Suspensões coloidais de microesferas de poliestireno carregadas proporcionam um sistema experimental excelente para estudar muitos problemas em física da matéria condensada. Sob condições apropriadas as partículas nessas suspensões podem se auto-organizar em um cristal com ordem de longo alcance, o chamado cristal coloidal. Neste trabalho apresentamos resultados de simulações por Dinâmica Molecular relacionados a defeitos pontuais, vacâncias e interstícios, em um cristal coloidal 2D. Calculamos a energia de formação e a interação destes defeitos pontuais, mostrando que um interstício é mais provável de ser criado do que uma vacância e que a interação entre os defeitos (vacância-vacância e interstício-interstício) é atrativa. Em conjunto esses resultados apontaram que os defeitos pontuais podem afetar o mecanismo de fusão do cristal coloidal 2D. Com relação à dinâmica dos defeitos, o foco foi sobre as vacâncias. Calculamos as entalpias de migração deste defeito de uma forma original, baseada na troca de topologias. Concluímos que a vacância não difunde de acordo com um único mecanismo, mas sim um misto de dois comportamentos, são eles: relação de Arrhenius corrigida e relação de potência com a temperatura. Calculamos também as entalpias e entropias relativas de formação das topologias da vacância, o que possibilitou identificar as topologias mais estáveis. Acreditamos que esses resultados serão importantes para trabalhos experimentais envolvendo interfaces e superfícies sólidas. / Colloidal suspensions of charged polystyrene microspheres provide an excellent experimental system to study many problems in condensed matter physics. Under appropriate conditions the particles in these suspensions organize themselves in a long-range-ordered crystal, the so-called colloidal crystal. In this thesis we report Molecular Dynamics simulations on point defects, vacancies and interstitials, in a 2D colloidal crystal. We have calculated the formation energy and interaction of these point defects, as well as the energy barriers between the various topological configurations that the defects may adopt while in thermal equilibrium. It is shown that the interstitials are more likely to be formed than the vacancies, and the interaction between defects (vacancy-vacancy and interstitial-interstitial) is attractive. Taken together, these results indicate that point defects may affect the melting process of a 2D colloidal crystal. With regard to the dynamics of the defects, emphasis was placed on the vacancies. The enthalpy for migration of a vacancy was calculated on the basis of exchanges between topologies. We concluded that the vacancy does not diffuse according to a single mechanism, but rather through a mixture of two processes: one is a modified Arrhenius mechanism and the other is represented by a power-law dependence on the temperature. We also calculated the relative enthalpies and entropies associated with the formation of the different topologies of vacancies, which allowed identification of the most stable topologies. We believe these results may have important bearing on experimental works involving interfaces and solid surfaces.

A utilização de nanopartículas magnéticas em biomedicina e biotecnologia vem recebendo elevado destaque nos últimos anos, graças à versatilidade de aplicações como reparo de tecidos, diagnósticos, ressonância magnética por imagem, tratamento contra o câncer, separação celular, transporte controlado de drogas, entre outras. Atualmente, as nanopartículas com potencialidade de aplicação em biomedicina se restringem aos óxidos magnéticos de ferro, os quais apresentam comportamento superparamagnético a temperatura ambiente e magnetização da ordem de 300 emu/cm3. Entretanto, há necessidade inerente da funcionalização da superfície para possibilitar aplicações biomédicas tornando as nanopartículas biocompatíveis e/ou biosseletivas. Essa funcionalização adicional é obtida geralmente introduzindo camadas de materiais diamagnético e/ou paramagnéticos na superfície das NP, as quais baixam a eficiência das propriedades magnéticas exigindo o desenvolvimento de núcleos com elevado valor de magnetização de saturação. Desta forma, nesse trabalho foram sintetizadas nanopartículas magnéticas metálicas de FePt recobertas com óxido de ferro obtidas via processo poliol modificado combinado com a metodologia de crescimento mediado por sementes. Os núcleos magnéticos como-sintetizados foram recobertos com uma camada de sílica, seguido pelo recozimento em atmosfera redutora para elevar o valor da magnetização de saturação. Em seguida, sobre a superfície de sílica foram ancoradas moléculas luminescentes de rodamina B com o auxílio de moléculas de APTES atuando como grupo sililante e as NP resultantes foram novamente recobertas com uma fina camada de sílica. Os resultados permitem concluir que foi obtido um sistema bifuncional combinando em uma única nanopartícula a possibilidade de sensoriamento óptico e magnético, além de possuir sua magnetização de saturação intensificada cerca de 10 vezes em relação aos óxidos metálicos (64 emu/g), manter o caráter superparamagnético e possuir superfície biocompatível com possibilidades de funcionalizações adicionais, com grande potencial para aplicações em biomedicina. / In recent years, the magnetic nanoparticles uses in many biomedical and biotechnological areas have received great attention due to their several applications possibilities such as: tissue repair, diagnostics, magnetic resonance imaging, cancer treatment, cell separation, and controlled drug delivery, among others. Today, the potential magnetic nanoparticles applications are limited to magnetic iron oxides uses, which exhibit superparamagnetic behavior at room temperature and low saturation magnetization around 300 emu/cm3. However, for biomedical applications, the nanoparticle surface must be properly functionalized in order to confer biocompatibility and biosselectivity. These additional functionalizations are generally obtained by paramagnetic and/or diamagnetic materials incorporations onto the nanoparticle surface leading a dramatic decreasing in the already low saturation magnetization. In this context, the development of new magnetic nuclei with high magnetizations values is required. Thus, in this work iron oxide-coated metallic FePt magnetic nanoparticles were synthesized by using the modified polyol process combined with the seed mediated growth method. The magnetic as-synthesized nuclei were coated with a thin silica shell followed by thermal annealing under reducing atmosphere in order to increase the saturations magnetization of this material. After that, onto the silica-coated magnetic nanoparticles surface luminescent dye Rhodamine B molecules were supported using the APTES as intermediate sililant molecules. Then, the functionalized nanoparticles were coated again with an outer layer. In conclusion, according to the obtained results, a bifunctional system combining the optical and magnetic sensing in the same nanoparticle was reported. The obtained nanoparticles present superparamagnetic behavior and high saturation magnetization around 10 times higher (~64 emu/g) compared with the iron oxide nanoparticles synthesized at the same conditions. In addition, the luminomagnetic nanoparticle surface is biocompatible allowing additional future functionalizations with high potential to biomedical applications.

Per via degli svantaggi inerenti l’uso di bentonite nella produzione di vini bianchi, la ricerca di alternative ha assunto di recente una grande importanza. Il lavoro presentato in questa tesi ha l’obiettivo di valutare l’applicabilità di tre approcci innovativi alla stabilizzazione colloidale dei vini: l’uso di chitosano, l’applicazione dei PEF e il riutilizzo di colonne di scambio cationico. L’aggiunta di chitosano è risultata nella rimozione delle chitinasi dal vino, permettendo di raggiungere un soddisfacente livello di stabilità. Gli effetti sul colore e sugli aromi, quando non significativi, non sono risultati essere peggiori rispetto ai risultati ottenuti da trattamenti con bentonite. L’applicazione dei PEF aveva lo scopo di innescare la denaturazione e l’aggregazione delle proteine tramite un sistema di trattamento-raffreddamento e filtrazione finale. I risultati suggeriscono che un buon grado di stabilità viene raggiunto solo con trattamenti particolarmente energetici ma questo a danno del colore del prodotto. Infine, lo scopo dello studio sulle resine di scambio cationico era quello di valutare la rigenerazione di questo supporto per un molteplice utilizzo operativo. La rimozione delle proteine adsorbite sul supporto è risultata essere possibile in specifiche condizioni di pH e forza ionica, con un consumo di acqua relativamente basso. / The search for fining alternatives to bentonite has assumed great importance in white winemaking due to the drawbacks of bentonite application. The research here presented aimed at observing the viability of three innovative approaches to wine stabilization, namely chitosan addition, PEF treatments and cation exchange applicability. Chitosan successfully removed chitinases from wine, allowing at the same time a sufficient degree of colloidal stability. Collateral effects on color and aroma compounds were non-significant or acceptable when compared with the effects observed for bentonite applications reported in literature. The use of PEF was aimed at accelerating protein unfolding and aggregation and was coupled to an in-line cooling and filtration system for efficient removal of colloidal aggregates. The results collected suggested that the treatment was capable of inducing a satisfactory colloidal stability only in high- energetic double-treated wine samples, with some deleterious consequences on the color. Finally, the aim of the research for cation-exchange resins application was to find environmentally friendly cleaning procedures to regenerate the resin capacity and allow reuse of the same resin for further cycles of fining. The removal of proteins bound to the resin was possible under specific pH and ionic strength conditions with relatively low consumption of water.

