Les travaux de cette thèse concernent l'étude de l'influence des conditions de dépôt sur la microstructure et les propriétés optiques de monocouches dans le but de réaliser des filtres optiques particuliers commercialisables. La méthode de dépôt utilisée est l'évaporation par canon à électrons avec assistance ionique. L'un des deux projets a été de vérifier la faisabilité de filtres optiques infrarouges dans la gamme [2-15] µm avec des matériaux non toxiques. Les monocouches des trois fluorures étudiées ont montré des comportements différents suivant les conditions de dépôt, notamment suivant la température du substrat qui influe fortement sur leur microstructure. L'association du BaF₂ au germanium, avec des réglages optimisés, montre pour différents filtres réalisés des résultats proches de la théorie. Ces filtres sont donc commercialisables. Le second projet a été de développer une machine de dépôt dans le but de pouvoir réaliser des filtres complexes d'une centaine de couches d'épaisseur variable (de 15 à 300 nm) associant des monocouches de TiO₂ à des monocouches de SiO₂. L'étude de l'influence des paramètres de dépôts (pression, assistance ionique, préchauffage du matériau) au travers différentes caractérisations (MEB, AFM, ellipsométrie)  a permis une optimisation des réglages de l'enceinte de dépôt plus efficace et adaptée en fonction des spécifications des filtres optiques à réaliser. Puis, une étude ellipsométrique poussée de l'indice de réfraction des monocouches de TiO₂ en fonction de leur épaisseur a conduit à une nette évolution des résultats pour la réalisation du filtre complexe. / This thesis deals the study of deposition conditions 'effect on the microstructure and optical properties of monolayers in order to achieve marketable optical filters, with particular specifications. All filters and monolayers were deposited by ion-assisted electron-beam evaporation technique. One of the two projects was to test the feasibility of infrared optical filters in the range [2-15] µm with non-toxic materials. The study of monolayers of three fluorides showed different behaviors depending on the deposition conditions especially as a function of the substrate temperature that affects their microstructure. For different filters realized, the association of BaF₂ with germanium, settings of deposition optimized, shows results close to the theory and these filters are marketable. The second project was to develop a deposition chamber in order to realize complex filters built with one hundred layers of variable thickness (15 to 300 nm) associating monolayers of TiO₂ with monolayers of SiO₂. The study of the influence of deposition parameters (pressure, ionic assistance, preheating of material) through different characterizations (SEM, AFM, ellipsometry) allowed the optimization of deposition's parameter settings more effective, and adapted according to the specifications of the optical filters to realize. Then, an ellipsometric advanced study of the refractive index of TiO₂ monolayers depending on their thickness led to a significant change in results for the realization of complex filter.

É conveniente que as políticas ambientais municipais contem não apenas com os instrumentos previstos na legislação federal, mas também com instrumentos urbanístico-ambientais a serem inseridos na legislação de parcelamento, uso e ocupação do solo. Assim, objetivou-se neste trabalho desenvolver um tal instrumento. Para tanto, estabeleceu-se: a) requisitos do instrumento: simplicidade, flexibilidade e embasamento teórico; b) objetivos ambientais considerados: promoção da qualidade ecossistêmica, melhoria do microclima e promoção do controle de drenagem na fonte; c) desenvolvimento de métricas: para os dois primeiros objetivos ambientais, demonstrou-se teoricamente ser satisfatório como indicador único uma simplificação do conceito de ecoexergia devido a Jørgensen e, para o último objetivo ambiental, o pico da vazão de saída do lote; d) estabelecimento de padrões: para os dois primeiros objetivos, definição de valores mínimos da ecoexergia simplificada para lotes em diferentes locais e com diferentes usos e taxas de ocupação, enquanto para o último objetivo, impacto zero. Coincidentemente, enquanto esse instrumento era desenvolvido a Prefeitura do Município de São Paulo (Brasil) procedia a uma revisão da lei de parcelamento, uso e ocupação do solo, tendo sido aceito que o instrumento teórico acima servisse como base para o desenvolvimento de um novo instrumento denominado Quota Ambiental (QA). A transformação do instrumento teórico acima na Quota Ambiental, que terminou por ser inserida no projeto de lei encaminhado à Câmara Municipal e depois aprovado por ela, foi objeto de um estudo sui generis, visto que o autor participou ativamente do desenvolvimento da QA como servidor público. Tal demandaria um método