Plinia edulis (Myrtaceae), espécie arbórea popularmente conhecida como cambucá, é nativa da Mata Atlântica brasileira. Apesar do emprego na medicina tradicional em diversas moléstias, incluindo distúrbios gástricos, não existem estudos relacionando as atividades biológicas e os constituintes químicos da espécie. Esta tese relata a avaliação da gastroproteção, da atividade antioxidante, da citotoxicidade e da mutagenicidade do extrato etanol/água de folhas de P. edulis e das frações. Com o objetivo de correlacionar os metabólitos secundários com a eficácia da droga vegetal na medicina tradicional, o extrato foi submetido à partição e posterior fracionamento cromatográfico. O extrato apresentou atividade gastroprotetora significativa em modelo de indução de úlceras por etanol acidificado em ratos em doses de 100, 200 e 400 mg/kg via oral, sendo mais ativo que o fármaco de referência lansoprazol. Entre as frações, a hexânica (100 mg/kg p.o.) foi a mais eficaz, mas apresentou menor atividade do que o extrato bruto. A gastroproteção do ácido ursólico também foi avaliada, mas embora outros triterpenos sejam conhecidos como gastroprotetores, o ácido ursólico (50 mg/kg p.o.) reduziu a área lesionada, mas não apresentou atividade significativa no modelo empregado. O extrato não evidenciou mutagenicidade na concentração de 20 mg/placa no Ensaio de Ames e apresentou atividade antioxidante pronunciada, com CE50 de 5,75 µg/mL no ensaio com DPPH e valor de ORAC de 3.948 µmol de Trolox/g de extrato. O extrato e as frações foram avaliados quanto à citotoxicidade em linhagens de células tumorais humanas de UACC62 (melanoma), MCF-7 (mama), NCI 460 (pulmão), OVCAR03 (ovário), PC-03 (próstata), HT-29 (cólon), 786-0 (rins), NCI-ADR (mama com fenótipo de resistência a múltiplos fármacos) e linhagem de células normais de ovário de hamster chinês (CHO) in vitro. O extrato e as frações apresentaram citotoxicidade seletiva dose-dependente em células cancerígenas e atividade proliferativa em células normais. A partir das frações de hexano e acetato de etila foram identificados β-amirina, lupeol, β-sitosterol, ácido oleanólico, ácido ursólico, ácido maslínico, ácido corosólico, galato de etila, ácido gálico, quercitrina, miricitrina e quercetina por meio de análises espectrométricas. Estes resultados dão suporte à utilização popular desta espécie e estão provavelmente associados à presença dos flavonóides e triterpenos identificados no extrato. / Plinia edulis (Myrtaceae), an arboreous species popularly known as cambucá, is native in Brazilian Atlantic Rain Forest. Despite its traditional uses in many diseases, which include gastric disorders, no reports are available on the relationship between the biological activities of its extract and its chemical constituents. This thesis reports the evaluations of the the aqueous ethanol extract of leaves of P. edulis and its fractions on gastroprotective effect, antioxidant capacity, cytotoxicity and mutagenicity of. In order to correlate the secondary metabolites and the efficacy of the crude drug in traditional medicine, the extract was submitted to solvent partition followed by chromatographic fractionation. The extract exhibited significant gastroprotective effect on HCl/ethanol-induced ulcers in rats at doses of 100, 200 and 400 mg/kg p.o., even more active than the reference drug lansoprazole. Among the fractions, the hexane fraction (100 mg/kg p.o.) was the most effective, but showed lower activity than the crude extract. In addition, the gastroprotective effect of ursolic acid was evaluated. Although others triterpenes are well known as gastroprotective agents, ursolic acid (50 mg/kg p.o.) reduced the lesion area, but did not show significant activity on this model. The extract did not show mutagenicity at the concentration of 20 mg/plate in the Ames test and exhibited high antioxidant activity, with EC50 of 5.75 µg/mL on the DPPH assay and ORAC value of 3948 µmol Trolox/g of extract. The extract and its fractions were evaluated for cytotoxic activity against human tumour cell lines as UACC62 (melanoma), MCF-7 (breast), NCI 460 (lung, non-small cells), OVCAR03 (ovarian), PC-03 (prostate), HT-29 (colon), 786-0 (renal), NCI-ADR (breast expressing phenotype multiple drugs resistance) and CHO (Chinese Hamster Ovary) normal cell line in vitro. The extract and its fractions showed selectively dose-dependent cytotoxicity against cancer cells and proliferative activity in normal cells. The hexane and ethyl acetate fractions yielded β-amyrin, lupeol, β-sitosterol, oleanolic acid, ursolic acid, maslinic acid, corosolic acid, ethyl gallate, gallic acid, quercitrin, myricitrin and quercetin, which were identified based on spectrometric analyses. These results provide scientific support to the traditional use of this species, which are probably associated with the flavonoids and triterpenoids identified in the extract.