Novel photovoltaic cells receive considerable attention from researchers as evidenced by high numbers of published articles. Different types of materials are currently being examined in order to reduce the cost and improve the efficiency of solar cells. Essentially, solar cells are constructed by placing layers of light absorber between electron and hole transport materials. Electricity generation by solar cells involves multiple processes. These processes require an understanding of the physical properties of the surfaces and interfaces of the materials. In this thesis, materials for novel photovoltaic cells are studied by X ray photoelectron spectroscopy (XPS), a surface and interface characterisation technique. The materials studied in this thesis are colloidal quantum dots (CQDs) of the core/shell systems CdTe/CdSe and PbS/CdS, and CQDs that have been surface passivated using Cl- (CdTe/Cl) and CdS (CdTe/CdSe/CdS and PbS/CdS). Moreover, CsSnI3, a perovskite material, is also studied in both bulk and thin film form. CQDs can be used as light absorbers in solar cells while CsSnI3 can be employed as the hole transport material. The role of the core shell structure and surface passivation treatment is to improve or maintain charge transport as well as acting as a protective layer to the CQDs. Depth profiling synchrotron radiation XPS is used to determine these structures. In the CdTe/CdSe samples, the elemental ratio between Se (shell) and Te (core) increases with decreasing sampling depth, demonstrating the presence of a CdSe shell located at the surface of the CQDs. The shell thicknesses of the core-shell systems are estimated from XPS and show that the addition of the third thin shell (of CdS) protects the CQD during ligand exchange. Cl- passivation is shown to reduce the energy the valence band maximum and the energy gap of CdTe CQDs. This is associated with the passivation of midgap trap states due to the removal of dangling bonds at the surface of CQDs. Surface passivation is shown to improve the stability of CQDs to air exposure. This is indicated by a significant reduction of the surface oxide species in the passivated PbS/CdS samples. In the unpassivated core-only PbS samples, however, oxidation rapidly occurs which affects the electronic states required for charge transport in solar cells. XPS studies of CsSnI3 show that this material is reactive to air exposure. Surface preparation techniques are performed to remove the contamination layer and reveal the physical properties of the perovskite itself. This is confirmed by the elemental ratios from XPS. The metallic character of CsSnI3 is also observed in the valence band spectra as evidenced by the appearance of the Fermi edge.

Latex d’Hevea brasiliensis est composé principalement de particules de caoutchouc dont le noyau est constitué de cis-1,4-polyisoprène et la membrane de composés dit non-isoprène. Sa stabilité dans l'arbre est assurée par les charges négatives de la membrane en raison de la présence de protéines et de lipides. Le latex d’Hevea brasiliensis coagule après acidification pour former un gel colloïdal qui est la première étape de sa transformation en caoutchouc naturel.Dans cette thèse, nous avons étudié l’agrégation et la gélification induite par ajout d’un acide et les propriétés des gels obtenus. Pour cela, un latex de caoutchouc naturel commercial constitué par des particules de caoutchouc (1 µm de diamètre), a été utilisée. L'agrégation a été induite par l'hydrolyse d'un composé appelé glucano-delta-lactone (GDL). Cette agrégation a été suivie par différentes techniques basées sur la diffusion de la lumière (turbidimétrie, DWS, SLS). La gélification a été suivie in situ par la rhéologie. Ensuite, les propriétés rhéologiques de gels colloïdaux formés à pH 4 ont été caractérisées dans les régimes linéaires et non-linéaires.La dépendance à la fraction volumique et le pH de l'apparition de l'agrégation ont été observée. La non-redispersion des agrégats montre les interactions fortes entre les particules de caoutchouc. Trois comportements d’état différents (solution stable, la séparation de phase et gel) peuvent être prédits à partir d'un diagramme d’état fraction volumique-pH qui a été établi pendant 5 semaines. L'état de gel présente une structure fractale, caractérisé par une relation de loi de puissance entre le module élastique G' et la fraction volumique. Pour des fortes déformations, une réorganisation irréversible sous contrainte a abouti à un durcissement irréversible du matériau. Nous