a meio caminho entre o estudo de caso e a observação participante, tendo-se optado por um método análogo ao fenomenológico. Para o desenvolvimento da QA foi formado um pequeno grupo de trabalho do qual o autor participou. O instrumento teórico recebeu diversas modificações não só para conformação a diretrizes e decisões políticas, como para amadurecimento de conceitos e cálculos, mostrando-se viável como base para o desenvolvimento da QA. Diversos grupos de interesse influenciaram o desenvolvimento da QA em diferentes fases e em diferentes níveis, chegando a ocorrer de eles se manifestarem diretamente junto ao grupo de trabalho. A Superior Administração prestigiou o processo, mas mostrou-se às vezes dividida em relação ao conflito entre aspectos ambientais e sociais. O grupo teve sucesso em potencializar os ganhos decorrentes da complementaridade de expertises decorrentes da heterogeneidade em termos de formação e experiência dos membros do grupo. Ele procurou harmonizar as diferentes pressões, muitas vezes até se antecipando a elas. Para tanto, o grupo de trabalho desenvolveu uma dinâmica para chegar a consensos internos e para prever, internalizar e posicionar-se frente a pressões, frequentemente conflitantes. As pressões mais severas provieram da própria burocracia municipal. Em todos esses processos a simplicidade, como requisito, foi perdendo-se. A Quota Ambiental mostrou-se um instrumento inovador, aparentando dar satisfação aos reclamos de diversos grupos de interesse e, principalmente, representando uma cunha ambiental inserida na legislação de parcelamento, uso e ocupação do solo. / It is appropriate that municipal environmental policies incorporate not only the instruments provided for in federal legislation, but also the urban-environmental instruments to be inserted in the urban legislation. Thus, it was aimed in this work to develop such an instrument. To do so, it was established the following: a) requirements of the instrument: simplicity, flexibility and theoretical background; b) environmental objectives considered: promotion of ecosystem quality, improvement of microclimate and promotion of drainage control at source; c) development of metrics: a simplification of the concept of eco-exergy due to Jørgensen has been theoretically proven to be satisfactory as a single indicator of the first two environmental objectives; for the last environmental objective, the lot peak output flow; d) establishment of legal standards: for the first two objectives, definition of minimum values of simplified eco-exergy for lots in different locations and with different uses and occupation rates, whereas for the last objective, zero impact. Coincidentally, while this instrument was being developed, the City of São Paulo (Brazil) proceeded to a review of the zoning law, thus being accepted that the above theoretical instrument should serve as the basis for the development of a new instrument called Environmental Quota (Quota Ambiental, QA, in Portuguese). The transformation of the above theoretical instrument into the QA, which ended up being inserted in the bill forwarded to the City Council and later approved by it, was the subject of a sui generis study, as the author participated actively in the development of QA as a public servant. This would require a method halfway between the case study and the participant observation. A method analogous to the phenomenological one was chosen. A small working group in which the author participated was formed for the development of QA. The theoretical instrument received several modifications not only to conform to political guidelines and decisions, but to maturation of concepts and calculations as well, proving feasible as a basis for the development of QA. Several special interest groups influenced the development of QA in different phases and at different levels; it even occurred to interest groups to directly sue the working group. The High Administration supported the process, but it became sometimes divided in relation to the conflict between environmental and social aspects. The group succeeded in enhancing the gains derived from the complementarity of skills resulting from the heterogeneity in terms of training and experience of the working group members. It sought to harmonize the different pressures, often even foreseeing them. To this end, the working group has developed a dynamic to reach internal consensus and to anticipate, internalize and position itself in the face of frequently conflicting pressures. The most severe pressures came from the municipal bureaucracy itself. In all these processes simplicity, as a requirement, was lost. The Environmental Quota proved to be an innovative instrument, appearing to satisfy the demands of various interest groups and, mainly, representing an environmental wedge inserted in the zoning law.

