La caractérisation des ions multichargés dans le plasma d'une source ECR utilise comme moyen de diagnostic non perturbatif la spectroscopie dans le domaine de l'ultraviolet sous vide. Dans ce type de source, les électrons sont chauffés par interaction avec une onde HF et confinés magnétiquement par effet miroir. Les électrons interagissent avec l'onde HF à la résonance cyclotronique au cours de leurs allers et retours successifs dans le miroir magnétique. Ils acquièrent ainsi l'énergie nécessaire pour dépasser les potentiels d'ionisation de chacun des états de charge de l'élément injecté dans la source. L'amélioration des performances d'une source ECR en courant d'ions extraits et en états de charge obtenus passe par la connaissance des grandeurs physiques fondamentales des espèces présentes dans le plasma. Le but de la spectroscopie V.U.V. est de déterminer la densité et la température électronique d'une part et la densité et le temps de confinement des ions d'autre part. Nous avons utilisé des galettes de micro canaux comme détecteurs de position sur un spectromètre à incidence rasante muni d'un réseau de 3 mètres de rayon de courbure comportant 600 traits/mm. On effectue l'étalonnage en intensité de l'ensemble réseau-détecteur par 2 méthodes. Ce sont les méthodes des rapports de branchement et d'échanges de charge. L'identification des raies émises par le plasma qui regroupe l'ensemble des états de charge possibles de l'élément étudié est nécessaire pour faire une étude exhaustive de l'état du plasma. Finalement, la détermination des paramètres du plasma sur la base théorique de 2 sources ECR disponibles au laboratoire a été réalisée pour la première fois.

<p>Gold nanoparticles exhibit remarkable optical properties and could prove useful in sensitive biosensing applications. Upon illumination gold nanoparticles produce localized surface plasmons, which influence nearby fluorophores and an enhancement in their fluorescence intensity can be observed. This property makes gold nanoparticles attractive for enhancing optical signals.</p><p>In this project gold nanoparticles were functionalized with an antibody and immobilized to the surface of an existing biochip platform based on fluorescence. The aim was to investigate the possibility of obtaining an increased fluorescence signal from the gold nanoparticles. Two different conjugation procedures were investigated, direct physisorption and covalent attachment of the antibodies to the particles. Activity of bound antibodies was confirmed in both cases.</p><p>The on-chip fluorescence intensity produced by the different conjugates was monitored by use a specialized fluorescence reader designed for point-of-care use. AFM and SEM were used to determine the surface concentration of particles. A correlation between the produced fluorescence intensity and the surface concentration could be seen.</p>

Gold nanoparticles exhibit remarkable optical properties and could prove useful in sensitive biosensing applications. Upon illumination gold nanoparticles produce localized surface plasmons, which influence nearby fluorophores and an enhancement in their fluorescence intensity can be observed. This property makes gold nanoparticles attractive for enhancing optical signals. In this project gold nanoparticles were functionalized with an antibody and immobilized to the surface of an existing biochip platform based on fluorescence. The aim was to investigate the possibility of obtaining an increased fluorescence signal from the gold nanoparticles. Two different conjugation procedures were investigated, direct physisorption and covalent attachment of the antibodies to the particles. Activity of bound antibodies was confirmed in both cases. The on-chip fluorescence intensity produced by the different conjugates was monitored by use a specialized fluorescence reader designed for point-of-care use. AFM and SEM were used to determine the surface concentration of particles. A correlation between the produced fluorescence intensity and the surface concentration could be seen.