In advanced process control, the Model Predictive Control (MPC) may be considered the most important innovation in recent years and the standard tool for industrial applications due to the fact that it keeps the plant operating in the constraints more profitable. However, like every control algorithm, the MPC after some time in operation rarely works as originally designed. Thus, to preserve the benefits of MPC systems for a long period of time, their performance needs to be monitored and evaluated during the operation. This task require the presence of reliable and effective tools to detect when the controller performance is below of the desirable, to define the need, or not, of recommissioning the system. Thus, the objective of this work is development of techniques for monitoring and evaluating the performance of multivariable predictive controllers, being developed two new tools: LQG benchmark Modified and IHMC benchmark. The results obtained from numerical simulations were satisfactory and consistent with the technical literature applied in the developments of the evaluators, which were used in the monitoring of the control system MPC of the oil-water-gas three-phase separation process, offering an appropriate solution and providing subsidies for implementations in real industrial systems. / Em controle avançado de processos, o controlador preditivo ou MPC (Model Predictive Control) pode ser considerado como a mais importante inovação dos últimos anos e a ferramenta padrão para aplicações industriais, devido ao fato do MPC manter a planta operando dentro das suas restrições de forma mais lucrativa. Entretanto, como todo algoritmo de controle, o MPC depois de algum tempo em operação dificilmente funciona como quando fora inicialmente projetado. Desta forma, com o objetivo de manter os benefícios dos sistemas MPC por um longo período de tempo, seu desempenho precisa ser monitorado e avaliado durante a operação. Esta tarefa requer a presença de ferramentas efetivas e confiáveis para detectar quando o desempenho do controlador estiver abaixo do desejável, para definir a necessidade, ou não, de um recomissionamento do sistema. Destarte, aborda-se neste trabalho o desenvolvimento de técnicas para monitoramento e avaliação de desempenho de controladores preditivos multivariáveis, sendo desenvolvidas duas novas ferramentas: LQG benchmark Modificado e IHMC benchmark. Os resultados obtidos a partir de simulações numéricas foram satisfatórios e coerentes com a literatura técnica aplicada no desenvolvimento dos avaliadores, os quais foram utilizados no monitoramento do sistema de controle MPC do processo de separação trifásica água-óleo-gás, oferecendo assim uma solução apropriada e fornecendo subsídios para implementações em sistemas industrias reais.