É conveniente que as políticas ambientais municipais contem não apenas com os instrumentos previstos na legislação federal, mas também com instrumentos urbanístico-ambientais a serem inseridos na legislação de parcelamento, uso e ocupação do solo. Assim, objetivou-se neste trabalho desenvolver um tal instrumento. Para tanto, estabeleceu-se: a) requisitos do instrumento: simplicidade, flexibilidade e embasamento teórico; b) objetivos ambientais considerados: promoção da qualidade ecossistêmica, melhoria do microclima e promoção do controle de drenagem na fonte; c) desenvolvimento de métricas: para os dois primeiros objetivos ambientais, demonstrou-se teoricamente ser satisfatório como indicador único uma simplificação do conceito de ecoexergia devido a Jørgensen e, para o último objetivo ambiental, o pico da vazão de saída do lote; d) estabelecimento de padrões: para os dois primeiros objetivos, definição de valores mínimos da ecoexergia simplificada para lotes em diferentes locais e com diferentes usos e taxas de ocupação, enquanto para o último objetivo, impacto zero. Coincidentemente, enquanto esse instrumento era desenvolvido a Prefeitura do Município de São Paulo (Brasil) procedia a uma revisão da lei de parcelamento, uso e ocupação do solo, tendo sido aceito que o instrumento teórico acima servisse como base para o desenvolvimento de um novo instrumento denominado Quota Ambiental (QA). A transformação do instrumento teórico acima na Quota Ambiental, que terminou por ser inserida no projeto de lei encaminhado à Câmara Municipal e depois aprovado por ela, foi objeto de um estudo sui generis, visto que o autor participou ativamente do desenvolvimento da QA como servidor público. Tal demandaria um método a meio caminho entre o estudo de caso e a observação participante, tendo-se optado por um método análogo ao fenomenológico. Para o desenvolvimento da QA foi formado um pequeno grupo de trabalho do qual o autor participou. O instrumento teórico recebeu diversas modificações não só para conformação a diretrizes e decisões políticas, como para amadurecimento de conceitos e cálculos, mostrando-se viável como base para o desenvolvimento da QA. Diversos grupos de interesse influenciaram o desenvolvimento da QA em diferentes fases e em diferentes níveis, chegando a ocorrer de eles se manifestarem diretamente junto ao grupo de trabalho. A Superior Administração prestigiou o processo, mas mostrou-se às vezes dividida em relação ao conflito entre aspectos ambientais e sociais. O grupo teve sucesso em potencializar os ganhos decorrentes da complementaridade de expertises decorrentes da heterogeneidade em termos de formação e experiência dos membros do grupo. Ele procurou harmonizar as diferentes pressões, muitas vezes até se antecipando a elas. Para tanto, o grupo de trabalho desenvolveu uma dinâmica para chegar a consensos internos e para prever, internalizar e posicionar-se frente a pressões, frequentemente conflitantes. As pressões mais severas provieram da própria burocracia municipal. Em todos esses processos a simplicidade, como requisito, foi perdendo-se. A Quota Ambiental mostrou-se um instrumento inovador, aparentando dar satisfação aos reclamos de diversos grupos de interesse e, principalmente, representando uma cunha ambiental inserida na legislação de parcelamento, uso e ocupação do solo. / It is appropriate that municipal environmental policies incorporate not only the instruments provided for in federal legislation, but also the urban-environmental instruments to be inserted in the urban legislation. Thus, it was aimed in this work to develop such an instrument. To do so, it was established the following: a) requirements of the instrument: simplicity, flexibility and theoretical background; b) environmental objectives considered: promotion of ecosystem quality, improvement of microclimate and promotion of drainage control at source; c) development of metrics: a simplification of the concept of eco-exergy due to Jørgensen has been theoretically proven to be satisfactory as a single indicator of the first two environmental objectives; for the last environmental objective, the lot peak output flow; d) establishment of legal standards: for the first two objectives, definition of minimum values of simplified eco-exergy for lots in different locations and with different uses and occupation rates, whereas for the last objective, zero impact. Coincidentally, while