avons observé par rheo-ultrasound qu'au-dessus de 50% de déformation, une déstructuration homogène est produite dans le gel. / Natural rubber latex is mainly composed by rubber particles whose core is made of cis-1,4-polyisoprene and the shell of non-isoprene compounds. It stability in the tree is provided by the negative charge of the shell due to the presence of proteins and lipids. Natural rubber latex coagulates after acidification to form a colloidal gel that is the first step of its transformation into natural rubber.In this PhD thesis, we studied this acid-induced aggregation and gelation and the properties of the resulting gels. For this, a commercial natural rubber latex composed by rubber particles (1 µm in diameter), was used. Aggregation was induced by hydrolysis of a compound called glucano-delta-lactone (GDL). The aggregation was followed by different techniques based on light scattering (turbidimetry, DWS, SLS). Gelation was followed in situ by rheology. Then, the rheological properties of colloidal gels formed at pH 4 were characterized in the linear and non-linear regimes.Dependence to the volume fraction and the pH of the onset of aggregation was observed. The non-redispersion of aggregates proves the strong interactions between rubber particles. Three different state behaviors (stable solution, phase separation and gel) can be predicted from a state diagram pH-volume fraction that was established over 5 weeks. The gel state exhibits a fractal structure, characterized by a power law relationship between the elastic modulus G’ and the volume fraction. At high deformations, an irreversible reorganization under stress resulted in an irreversible strain hardening of the material. We observed by rheo-ultrasound that above 50% deformation, an homogenous destructuration occurred in the gel.

Foram sintetizadas duas séries de tensoativos catiônicos de estruturas gerais RCONH(CH2)2-N+(CH3)3 Cl- e RCONH(CH2)2-N+(CH3)2-CH2-C6H5 Cl-, sendo RCO uma cadeia acílica contendo 10, 12, 14 e 16 átomos de carbono. Estes tensoativos foram sintetizados pela reação do ácido carboxílico puro com N,N-dimetiletilenodiamina resultando na amidoamina correspondente. A quaternização desta última foi feita pela reação com cloreto de benzila ou com iodeto de metila. Os iodetos foram convertidos nos correspondentes cloretos por troca-iônica. A localização média da interface micelar e a conformação do grupo hidrofílico na micela foram investigadas por IV e RMN. A adsorção na interface solução-ar e a micelização foram estudadas por diversas técnicas: calorimetria, condutância, FEM (força eletromotriz), IV de FT, RMN e tensão superficial. Os resultados foram comparados com os de tensoativos catiônicos comuns, como R\'N+(CH3)3R\" Cl-, sendo R\' = grupo alquílico contendo de 10 a 16 carbonos e R\" = um grupo metila ou benzila. A adsorção e a micelização dos tensoativos contendo o \"espaçador\" (CONH-CH2-CH2) são mais favoráveis. Os valores de ΔGºads e ΔGºmic mais negativos para estes tensoativos, refletem principalmente a transferência mais favorável do grupo polar da solução aquosa para a interface solução/ar e/ou para a micela. Isto ocorre devido à formação de ligações de H, diretas e/ou via água, entre os grupos amida dos monômeros de tensoativo na interface e micela. As diferenças nos valores de ΔGºcabeça+CH3 dos tensoativos com e sem o grupo amida na adsorção (ΔΔGº ads cabeça+CH3 = -17.2 kJ mol-1) e micelização (ΔΔGº ads cabeça+CH3 = -5 a -7 kJ mol-1) estão de acordo com a energia de ligações de H fracas. Os resultados de IV de FT e RMN de 1H comprovaram a formação destas ligações de H e indicaram que a carbonila está presente na interface e o grupo benzila está voltado para o interior da micela. / Two series of cationic surfactants have been synthesized: benzyl-(2acylaminoetil) dimethylammonium chlorides, RCONH(CH2)2-N+(CH3)3 Cl-, and (2-acylaminoethyl)dimethylammonium chlorides, RCONH(CH2)2-N+(CH3)2-CH2-C6H5 Cl-, where RCO refers to an acyl group with 10, 12, 14 and 16 carbon atoms. These surfactants were obtained by reacting chromatographically pure carboxylic acids with N,N-dimethylethylenediamine to give an intermediate amidoamine. The latter was quaternized with benzyl chloride or methyl iodide. Surfactants with iodide counter-ion were transformed into the corresponding chlorides by ion exchange on a macro-porous resin. The average position of micellar interface and conformation of the headgroup were studied by FTIR and NMR. A multi-technique approach has been employed in