Cette étude se situe dans le cadre des recherches menées par le CEAEA sur la production massive d'hydrogène, sans émission de gaz à effet de serre, via un cycle thermo-chimique de décomposition de l'eau couplé à une source de chaleur à haute température d'origine nucléaire. Dans le cas particulier du cycle dit« Iode-Soufre», on doit extraire H2 à partir d'un mélange H2/HI/H20 très corrosif, opération pour laquelle des procédés membranaires ont été proposés. L'objectif de ce travail est le développement de membranes zéolithiques de type MFI susceptibles d'être utilisées dans ce contexte. Nous présentons les différents matériaux utilisés, la méthodologie de synthèse de couches minces de Silicalite-1 et de ZSM-5 synthétisée sans structurant organique, les techniques de caractérisation des membranes. Une étude cinétique nous a permis d'optimiser et de contrôler les conditions d'obtention de ces couches minces déposées sur des substrats tubulaires en Ti02 et plans en Al2O3-α. De nombreuses expériences de perméation ont été réalisées, pour des gaz simples (H2, He, Ar, N 2, C02, SF6) et des mélanges gazeux (H2/H20/Ar) et (H2/H20/HI/Ar). Les effets de la température, de la pression amont, de l'épaisseur et de la longueur de la couche mince ainsi que du gaz vecteur ont été étudiés en détail. Il apparaît que la présence de molécules d'H20 dans le système joue un rôle prépondérant sur la perméation des autres molécules. / In the general context of massive and "carbon free" hydrogen production studies, the aim of this work was the development of zeolitic MFI membranes for hydrogen extraction and separation. The methodology of synthesis, the membranes characterization techniques as well as the permeation experimental setup are presented. Optimization and control of the elaboration of Ti02 supported Silicalite-1 and template free ZSM-5 membranes have been reached. Details of the full kinetic study that we performed are given. Numerous permeation experiments, involving pure gas (H2, He, Ar, N2, C02, SF6) and mixtures (H2/H20/Ar) and (H2/H 20/HI/Ar) have been carried on. The effects of temperature, feed pressure, thickness and length of the membranes, as well as the role of the sweeping gas have been emphasized. In the case of gas mixtures, the presence of H20 molecules appears to be a predominant factor.

Die FEM-MKS-Kopplung erfordert Modellordnungsreduktions-Verfahren, die mit kleiner reduzierter Systemdimension das Übertragungsverhalten mechanischer Strukturen abbilden. Rationale Krylov-Unterraum-Verfahren, basierend auf dem Arnoldi-Algorithmen, ermöglichen solche Abbildungen in frei wählbaren, breiten Frequenzbereichen. Ziel ist der Entwurf einer fehlerüberwachten Modelreduktion auf Basis von Krylov-Unterraumverfahren und Anwendung auf ein strukturmechanisches Model. Auf Grundlage der Software MORPACK wird eine Arnoldi-Funktion erster Ordnung um interpolativen Startvektor, Eliminierung der Starrkörperbewegung und Reorthogonalisierung erweitert. Diese Operationen beinhaltend, wird ein rationales, interpolatives SOAR-Verfahren entwickelt. Ein rationales Block-SOAR-Verfahren erweist sich im Vergleich als unterlegen. Es wird interpolative Gleichwichtung verwendet. Das Arnoldi-Verfahren zeichnet kleiner Berechnungsaufwand aus. Das rationale, interpolative SOAR liefert kleinere reduzierte Systemdimensionen