this instrument was being developed, the City of São Paulo (Brazil) proceeded to a review of the zoning law, thus being accepted that the above theoretical instrument should serve as the basis for the development of a new instrument called Environmental Quota (Quota Ambiental, QA, in Portuguese). The transformation of the above theoretical instrument into the QA, which ended up being inserted in the bill forwarded to the City Council and later approved by it, was the subject of a sui generis study, as the author participated actively in the development of QA as a public servant. This would require a method halfway between the case study and the participant observation. A method analogous to the phenomenological one was chosen. A small working group in which the author participated was formed for the development of QA. The theoretical instrument received several modifications not only to conform to political guidelines and decisions, but to maturation of concepts and calculations as well, proving feasible as a basis for the development of QA. Several special interest groups influenced the development of QA in different phases and at different levels; it even occurred to interest groups to directly sue the working group. The High Administration supported the process, but it became sometimes divided in relation to the conflict between environmental and social aspects. The group succeeded in enhancing the gains derived from the complementarity of skills resulting from the heterogeneity in terms of training and experience of the working group members. It sought to harmonize the different pressures, often even foreseeing them. To this end, the working group has developed a dynamic to reach internal consensus and to anticipate, internalize and position itself in the face of frequently conflicting pressures. The most severe pressures came from the municipal bureaucracy itself. In all these processes simplicity, as a requirement, was lost. The Environmental Quota proved to be an innovative instrument, appearing to satisfy the demands of various interest groups and, mainly, representing an environmental wedge inserted in the zoning law.

Les sarcomes épithélioides sont caractérisés dans 85% des cas par une perte d'expression nucléaire de la protéine SMARCB1, codée par un gène suppresseur de tumeurs situés en 22q11 impliqué dans la génèse des tumeurs rhabdoides malignes. L'exploration par BAC-FISH (Bacterial Artificial Chromosome- Fluorescence In Situ Hybridization) d'une série de 40 sarcomes épithélioides a permis d'établir que cette perte d'expression était secondaire dans 85% des cas à des délétions homozygotes et a mis en évidence le premier cas de sarcome épithélioide associé à une délétion germinale de SMARCB1, altération jusqu'alors uniquement identifiée dans les tumeurs rhabdoides malignes. Nous avons par la suite testé le gène suppresseur de tumeurs SMARCA4 comme gène candidat impliqué dans les sarcomes épithélioides SMARCB1-conservés à partir d'une série rétrospective de 16 cas. SMARCA4 code la sous-unité ATPase du complexe BAF dont SMARCB1 représente une sous unité. Ce screening initial a permis d'identifier 6 cas de sarcomes SMARCA4-inactivés dont la localisation était exclusivement thoracique et dont les caractéristiques clinique et anatomopathologique stéréotypées ont permis le recrutement prospectif et rétrospectif de nouveaux cas. L'étude par RNA-sequencing d'une fraction de notre cohorte (n=13/19) a confirmé leur homogénéité transcriptomique et souligné leur parenté avec les tumeurs rhabdoides SMARCB1 et SMARCA4 déficientes. L'absence de mutation germinale fréquente (n=1/11) a fait proposer le terme de sarcome thoracique SMARCA4-déficient (SMARCA4-DTS) en proscrivant l'utilisation du qualificatif « rhabdoide ». La parenté transcriptomique de ces tumeurs laisse entrevoir des vulnérabilités thérapeutiques communes qui restent à identifier / Epithelioid sarcomas (ES) display loss of SMARCB1 nuclear expression in 85% of cases. SMARCB1 is encoded by a tumor suppressor gene located in 22q11 which was first linked to cancer in malignant rhabdoid tumors. While investigating a series of 40 epithelioid sarcomas with BAC-FISH (Bacterial Artificial Chromosome-Fluorescence In Situ Hybridization), we demonstrated that SMARCB1 loss in ES occurred through genomic deletions in 85% of cases. We were also able to highlight the first case of ES associated