order to study the effects of the presence of the \"spacer\" group (-CONH- CH2-CH2) on the adsorption and aggregation of these surfactants. The techniques employed were: calorimetry, conductance and EMF measurements, FTIR, NMR, surface tension, and Iight scattering. Surfactants with the spacer group (CONH-CH2-CH2) have more favorable Gibbs free energies of adsorption and/or micellization due to the more favorable transfer of the head-group from bulk phase to the interface and/or the micelle. This is attributed to the formation of direct, and/or water-mediated H-bonding between the surfactant amide groups. Differences in values of ΔGºHead-group+CH3 of surfactants with and without spacer group (ΔΔGº ads Head-group+CH3 = -17.2 kJ mol-1 and ΔΔGº ads Head-group+CH3 = -5 a -7 kJ mol-1 for adsorption and/or micellization, respectively) are in agreement with weak hydrogen bonding. Additional evidence for H-bond formation and for the (average) conformation of the benzyl head-group in the micelle was provided by FTIR and NMR data. The former showed that the amide group is highly hydrated, whereas the latter showed shielding/deshielding of the methylene groups of the surfactant hydrophobic tail, in agreement with a conformation in which the benzyl group is \"bent\" toward the micellar interior.

Esta dissertação apresenta os resultados obtidos na caracterização reológica, utilizando ensaios rotacionais e oscilatórios, de sistemas de cristais líquidos liotrópicos nemáticos e colestéricos à base de cloreto de decilamônio (CDA). Os sistemas colestéricos foram obtidos pela adição às matrizes nemáticas de indutores quirais hidrofóbico (Colesterol) ou hidrofilico (D-(+)Manose) que conferem à estrutura liquidocristalina um arranjo helicoidal. Procuramos analisar os efeitos da concentração do indutor no comportamento reológico, bem como da sua natureza e da quantidade de solvente presentes nestes sistemas mesomórficos. Os ensaios rotacionais foram realizados utilizando-se taxas de cisalhamento constante e variadas. Os resultados obtidos mostraram que ocorre uma mudança no comportamento reológico dependente da natureza do indutor quiral. Fases com indutor hidrofóbico têm sua viscosidade diminuída com a adição de colesterol, enquanto as fases com D-(+)-Manose têm sua viscosidade aumentada. Também foram observadas mudanças no comportamento reológico segundo a quantidade de solvente presente na mesofase. Para sistemas com colesterol e com maior quantidade de água em sua composição, a viscosidade aumenta ao longo do tempo até atingir um valor máximo, seguido de uma diminuição. Este comportamento deve indicar que nestes sistemas, as fases devem primeiro sofrer uma deformação atingindo um máximo de tensão, a partir da qual começa a ocorrer uma melhor acomodação da sua estrutura, provocando a diminuição da viscosidade. Nos sistemas com indutor hidrofóbico e com menor. quantidade de solvente, a viscosidade diminui até atingir um valor mínimo. Pode-se observar que quanto maior for a concentração de indutor, maior é o tempo necessário para se atingir este mínimo. A partir deste ponto há um aumento da viscosidade até um valor constante. Isto sugere a ocorrência de uma quebra da estrutura do sistema, seguida por sua reorientação por fluxo. Em sistemas em que o indutor é D-(+)-Manose, o comportamento reológico observado é semelhante tanto em fases com maior ou menor quantidade de solvente, ou seja, aumento da viscosidade até um valor máximo, seguido pela sua diminuição. A diferença observada é que em sistemas com maior quantidade de solvente, o máximo é atingido mais cedo. O aumento da viscosidade deve caracterizar uma deformação da estn1tura que após atingir uma tensão máxima, começa a se orientar em uma direção preferencial, causando a diminuição da viscosidade sem quebra do edifício colestérico. A determinação da entalpia livre de ativação de fluxo (ΔH≠) mostra que para os sistemas em que o colesterol foi usado como indutor, a energia diminui com o aumento da concentração de indutor, quando D-(+)-Manose é utilizado, a energia aumenta. No caso do indutor hidrofóbico, a força quiral auxiliaria na orientação por fluxo das micelas, pois ao se movimentar uma micela, as outras seriam arrastadas pelas forças elásticas, diminuindo a entalpia de ativação de fluxo. Quando o indutor utilizado é hidrofílico, a entalpia de ativação aumenta, possivelmente devido à natureza do indutor, que possui uma interação maior com o solvente, agindo como uma barreira para a movimentação e orientação das micelas por fluxo. Os