Les biofilms sont des communautés de microorganismes emprisonnés dans une matrice de polymères organiques extracellulaires (EPS) permettant de stabiliser ces édifices tridimensionnels. La cohésion des EPS polyanioniques dans un environnement hydraté est assurée par des microdomaines hydrophobes. La localisation de ces sites hydrophobes est très importante pour comprendre la variabilité ainsi que la réactivité des EPS. Notre travail vise la synthèse de nouvelles sondes fluorescentes hydrophiles ou amphiphiles capables de marquer les EPS. Dans ce but, nous avons synthétisé une série de nanocristaux fluorescents à coeur CdSe, appelés Quantum Dots (QDs), modifiés à leur périphérie par des ligands hydrophiles (acide 3-mercaptopropionic) ou amphiphiles (acide dihydrolipoique couplé à des acides aminés hydrophobes tels que la Leucine ou la Phénylalanine). Par microscopie confocale de fluorescence et spectroscopie de corrélation de fluorescence (FCS), nous avons montré que les QDs fonctionnalisés s'associaient fortement aux EPS des biofilms de la bactérie S. oneidensis. La distribution de ces nanoparticules dans les EPS est dépendante de la structure du ligand et de sa densité à la périphérie des QDs. Une dispersion homogène des QDs hydrophiles dans l'ensemble du biofilm et une clusterisation des QDs amphiphiles dans des microdomaines hydrophobes ont notamment été observés. Les nouvelles sondes fluorescentes développées dans ce travail permettront de suivre le développement ainsi que la réorganisation de matrices biologiques complexes telles que les biofilms. / Microorganisms predominantly live in communities, such as biofilms, in which extracellular polymeric substances (EPS) form the matrix and stabilize the three-dimensional structure. Hydrophobic microdomains allow the cohesiveness of these hydrophilic, polyanionic systems. The localization of these hydrophobic sites is very important to understand the variability and the reactivity of the EPS. The objective of our work was to engineer new fluorescent probes with amphiphilic or hydrophilic properties able to label the EPS. For that purpose, we have synthesized a series of fluorescent CdSe-core nanocrystals, also called Quantum Dots (QDs), modified at their periphery with hydrophilic (3-mercaptopropionic acid) or amphiphilic ligands (dihydrolipoic acid coupled to hydrophobic aminoacids like Leucine or Phenylalanine). Using confocal fluorescence microscopy and fluorescence correlation spectroscopy (FCS), we demonstrated that the functionalized QDs strongly associated with the EPS of S. oneidensis biofilms and allow imaging of these microbial communities. The location of these probes within the EPS was dependent on the surface ligand structure and on its density at the periphery of QDs. A homogeneous dispersion of hydrophilic QDs in the whole biofilm was observed, while amphiphilic QDs clusterized in the small hydrophobic domains. These new fluorescent probes will be of great use to understand the development and the reorganization of complex biological matrix like biofilms.

Neste trabalho utilizamos o método k.p na aproximação de função envelope, que é uma ferramenta muito útil para a solução de problemas relacionados a heteroestruturas em geral. Apresentamos a análise de heteroestruturas semicondutoras com confinamento espacial nas três direções de crescimentos {Quantum Dots}, utilizando o Hamiltoniano de Kane (8x8) em sua forma generalizada para descrever os estados do elétrons na banda de condução e na banda valência. Fazendo uso dessa ferramenta foram realizadas simulações de estruturas de banda em sistemas quase zero-dimensionais de InAs em matrizes de GaAs, em vários formatos e dimensões e sob diferentes estados de tensionamento. Um estudo sistemático de como as propriedades geométricas e as dimensões de um dado sistema podem influenciar os estados eletrônicos do mesmo foi também realizado, onde puderam ser confirmadas a presença de estados localizados e a sensibilidade do comportamento dos estados eletrônicos a estas propriedades. Pudemos observar um deslocamento para o vermelho no espectro de fotoluminescência com o aumento das dimensões do sistemas estudados. Foram ainda realizados cálculos de {Quantum Dots} de InN em matriz de GaN, que permitem explorar outras regiões do espectro eletromagnético e observamos o comportamento dos mesmos sob estados de tensionamentos diferentes. Com base nos autoestados do sistema foram calculados espectros de fotoluminescência para as heteroestruturas aqui estudadas, permitindo uma comparação direta com resultados experimentais. Como pode-se verificar o strain exerce importância primordial na determinação dos estados eletrônicos dos sistemas estudados e na presença do hidrostático pode-se verificar mudanças apreciáveis na resposta óptica do material, onde pode ser observado um deslocamento para o azul quando levado em consideração a presença de um hidrostático. / In this work, we use the k.p method in the approximation of the envelope function, that is a very useful tool, to the solution of heterostructure related problems. We present a semiconductor heterostructure analysis with confinement on the three directions (Quantum Dots), using the Kane Hamiltonian (8x8) on its generalized form to describe electron eigenstates on the conduction and valence bands. Using this tool, we have made band structure simulations in quasi zero-dimensional systems of InAs in GaAs matrices, in diverse shapes and dimensions and on different tension states. A systematic study of how the geometrical properties and dimensions of a given system could influence the electronic states was also done. There can be confirmed the presence of localized states and the sensitivity of the electronic states to these properties.We could observe a deviation to the red on the photoluminescence spectrum with the increase of the system dimensions. There were also made calculations on InN dots in a GaN matrix, which allow to explore other electromagnetic spectral regions and we have studied their behavior under different tension states. From the system eigenvalues, we calculated the photoluminescence spectra from the heterostructures studied here, allowing a direct comparison with experimental results. It can be verified that the strain is is extremely important on the determination of the electronic states of the studied systems in the presence of an hydrostatic strain. We could observe important modifications on the optical responseof the material, where there is a deviation to the blue when it is considered the presence of the hydrostatic strain.