für gleichen abgebildeten Frequenzbereich. Die Funktionen werden auf Rahmen-, Getriebegehäuse- und Treibsatzwellen-Modelle angewendet. Zur Fehlerbewertung wird eigenfrequenzbasiert ein H2-Integrationsbereich festgelegt und der übertragungsfunktionsbasierte, relative H2-Fehler berechnet. Es werden zur Lösung linearer Gleichungssysteme mit Matlab entsprechende Löser-Funktionen, auf Permutation und Faktorisierung basierend, implementiert.:1. Einleitung 1.1. Motivation 1.2. Einordnung 1.3. Aufbau der Arbeit 2. Theorie 2.1. Simulationsmethoden 2.1.1. Finite Elemente Methode 2.1.2. Mehrkörpersimulation 2.1.3. Kopplung der Simulationsmethoden 2.2. Zustandsraumdarstellung und Reduktion 2.3. Krylov Unterraum Methoden 2.4. Arnoldi-Algorithmen erster Ordnung 2.5. Arnoldi-Algorithmen zweiter Ordnung 2.6. Korrelationskriterien 2.6.1. Eigenfrequenzbezogene Kriterien 2.6.2. Eigenvektorbezogene Kriterien 2.6.3. Übertragungsfunktionsbezogene Kriterien 2.6.4. Fehlerbewertung 2.6.5. Anwendung auf Systeme sehr großer Dimension 3. Numerik linearer Gleichungssysteme 3.1. Grundlagen 3.2. Singularität der Koeffizientenmatrix 3.2.1. Randbedingungen des Systems 3.2.2. Verwendung einer generellen Diagonalperturbation 3.3. Iterative Lösungsverfahren 3.4. Faktorisierungsverfahren 3.4.1. Cholesky-Faktorisierung 3.4.2. LU-Faktorisierung 3.4.3. Fillin-Reduktion durch Permutation 3.4.4. Fazit 3.5. Direkte Lösungsverfahren 3.6. Verwendung externer Gleichungssystem-Löser 3.7. Zusammenfassung 4. Implementierung 4.1. Aufbau von MORPACK 4.2. Anforderungen an Reduktions-Funktionen 4.3. Eigenschaften und Optionen der KSM-Funktionen 4.3.1. Arnoldi-Funktion erster Ordnung 4.3.2. Rationale SOAR-Funktionen 4.4. Korrelationskriterien 4.4.1. Eigenfrequenzbezogen 4.4.2. Eigenvektorbezogen 4.4.3. Übertragungsfunktionsbezogen 4.5. Lösungsfunktionen linearer Gleichungssysteme 4.5.1. Anforderungen und Aufbau 4.5.2. Verwendung der Gleichungssystem-Löser 4.5.3. Hinweise zur Implementierung von Gleichungssystem-Lösern 5. Anwendung 5.1. Versuchsmodelle 5.1.1. Testmodelle kleiner Dimension 5.1.2. Getriebegehäuse 5.1.3. Treibsatzwelle 5.2. Validierung der Reduktionsmethoden an kleinem Modell 5.2.1. Modifizierte Arnoldi-Funktion erster Ordnung 5.2.2. Rationale SOAR-Funktionen 5.2.3. Zusammenfassung 5.3. Anwendung der KSM auf große Modelle 5.3.1. Getriebegehäuse 5.3.2. Treibsatzwelle 5.4. Auswertung 6. Zusammenfassung und Ausblick 6.1. Zusammenfassung 6.2. Ausblick / FEM-MKS-coupling requires model order reduction methods to simulate the frequency response of mechanical structures using a smaller reduced representation of the original system. Most of the rational Krylov-subspace methods are based on Arnoldi-algorithms. They allow to represent the frequency response in freely selectable, wide frequency ranges. Subject of this thesis is the implementation of an error-controlled model order reduction based on Krylov-subspace methods and the application to a mechanical model. Based on the MORPACK software, a first-order-Arnoldi function is extended by an interpolative start vector, the elimination of rigid body motion and a reorthogonalization. Containing these functions, a rational, interpolative Second Order Arnoldi (SOAR) method is designed that works well compared to a rational Block-SOAR-method. Interpolative equal weighting is