ensaios oscilatórios, por sua vez, mostram que a capacidade de armazenamento e devolução de energia, determinada pelo valor do módulo de armazenamento (G\') é maior que capacidade de dissipação desta por calor ou difusão das partículas, obtida pelo módulo de perda (G\"). Ambos os módulos apresentam uma dependência em relação quantidade de indutor, natureza de indutor e quantidade de água disponível, porém não foi possível se determinar nenhuma relação direta entre esses fatores. Esse sistema liotrópico pode ser descrito pelo modelo de Burger, contanto que seja levado em consideração que a componente elástica do elemento de Maxwell possua uma dependência temporal. Esse efeito provavelmente é devido à própria inércia do sistema. / This dissertation shows the results obtained on the rheological characterization, using rotation and oscillatory essays, for nematics and cholesterics lyotropic liquid crystals based on decylammonium chloride (CDA). The cholesteric systems were obtained adding chiral inductors, hydrophobic (Cholesterol) or hydrophilic (D-(+)-Mannose) to nematic matrixes, inducing a helical arrangement on the liquid crystalline stn1cture. The effect of the inductor concentration besides of its nature and the amount of solvent in these mesomorphic systems were correlated to the rheological properties obtained. The rotation essays were done using constant and varied shear rates. The obtained results showed a change in the rheological behavior dependent of the chiral inductor nature. Phases with hydrophobic inductor presented viscosity decreased with the increase of cholesterol concentration, while the increase of D-(+)-Mannose concentration leads to the viscosity increase. Changes in the rheological behavior were also observed according to the amount of solvent present on the phase. For systems with cholesterol and larger amount of water, the viscosity increases along the time until reaching a maximum value, followed by a decrease. This behavior should indicate that in these systems, the phases should suffer some kind of deformation until reaching a maximum of tension. After that, an accommodation process of the structure causes the viscosity decrease. For the systems with hydrophobic inductor and with smaller amount of solvent, the viscosity decreases until reach a minimum value, that is reached later as larger it is the inductor concentration. After that, there is an increase of the viscosity until a constant value be obtained. It suggests the occurrence of a breakdown of the stn1cture, proceeded by its reorientation by flow. For the systems with D-(+)-Mannose, the rheological behavior observed is quite similar for phases with larger or smaller amount of solvent, i.e., increase of the viscosity to a maximum value, followed proceeded by its decrease. The difference is that in systems with larger amount of solvent, the maximum is reached earlier. The increase of the viscosity should characterize a deformation of the stn1cture that after reaching a maximum tension, it will be orientated in a preferential direction, causing the decrease of the viscosity without break of the cholesteric building. The flow activation free enthalpy (ΔH≠) determination shows a decrease of energy value for increase of inductor concentration in lyotropic cholesteric liquid crystal that used cholesterol as inductor. When D-(+)-Mannose was used, the flow activation free enthalpy value increases. In the systems that hydrophobic inductor is used, the chiral forces should help in micelles flow orientation process, seemingly, after the movement of a micelle, the others would be dragged by the elastic forces, decreasing the flow activation enthalpy. When it is used a hydrophilic inductor, flow activation enthalpy increases with increases of inductor concentration, probably because the inductor nature that has a greater interaction with the solvent, acting as a barrier against the micelles flow orientation. The oscillatory essays show that the storage energy capacity, determined by the value of the storage modulus (G\') is larger than heat or diffusion dissipation capacity of the particles, obtained by the loss modulus (G\"). Both modulus (G\' and G\") decrease for the phases with smaller amount of available water and stay constant for the systems with larger amount of water. The lyotropic mesophase studied can be described by a Burger model modified by taken into account a temporary dependence to the elastic Maxwell component. This effect should be probably due to the inertia of the system.