Le sujet de la thèse initié dans le cadre de l'ANR UV-Borate s'inclut dans le projet UV-Conversion labellisée par 2 pôles de compétitivité (Matériala - Lorraine - et Route des lasers - Aquitaine -) soumis à l'ANR en 2011. Les études se portent particulièrement sur les borates YxLaySc4-(x+y)(BO3)4 (LYSB) et YAl3(BO3)4 (YAB), cristaux Optiques Non Linéaires (ONL) possédant la même structure cristallographique (R32). La croissance de ces cristaux est effectuée par les collaborateurs industriels et universitaires de l'ANR. Ces deux matériaux présentent en effet des possibilités de conversion de fréquence jusqu'à des longueurs d'onde λ < 300 nm, de plus une non hygroscopicité procure une plus grande durée de vie des échantillons et par conséquent un net intérêt pour les applications industrielles. L'endommagement laser étant lié à l'absorption et ainsi, en partie, aux impuretés, une étude de la qualité cristalline et de l'homogénéité de nos cristaux a été effectuée. Les résultats ont permis de relier des défauts de structure (dislocations et etch pits) à la croissance de la maille rhomboédrique via des caractérisations par ombre portée (Photography Schlieren) et par attaque chimique suivi d'une observation par microscopie optique, MEB et MFA. Par ailleurs, des études théoriques et expérimentales d'accord de phase (détermination de θ et φ) lors de conversions de type I principalement ont été réalisées sur les cristaux de YAB, LYSB ainsi que sur des cristaux de référence tel que β-BaB2O4 (β-BBO). L'aspect de l'endommagement laser dans les matériaux ONL a été abordé dans les locaux de l'Institut Fresnel de Marseille au sein de l'équipe Interaction Laser Matière (ILM) sur des échantillons de Li2B4O7 (LTB). L'équipe a effectivement développé un dispositif de mesure de la probabilité d'endommagement laser et de mesure de tenue du seuil d'endommagement laser des matériaux optiques. Par ailleurs, un effort a été mené dans la conception d'un dispositif de mesure de la transmission optique et absorption à température ambiante et aux basses températures afin de révéler des défauts absorbants. Des premiers résultats ont été obtenus et discutés sur des échantillons de β-BBO et LYSB.

The synergistic effect of nitric oxide toward dephosphorylation reactions involving phosphate esters was the subject of investigation in this research. Sodium nitroprusside under UV irradiations at 254nm, 365nm and white light was utilized as nitric oxide donor in solutions. The effects of cobalt trimethylenediamine and nitroprusside towards dephosphorylation of nitrophenylphosphate and pyrophosphate which were modeled as organophosphate ester substrates were also investigated. The activated substrate models showed more rate enhancement than the unactivated models in all cases. The direct interaction of nitric oxide with the phosphorus centre is presumed to be the reason for enhanced hydrolysis. This study demonstrates the possible role of nitric oxide in decontamination reactions of poorly biodegradable phosphate esters in the biosphere. / Chemistry / M. Sc. (Chemistry)