with a heterozygous SMARCB1 deletion in the germ line, which feature was previously thought to be restricted to malignant rhadboid tumors (MRT). We subsequently investigated a series of 16 SMARCB1-retained ES to identify its underlying culprit gene with a focus on the candidate tumor suppressor gene SMARCA4. SMARCA4 encodes one of the ATPase subunit of BAF complexes. Interestingly, SMARCB1 is also a core submit of these complexes which regulate chromatin remodeling. We were able to identify a set of 6 cases displaying SMARCA4 inactivation with this discovery cohort. The review of medical records highlighted these cases had similar presentation : all tumors presented with large compressive and aggressive mediastinopulmonary masses. We further recruited 13 cases based on these characteristics including 5 prospective cases. The characterization of their transcriptomes by RNA-sequencing (n=13/19) confirmed their remarkable homogeneity, all our samples clustering together with MRT. However our variant diverge from malignant rhabdoid tumors as it lacks SMARCA4 alteration in the germline (n=0/11) and displays complex polyploidy genetic profiles. We therefore called this new tumor variant “SMARCA4-deficient thoracic sarcoma” (SMARCA4-DTS). The transcriptomic vicinity of SMARCA4-DTS and MRT let foresee they share common therapeutic vulnerabilities

No description available.

No description available.

Les travaux de cette thèse concernent l'étude de l'influence des conditions de dépôt sur la microstructure et les propriétés optiques de monocouches dans le but de réaliser des filtres optiques particuliers commercialisables. La méthode de dépôt utilisée est l'évaporation par canon à électrons avec assistance ionique. L'un des deux projets a été de vérifier la faisabilité de filtres optiques infrarouges dans la gamme [2-15] µm avec des matériaux non toxiques. Les monocouches des trois fluorures étudiées ont montré des comportements différents suivant les conditions de dépôt, notamment suivant la température du substrat qui influe fortement sur leur microstructure. L'association du BaF₂ au germanium, avec des réglages optimisés, montre pour différents filtres réalisés des résultats proches de la théorie. Ces filtres sont donc commercialisables. Le second projet a été de développer une machine de dépôt dans le but de pouvoir réaliser des filtres complexes d'une centaine de couches d'épaisseur variable (de 15 à 300 nm) associant des monocouches de TiO₂ à des monocouches de SiO₂. L'étude de l'influence des paramètres de dépôts (pression, assistance ionique, préchauffage du matériau) au travers différentes caractérisations (MEB, AFM, ellipsométrie) a permis une optimisation des réglages de l'enceinte de dépôt plus efficace et adaptée en fonction des spécifications des filtres optiques à réaliser. Puis, une étude ellipsométrique poussée de l'indice de réfraction des monocouches de TiO₂ en fonction de leur épaisseur a conduit à une nette évolution des résultats pour la réalisation du filtre complexe.

Virtual three-dimensional auditory displays (V3DADs) use digital signal processing to deliver sounds (typically through headphones) that seem to originate from specific external spatial locations. This set of studies investigates the delivery of V3DADs through bone-conduction transducers (BCTs) in addition to conventional headphones. Although previous research has shown that spatial separation can be induced through BCTs, some additional signal adjustments are required for optimization of V3DADs, due to the difference in hearing pathways. The present studies tested a bone-conduction adjustment function (BAF) derived from equal-loudness judgments on pure tones whose frequencies were spaced one critical band apart. Localization performance was assessed through conventional air-conduction headphones, BCTs with only transducer correction, and BCTs with a BAF. The results showed that in the elevation plane, the BAF was effective in restoring the spectral cues altered by the bone-conduction pathway. No evidence for increased percept variability or decreased lateralization in the bone-conduction conditions was found. These findings indicate that a V3DAD can be implemented on a BCT and that a BAF will improve performance, but that there is an apparent performance cost that cannot be addressed with BAFs measured using the methodology in the present studies.

No description available.