Gold nanoparticles, are one of the most widely investigated nanoparticles (NP) and are normally synthesized by the reduction of metal salts in citrate solution. The reason for studying this nanostructured material from a technological standpoint is mainly the anticipated application in different areas based on optical properties explained with plasmon resonance. The main work of this study was to develop different sensing systems using gold nanoparticles. Three techniques have been utilized, being lateral flow immunoassay (LFIA), surface plasmon resonance (SPR), and surface-enhanced Raman scattering (SERS). A one-step semi-quantitative LFIA strip test was developed using colloidal gold coated by a partially-purified polyclonal antibody (pAb) raised in sheep as a signal generator, and bovine serum albumin-Estriol-16-glucuronide (BSA-E3-16G) conjugates as the capture agent spotted onto a nitrocellulose membrane as the test line. In this system, gold nanoparticles were applied for visualising the response. The application of the strip sensor to urinary samples from pregnant woman proved successful. A quantitative evaluation of low levels of E3-16G in liquid media was developed based on SPR, which used the same pAb-nanogold conjugates employed for the LFIA analysis. The assay can be carried out directly on any urine samples without sample pretreatment. In this system, gold nanoparticles were utilized as high mass label to improve the sensitivity of the assay. A SERS probe was developed which comprised of Raman reporter molecules (RRM) and gold NPs. Results showed that the conducting polymer materials of 3’-[(E)-2-(4-R-phenyl)ethenyl]-2’2’:5’,2”-terthiophene (R-pe3T, where R is NO2 or NH2) showed significant enhancement. Moreover, high bio-activity groups included in the compounds make them potential candidates for the development of a SERS based sensing system.

Ce travail expérimental cherche à mieux caractériser les effets du cisaillement sur le vieillissement d'un verre colloidal au niveau microscopique. La dynamique des réarrangements d'un tel système est étudiée au moyen d'une technique de diffusion multiple de la lumière (MSDWS) développée au cours de cette thèse. Nous montrons que la cessation d'un cisaillement de forte amplitude est, au niveau microscopique, l'équivalent pour ces systèmes d'une trempe thermique pour d'autres systèmes vitreux. Notre système est en effet rajeuni par un fort cisaillement puis présente un comportement de vieillissent classique à la cessation de celui-ci. De surcroît, nous montrons qu'un cisaillement de faible amplitude permet au système de vieillir plus vite. Nous appelons ce comportement le survieillissement. Ces deux effets antagonistes (rajeunissement et survieillissement) sont aussi observés sur des polymères vitreux soumis à des marches de température. Nous montrons enfin que le modèle SGR fournit une description unifiée de ces comportements similaires pour différents types de perturbation. Ceux-ci mettent en lumière l'élargissement de la distribution de temps de relaxation au sein de ce type de matériaux soumis à des perturbations extérieures.

The research presented has been focused on understanding the surface effects on the optical and electronic properties of some metallic and semiconductor nanomaterials. When the particle sizes are on the nanometer length scale, a large fraction of atoms in the particles are on the surface. The bonding of the surface atoms being unsaturated could cause trapping and introduce defects that interact with the excited electrons. The effect of the surface on the optical and electronic properties of some semiconductor and metallic nanoparticles is investigated. When the size and shape of nanomaterials change, both the electron density of the excited electrons on the surface and the electronic structure change. Therefore, it becomes important to understand how these changes affect the electronic motion in the particles in order to exploit their full potential in a variety of applications. Semiconductor nanoparticles studied include cadmium selenide (CdSe) and cadmium sulfide (CdS). Effect of changing CdSe shape and size on optical and electronic properties has been investigated and the ability for the CdS nanoparticles to show optical gain (stimulated emission) in solution at room temperature is reported. Effect of surface phonon contribution on the exited electron relaxation in copper nanoparticles is investigated. For the particles size smaller than the mean free path of the electrons in the metal, electron-surface phonon coupling becomes an important factor (contribution) for hot electron relaxation. In the thesis presented, it is shown for the first time the size depended electronic relaxation in copper nanoparticles. Fluorescence due to surface plasmon field enhancement is observed for copper nanoparticles to be million times stronger than the fluorescence observed from bulk copper.