Des oxydes semi-conducteurs, en particulier TiO2 commercialement disponible ou des échantillons mésoporeux synthétisés, ont été testés comme photocatalyseurs de l'oxydation ménagée et aérobie d'alcools dans l'acétonitrile sous UV. L'alcool benzylique a été oxydé principalement en benzaldéhyde (rendement = 60%) en présence de TiO2-P25. Malheureusement, ce catalyseur tend à se désactiver. Le rôle du dioxygène dans le processus d'oxydation a été souligné après avoir testé différents solvants. Les alcools aliphatiques ont également été étudiés. Ainsi, le cyclohexanol a donné principalement de la cyclohexanone (rendement = 70%). Parallèlement, une approche colloïdale a été développée pour déposer les nanoparticules d'oxyde de titane sur des supports de silice mésoporeux SBA-15 transparents aux UV afin d'éviter les phénomènes d'agrégation lors des tests. Après optimisation de leur synthèse (quantité d'eau, nature de l'acide et de l'alcool), des nanoparticules sphériques non cristallines stables de 5 nm de diamètre ont été obtenues. En utilisant la méthode d'imprégnation à "deux solvants", ces dernières ont été introduites avec succès dans les mésopores de deux échantillons de SBA-15, l'un avec un diamètre moyen des pores de 6 nm, l'autre de 8. Les analyses MET ont souligné que le matériau SBA-15 avec les pores les plus grands a conduit à l'incorporation de davantage de nanoparticules. A priori, les interactions silice / oxyde de titane dans les matériaux résultants semblent favorables puisque les quantités inférieures de TiO2 dans les tests de photocatalyse correspondants ont conduit à de meilleurs taux de conversion que ceux obtenus avec P25 ou la suspension mère de colloïdes. / A series of metal oxides semiconductors, including commercially available TiO2 or synthesized mesoporous samples, were tested as photocatalysts for the aerobic mild oxidation of alcohols in acetonitrile under UV. Benzyl alcohol, used as a reference, was oxidized mainly into benzaldehyde. Best yield (60%) was obtained with TiO2-P25. Unfortunately, this catalyst tended deactivate with time. The role of dioxygen solubility in the oxidation process was emphasized through the test of different solvents. Aliphatic alcohols were also studied. Among them, cyclohexanol gave mainly cyclohexanone with a yield of 70%. Parallely, a colloidal approach was developed for the deposition of titanium oxide nanoparticles on UV transparent mesoporous silica supports in order to take advantage of their important specific surface area and avoid aggregation phenomena during the photocatalysis tests. After optimizing the synthesis protocol (amount of water, nature of the acid and alcohol), spherical, non-crystalline stable nanoparticles with 5 nm diameter were obtained. Using the “two-solvents” impregnation method, these particles were successfully introduced in the mesopores of two SBA-15 silica samples differing by their mean pore diameter (either 6 or 8 nm). TEM measurements emphasized that the SBA-15 material with the largest pores led to the incorporation of more nanoparticles in its mesopores. Clearly, silica/ titanium dioxide interactions in the resulting materials appeared to play a positive role since lower amounts of TiO2 in the corresponding photocatalysis tests led to improved conversion rates of benzylalcohol compared to those performed with P25 or the parent suspension of colloids.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Sitagliptin Phosphate is an oral anti-hyperglycemic belonging to a new class of medicine used in type 2 diabetes treatment, the dipeptidyl dipetidase -4 (DPP-4) enzyme inhibitors. This drug besides being safe and tolerated, stimulates the insulin secretion, lowers the glucagon release, delays the gastric emptiness and increases beta cells life. It is commercially available as covered pills. So far, there is not any monograph to analyze sitagliptin phosphate in its pharmaceutical form. In this work some methods were developed and validated to evaluate and quantify the drug. The methods used to quantify it were high pressure efficiency liquid chromatography (HPLC) and spectrophotometry. The system through HPLC was carried out in room temperature and in an isocratic way with Phenomenex C 18 (15 cm x 4.6mm) reverse phase column and the mobile phase composed by 0.025M pH 6.8 phosphate buffer: acetronytril (60:40, v/v) with 0.8 mL /min. flow. The detection was accomplished in PDA in 267nm. With the spectrophotometric method the solvent used was HCI 0.01N and its detection was accomplished in 267nm wave length. The methods show a good linearity, precision and accuracy and having no significant difference between them. Later, some dissolution tests were carried out with different bacthes of drug and with similar results. / O Fosfato de sitagliptina é um anti-hiperglicemico oral pertencente a uma nova classe de medicamentos utilizados para o tratamento da diabete tipo 2, os inibidores da enzima dipeptidil dipetidase-4 (DPP-4). Este medicamento além de ser seguro e bem tolerado estimula a secreção de insulina, diminuí a liberação de glucagon, retarda o esvaziamento gástrico e prolonga a vida das células beta. Encontra-se comercialmente disponível na forma de comprimidos revestidos. Não existem monografias até o presente momento para a análise do fosfato de sitagliptina em sua forma farmacêutica. Neste trabalho foram desenvolvidos e validados métodos para a avaliação e quantificação do fármaco. Os métodos utilizados para a quantificação do fármaco foram à cromatografia liquida de alta eficiência (CLAE) e a espectrofotometria. O sistema por CLAE foi realizado em temperatura ambiente e de maneira isocrática com coluna de fase reversa Phenomenex C18 (15cm x 4.6mm) e fase móvel composta por tampão fosfato 0.025M pH 6.8 : acetonitrila (60:40, v/v) com vazão de 0.8mL/min. A detecção foi realizada no PDA em 267nm. No método espectrofotométrico o solvente utilizado foi o HCl 0.01N e sua detecção foi realizada no comprimento de onda de 267nm. Os métodos mostram boa linearidade, precisão e exatidão e não demonstraram diferença significativa entre eles. Posteriormente foram realizados testes de dissolução com resultados semelhantes com medicamentos de diferentes lotes.