used. The first-order-Arnoldi method requires less computational effort compared to the rational, interpolative SOAR that is able to compute a smaller reduction size for same frequency range of interest. The methods are applied to the models of a frame, a gear case and a drive shaft. Error-control is realized by eigenfrequency-based H2-integration-limit and relative H2-error based on the frequency response function. For solving linear systems of equations in Matlab, solver functions based on permutation and factorization are implemented.:1. Einleitung 1.1. Motivation 1.2. Einordnung 1.3. Aufbau der Arbeit 2. Theorie 2.1. Simulationsmethoden 2.1.1. Finite Elemente Methode 2.1.2. Mehrkörpersimulation 2.1.3. Kopplung der Simulationsmethoden 2.2. Zustandsraumdarstellung und Reduktion 2.3. Krylov Unterraum Methoden 2.4. Arnoldi-Algorithmen erster Ordnung 2.5. Arnoldi-Algorithmen zweiter Ordnung 2.6. Korrelationskriterien 2.6.1. Eigenfrequenzbezogene Kriterien 2.6.2. Eigenvektorbezogene Kriterien 2.6.3. Übertragungsfunktionsbezogene Kriterien 2.6.4. Fehlerbewertung 2.6.5. Anwendung auf Systeme sehr großer Dimension 3. Numerik linearer Gleichungssysteme 3.1. Grundlagen 3.2. Singularität der Koeffizientenmatrix 3.2.1. Randbedingungen des Systems 3.2.2. Verwendung einer generellen Diagonalperturbation 3.3. Iterative Lösungsverfahren 3.4. Faktorisierungsverfahren 3.4.1. Cholesky-Faktorisierung 3.4.2. LU-Faktorisierung 3.4.3. Fillin-Reduktion durch Permutation 3.4.4. Fazit 3.5. Direkte Lösungsverfahren 3.6. Verwendung externer Gleichungssystem-Löser 3.7. Zusammenfassung 4. Implementierung 4.1. Aufbau von MORPACK 4.2. Anforderungen an Reduktions-Funktionen 4.3. Eigenschaften und Optionen der KSM-Funktionen 4.3.1. Arnoldi-Funktion erster Ordnung 4.3.2. Rationale SOAR-Funktionen 4.4. Korrelationskriterien 4.4.1. Eigenfrequenzbezogen 4.4.2. Eigenvektorbezogen 4.4.3. Übertragungsfunktionsbezogen 4.5. Lösungsfunktionen linearer Gleichungssysteme 4.5.1. Anforderungen und Aufbau 4.5.2. Verwendung der Gleichungssystem-Löser 4.5.3. Hinweise zur Implementierung von Gleichungssystem-Lösern 5. Anwendung 5.1. Versuchsmodelle 5.1.1. Testmodelle kleiner Dimension 5.1.2. Getriebegehäuse 5.1.3. Treibsatzwelle 5.2. Validierung der Reduktionsmethoden an kleinem Modell 5.2.1. Modifizierte Arnoldi-Funktion erster Ordnung 5.2.2. Rationale SOAR-Funktionen 5.2.3. Zusammenfassung 5.3. Anwendung der KSM auf große Modelle 5.3.1. Getriebegehäuse 5.3.2. Treibsatzwelle 5.4. Auswertung 6. Zusammenfassung und Ausblick 6.1. Zusammenfassung 6.2. Ausblick

Anhand einer Fallstudie wird die Arbeit mit dem von der Freiberg Institut für Energie und Klimaökonomie GmbH erschaffenen H2-Tankstellen-Konfigurators dargestellt. Durch die Variation der Wasserstoffversorgung einer fiktiv geplanten H2-Tankstelle wird verdeutlicht, wie die Optimierungssoftware Edgar die Dimensionierung der Anlagentechnik für eine optimale Konfiguration und minimale Kosten verändert. / A case study is used to illustrate the work with the H2 filling station configurator created by the Freiberg Institute for Energy and Climate Economics GmbH. By varying the hydrogen supply of a fictitiously planned H2 filling station, it is illustrated how the optimization software Edgar changes the dimensioning of the plant technology for an optimal configuration and minimal costs.