Extensive theoretical studies on the ground and excited state properties of systems containing heavy atoms have shown that accurate prediction of transition energies and related properties requires the incorporation of both relativistic and higher order correlation and relaxation effects as these effects are strongly inter- wined. The relativistic and dynamical electron correlation effects can be incor- porated in many-electron systems through a variety of many-body methods like configuration interaction (CI), coupled cluster method (CCM) etc. which are very powerful and effective tool for high precision description of electron correlation in many-electron systems. In this thesis, we investigate the relativistic and correlation effects in heavy atomic and molecular systems using these two highly correlated many-body methods. It is well recognized that, heavy polar diatomic molecules such as BaF, YbF, TlF, PbO, etc. are the leading experimental candidates for the search of violation of Parity (P ) and Time-reversal (T ) symmetry. The experimental detection of such P,T-odd effects in atoms and molecules has important consequences for the theory of fundamental interactions or for physics beyond the standard model (SM). For instance, a series of experiments on TlF have already been reported which provide the tightest limit available on the tensor coupling constant C , proton electric dipole moment (EDM) dp , etc. Experiments on YbF and BaF molecules are also of fundamental significance to the study of symmetry violation in nature, as these experiments have the potential to detect effects due to the electron EDMde. It is therefore imperative that high precession calculations are necessary to interpret these ongoing (and perhaps forthcoming) experimental outcome. For example, the knowledge of the effective electric field E(characterized by Wd) at the unpaired electron is required to link the experimentally determined P,T-odd frequency shift with the electron EDM de. We begin with a brief review of P,T-odd effects in heavy atoms and polar diatomics and the possible mechanisms which can give rise to such effects, in particular, the one arises due to the intrinsic electron EDM de. The P,T-odd interaction constant Wd is computed for the ground (2∑ ) state of YbF and BaF molecules using all-electron DF orbitals at the restricted active space (RAS) CI level. The RASCI space used for both systems in this calculation is sufficiently large to incorporate important core-core, core-valence, and valence-valence electron correlation effects. In addition to Wd, we also report the dipole moment (µe ) for these systems to assess the reliability of the method. The basis set dependency of Wd is also analyzed. The single reference coupled cluster (SRCC) method, developed by the cluster expansion of a single determinant reference function, is one of the most sophisticated method for treating dynamical correlation effects in a size-extensive manner. The non-uniqueness of the exponential nature of the wave operator diversifies the methods in multi-reference context. The multi-reference coupled cluster (MRCC) strategies fall within two broad classes: (a) State-Universal (SU), a Hilbert-space approach and (b) Valence-Universal (VU), a Fock-space approach. In this thesis, we shall be mainly concerned with the VU-MRCC which unlike SU-MRCC uses a single wave operator that not only correlates the reference functions, but also all the lower valence (or the so called subdued) sectors, obtained by deleting the occupancies systematically. The linear response theory (LRT) or equation of motion (EOM) method is another possible alternative which is nowadays extensively used to compute the atomic and molecular properties. Although, the CCLRT or EOM-CC method is not fully extensive in nature, this method has some distinct advantages over the traditional VU-MRCC theory. Further, for one-valence problem like ionization processes, the CCLRT/EOM-CC is formally equivalent to VU-MRCC, and hence, size-extensive. In this thesis, the core-extensive CCLRT and core-valence extensive (all electron) VU-MRCC methods are applied to compute the ground and excited state properties of various atomic and molecular systems (HCl, CuH, Ag, Sr, Yb and Hg) using nonrelativistic and relativistic (for heavy atoms) spinors. The similarities and differences in the structure of these two formalisms are also addressed. We also investigate the ground and excited state properties of HCN which is a system of astrophysical importance. This system has raised interest among the astrophysicists due to its detection in the atmosphere of Titan and Carbon stars. HCN has also been identified via radio-techniques in both comets and interstellar atmosphere. In the ash-photolysis of oxazole, iso-oxazole, and thiozole a transient band system was observed in the region 2500-3050 Å. This band system was attributed to a meta-stable form of HCN, i.e, either HNC or triplet HCN. We carry out detailed theoretical investigations using CCLRT and complete active space self-consistent field (CASSCF) method to characterize this unidentified band and other experimentally observed transitions.