No description available.

Ten-millijoule, thirty-five femtosecond, 800 nm (~40 nm bandwidth) laser pulses are used to study high-order harmonic generation in helium- and neon-filled gas cells of various lengths. Harmonic orders in the range of 50 to 100 are investigated. A semi-infinite cell geometry produces brighter harmonics than cells of sub-centimeter length. In the semi-infinite geometry, the gas occupies the region from the focusing lens to a thin exit foil near the laser focus. Counter-propagating light is used to directly probe where the high harmonics are generated within the laser focus and to investigate phase matching. The phase matching under optimized harmonic generation conditions was found to be unexpectedly good with phase zones many millimeters long. Restricting the laser beam with an 8 mm aperture in front of the focusing lens increases the emission of most harmonic orders observed by as much as an order of magnitude. Optimal harmonic generation pressures were found to be about 55 torr in neon and 110 torr in helium. The optimal position of the laser focus was found to be a few millimeters inside the exit foil of the gas cell. Probing with counter-propagating light reveals that in the case of neon the harmonics are generated in the last few millimeters before the exit foil. In helium, the harmonics are produced over a longer distance. Direct measurement shows that the re-absorption limit for mid-range harmonics in neon has been reached.

Cardiovascular diseases (CVDs) are a leading cause of death worldwide, emphasizing the need for advanced and effective intervention and treatment measures. Hypertension, a significant risk factor for CVDs, is characterized by reduced vascular compliance in arterial vessels. There is a significant rise in interest in exploring the viscoelastic properties of arteries in the last few years, for the treatment of these diseases. This study aims to develop an experimental setup using 3D Printing Technology to test viscoelastic arterial models for the validation of a diagnostic device for cardiovascular diseases. The research investigates the selection of polymer-based materials that closely mimic the viscoelastic properties of arterial vessels. An experimental setup is designed and fabricated to perform mechanical tests on 3D-printed specimens. The study utilizes a mathematical model to describe the viscoelastic behavior of the materials. The model's predictions are validated using experimental data obtained from the mechanical tests. This study demonstrates the potential of 3D printing technology in fabricating specimens using elastic and flexible resin materials. These specimens closely replicate the mechanical properties of native arteries, offering a tangible platform for controlled mechanical testing. Stress relaxation tests on the3D printed specimens highlight the viscoelastic properties of fabricated materials, shedding light on their behavior under strain. The study goes further to model the mechanics of these materials, utilizing the Fractional Voigt model to capture the intricate balance between elastic and resistive behaviors under varying deformation levels. The results highlight the successful fitting of the Fractional Voigt model to the experimental data, confirming the viscoelastic behavior of the specimens. The obtained values of α and RMSE indicate a good representation of arterial mechanical properties within the viscoelastic arterial model, under different loading conditions. This research contributes to improving cardiovascular device validation and offers a practical and reliable alternative to invasive experiments. Future works include exploring different materials and conditions for arterial modeling and enhancing the precision and scope of the viscoelastic model. Overall, this study advances the understanding of cardiovascular biomechanics, contributing to the development of more effective diagnostic devices for cardiovascular diseases.