exhibition.

De nos jours environ 200 molécules ont été observées dans le milieu interstellaire, environ 75% d'entre elles sont carbonées et 25% sont des hydrocarbures. Les grains de poussières contiennent également du carbone en grande quantité. La présence du carbone dans la majorité des molécules et dans les grains de poussières s'explique par son abondance et sa capacité à former des liaisons. Il est donc crucial de les étudier d'un point de vue astrochimique. Dans une première partie, ce travail présente les mesures des rapports de branchement et des énergies dissipées sous forme d'énergie cinétique dans les fragments neutres lors d'une collision à haute vitesse, des molécules carbonées suivantes : SiC, AlC, AlCH, C ₂ O, CN, CH ₂ et CH. Ces mesures ont été obtenues grâce au dispositif expérimental AGAT. Ce dernier est installé à demeure auprès de l'accélérateur Tandem d'Orsay. Il permet la collision molécule-atome en cinématique inverse et la détection 100% efficace de tous les fragments émis, y compris les neutres. Dans une seconde partie, l'effet de l'ajout ou la correction de nouveaux rapports de branchement d'hydrocarbures est discuté, sur la modélisation de la chimie de deux objets célèbres : la région de photo-dissociation de la nébuleuse de la Tête de Cheval et le nuage moléculaire TMC-1. Ces deux objets sont bien connus pour leur richesse en molécules observées. Ces nouveaux rapports de branchement diminuent les abondances calculées des espèces de la phase gazeuse, déjà trop basses par rapport aux observations. Une hypothèse stipule que des hydrocarbures sont dégagés dans la phase gazeuse via les grains de poussières carbonés. Suite à cette hypothèse, pour la première fois, les effets de l'incorporation de réactions de photo-production d'hydrocarbures par les grains de carbone amorphes hydrogénés ont été étudiés, sur la chimie de la phase gazeuse de la nébuleuse de la Tête de Cheval. L'ajout de ces réactions resserre l'écart entre la modélisation et les observations. / Nowadays, about 200 molecules have been observed in the interstellar medium, about 75% are carbon molecules and 25% hydrocarbons. Dust grains also contain carbon in large quantities. The presence of carbon in the majority of molecules of the gaseous phase and in the dust is due to its abundance and its ability to form bonds. So, it is crucial to study the carbon in an astrochemical point of view.In the first part, this work presents measurements of branching ratios and energy dissipated as kinetic energy in neutral fragments which are emitted in a high speed collision, of the following carbon molecules: SiC, AlC, AlCH, C ₂ O, CN, CH ₂ and CH. These measurements were obtained from the experimental setup AGAT. This setup is permanently installed at the Tandem Orsay facility. It allows molecule-atom collisions and 100% effective detection of all the transmitted fragments, including neutral ones.In the second part, the effect of the addition or correction of new hydrocarbon branching ratios is discussed, by modeling of chemistry of two famous objects: the photo-dissociation region of the Horsehead nebula and the molecular cloud TMC-1. Both objects are well known for their numerous observed molecules. These new branching ratios reduce the calculated abundances of species in the gas phase, even though these abundances were already too low compared to the observations. A hypothesis states that hydrocarbons are released into the gas phase via the carbonaceous interstellar dust. Following this assumption, for the first time, the effects of the incorporation of photo-production reactions of hydrocarbons from the hydrogenated amorphous carbons were studied on the chemistry of the gaseous phase of the Horsehead nebula. The addition of these reactions narrows the gap between modeling and observations.