Based on a comparative method of enquiry, this thesis analyses the process of self-definition expressed in the work of Gloria Fuertes (Madrid, 1917-1998) and Pilar Paz Pasamar (Jerez de la Frontera, 1933) as individual alternatives to the collective ethos and literary practices promoted within the patriarchal society of Franco’s Spain. Recognizing the poets’ cultural and socio-political context as determining factors in their experiences as women and poets, and therefore in their outlook and poetics, this context and how it is reflected in their poetry provides the starting point (Chapter 1). Both poets acknowledge that writing poetry can provide them with a metaphorical space of freedom that enables them to develop their identity and explore their preoccupations. Therefore, their thoughts about poetry provide an important theme that occurs in the poetry of both (Chapter 2). Closely related to this is the link they establish between poetic inspiration and the divine, which in the case of Pilar Paz Pasamar leads to the attempt to use the special qualities of poetic language to refer to a universal truth that she is aware of and which transcends the capabilities of language, while Gloria Fuertes regards poetry as a divine gift that can provide solace and is ultimately able to improve the world (Chapter 3). The fourth chapter focuses on specific elements of the two poets’ work that reveal the distinctive mechanisms of self-construction they develop. The section on Fuertes considers humour as a survival strategy that enables the poet to reach out to her readership and emphasize her focus on the here and now, while the discussion on Paz’s work looks at how the use of sea imagery allows her to convey abstract experiences based on introspection. Thus, it is argued that their poetry reflects the different strategies the two women develop – based on integration in the case of Fuertes and a more separate position in the case of Paz – to define themselves in relation to their world.

The detection of low-mass extra-solar planets through radial-velocity searches is currently limited by the intrinsic magnetic activity of the host stars. The correlated noise that arises from their natural radial-velocity variability can easily mimic or conceal the orbital signals of super-Earth and Earth-mass extra-solar planets. I developed an intuitive and robust data analysis framework in which the activity-induced variations are modelled with a Gaussian process that has the frequency structure of the photometric variations of the star, thus allowing me to determine precise and reliable planetary masses. I applied this technique to three recently discovered planetary systems: CoRoT-7, Kepler-78 and Kepler-10. I determined the masses of the transiting super-Earth CoRoT-7b and the small Neptune CoRoT-7c to be 4.73 ± 0.95 M⊕ and 13.56 ± 1.08 M⊕, respectively. The density of CoRoT-7b is 6.61 ± 1.72 g.cm⁻³, which is compatible with a rocky composition. I carried out Bayesian model selection to assess the nature of a previously identified signal at 9 days, and found that it is best interpreted as stellar activity. Despite the high levels of activity of its host star, I determined the mass of the Earth-sized planet Kepler-78b to be 1.76 ± 0.18 M⊕. With a density of 6.2(+1.8:-1.4) g.cm⁻³, it is also a rocky planet. I found the masses of Kepler-10b and Kepler-10c to be 3.31 ± 0.32 M⊕ and 16.25 ± 3.66 M⊕, respectively. Their densities, of 6.4(+1.1:-0.7) g.cm⁻³ and 8.1 ± 1.8 g.cm⁻³, imply that they are both of rocky composition – even the 2 Earth-radius planet Kepler-10c! In parallel, I deepened our understanding of the physical origin of stellar radial-velocity variability through the study of the Sun, which is the only star whose surface can be imaged at high resolution. I found that the full-disc magnetic flux is an excellent proxy for activity-induced radial-velocity variations; this result may become key to breaking the activity barrier in coming years. I also found that in the case of CoRoT-7, the suppression of convective blueshift leads to radial-velocity variations with an rms of 1.82 m.s⁻¹, while the modulation induced by the presence of dark spots on the rotating stellar disc has an rms of 0.46 m.s⁻¹. For the Sun, I found these contributions to be 2.22 m.s⁻¹ and 0.14 m.s⁻¹, respectively. These results suggest that for slowly rotating stars, the suppression of convective blueshift is the dominant contributor to the activity-modulated radial-velocity signal, rather than the rotational Doppler shift of the flux blocked by starspots.

PALEOFLUID CHEMISTRY OF OROGENIC GOLD DEPOSITS: NOVEL ANALYTICAL METHODS AND CASE STUDIES FROM THE BOHEMIAN MASSIF Tomáš Hrstka1 1 Charles University in Prague, Faculty of Science, Institute of Geochemistry, Mineralogy and Mineral Resources, Albertov 6, Praha 2, CZ-128 43 Abstract of the Ph.D. Thesis Fluid inclusions represent a unique tool for understanding the processes leading to the formation of mineral deposits and fluid-rock interactions in general. Orogenic gold deposits in the central part of the Bohemian Massif (Libčice and Kasejovice deposits) were studied in order to provide a better understanding of their genesis. A multifaceted approach was adopted including a broad spectrum of micro-analytical methods. While traditional methods were used as the basis of this study (e.g., microthermometry, SEM and optical microscopy), the application and improvement/development of modern analytical methods (e.g., LA-ICP- MS and Raman spectroscopy) or introduction of alternative innovative techniques (CLSM, Nano- tomography, QEMSCAN) constituted a significant part of this study. This study reveals the importance of the HCO3 - species in hydrothermal fluids (i.e., >100 řC to ~350 řC). Previously, the prevalence of Cl- and other anions was reported for hydrothermal paleofluids and the majority of studies suggested...

Ce travail experimental est consacre a l'etude de la multiplicite des electrons secondaires emis par des cibles minces de carbone bombardees par des protons, des atomes H0 et des ions moleculaires H2+ et H3+ d'energie variant de 0.25 a 2.2 MeV.<br /><br /> Le phenomene d'emission electronique secondaire par les surfaces des solides a l'impact de projectiles rapides resulte des interactions inelastiques des projectiles avec les electrons du solide. Une description phenomenologique te un rappel des differents modeles theoriques sont rassembles dans un premier chapitre.<br /><br /> Le second chapitre est consacre a la description du dispositif experimental utilise pour la mesure evenement par evenement du nombre d'electrons emis par les deux faces d'une cible mince de carbone lors du passage des projectiles incidents. Le traitement informatique des donnees experimentales, necessaire a la determination des distributions statistiques des electrons emis est egalement presente.<br /><br /> L'emission electronique induite par des atomes H0 a ete mesuree en correlation avec l'etat de charge des projectiles emergeant des cibles minces. Ces experiences, dont les resultats sont presentes dans le chapitre trois, nous ont permis de montrer le role particulier de l'electron d'un projectile selon qu'il reste ou non lie au projectile.<br /><br /> Le chapitre quatre est consacre a l'emission electronique induite par des ions polyatomiques H2+ et H3+. Les resultats sont intepretes en termes d'effets collectifs dans les interactions de tels ions avec les solides. le role de la proximite des protons, fragments des ions moleculaires, sur l'amplitude de ces effets collectifs est montre a partir des distributions statistiques des electrons secondaires emis par la face d'emergence des cibles.<br /><br /> Ces experiences ont permis de mettre en evidence des aspects particuliers des interactions d'atomes et d'ions polyatomiques avec les solides.

Nous avons analysé le rôle joué dans les processus de détection, par des agrégats métalliques de Pt et de Pd dispersés dans des films minces de SnO2 destinés à la détection des gaz polluants réducteurs comme le CO, H2S ou NOx. L'évolution de l'état d'oxydation des agrégats de platine a été suivie par Spectroscopie d'Absorption X (XAS) in situ. Lorsqu'elles sont incorporées en quantité très faible, les particules de platine changent, d'une façon réversible, leur état d'oxydation, selon la nature de l'atmosphère environnante. L'état d'oxydation des particules dépend fortement de leur taille, (entre 0,5 et 4,5 nm) les plus petites passant d'un état complètement oxydé à un état fortement réduit -les liaisons Pt - O laissant place à des Pt - C lorsque les films sont en présence de CO. L'évolution de la conductance électrique lorsque les films sont mis en présence de CO a été corrélée à la rapidité de la réaction du réduction de platine. Une interaction électronique métal-SnO2 est à l'origine du pic de conductance observé à basse température. Une étude comparative des réponses électriques des couches platinées et dopées palladium, en présence de CO, H2 et H2S, a permis de proposer différents mécanismes de détection relatifs à chacun des gaz étudiés.