Les synoviocytes jouent un rôle crucial dans la pathogénèse des maladies articulaires chroniques, et particulièrement dans la phase de destruction ostéoarticulaire en devenant résistants à l’apoptose. Une première étude a mise en évidence une efficacité antiproliférative du cadmium minéral sur ces synoviocytes. Une preuve de concept d’un nouveau produit thérapeutique intra-articulaire à base de cadmium a été élaborée. Cette préparation pharmaceutique innovante, développée pour éviter la dissémination du cadmium minéral dans l’organisme, contenait des nanoparticules à base de cadmium, administrable sous forme liquide à température ambiante et se gélifiait à la température corporelle, en formant des micelles contenant des nanoparticules, ne traversant ainsi pas la cavité synoviale. Initialement, la reproductibilité de l’effet antiprolifératif du cadmium entre la forme minérale et les nanoparticules a été vérifiée dans un modèle in vitro de synoviocytes humains atteints de polyarthrites rhumatoïdes. Une captation différente des nanoparticules selon l’environnement inflammatoire ou pathologique des synoviocytes a été ensuite expliquée par la modification accrue de leurs morphologies. Similairement, l’effet de l’inflammation sur les propriétés physiques des vésicules, sécrétées par les synoviocytes, ont consolidé le choix des caractéristiques de la formulation. Les essais sur des modèles d’arthrite chez le rat ont permis de démontrer l’efficacité de cette nouvelle préparation originale, facilement injectable en intra-articulaire, en réduisant les scores cliniques avec une unique injection. Cette thérapie locale peut être une technique rapide et réalisable en ambulatoire / Synoviocytes play a crucial role in the pathogenesis of chronic joint diseases, particularly in the osteoarticular destruction phase by becoming resistant to apoptosis. A first study has demonstrated an antiproliferative efficacy of cadmium mineral on these synoviocytes. A proof of concept of a new intra-articular cadmium-based therapeutic product has been developed. This innovative pharmaceutical preparation, developed to prevent the spread of mineral cadmium in the body, contained cadmium-based nanoparticles, which can be administered in liquid form at room temperature and gelled at body temperature, forming micelles containing nanoparticles, thus crossing the synovial cavity. Initially, the reproducibility of the antiproliferative effect of cadmium between the mineral form and the nanoparticles was verified in an in vitro model of human synoviocytes with rheumatoid arthritis. A different uptake of nanoparticles according to the inflammatory or pathological environment of synoviocytes was then explained by the massive modification of their morphologies. Similarly, the effect of inflammation on the physical properties of the vesicles, secreted by synoviocytes, consolidated the choice of the characteristics of the formulation.Tests on arthritis models in rats have demonstrated the effectiveness of this new original preparation, easily injectable intra-articular, reducing clinical scores with a single injection. This local therapy can be a quick technique and achievable in outpatient

Semiconductor nanostructures exhibit many remarkable electronic and optical properties. The key to designing and utilising semiconductor quantum structures is a physical understanding of the detailed excitation, transport and energy relaxation processes. Thus the nonequilibrium dynamics of semiconductor quantum structures have attracted extensive attention in recent years. Ultrafast spectroscopy has proven to be a versatile and powerful tool for investigating transient phenomena related to the relaxation and transport dynamics in semiconductors. In this thesis, we report investigations into the electronic and optical properties of various semiconductor quantum systems using a variety of ultrafast techniques, including up-conversion photoluminescence, pump-probe, photon echoes and four-wave mixing. The semiconductor quantum systems studied include ZnO/ZnMgO multiple quantum wells with oxygen ion implantation, InGaAs/GaAs self-assembled quantum dots with different doping, InGaAs/InP quantum wells with proton implantation, and silicon quantum dots. The spectra of these semiconductor nanostructures range from the ultraviolet region, through the visible, to the infrared. In the UV region we investigate excitons, biexcitons and oxygen implantation effects in ZnO/ZnMgO multi-quantum wells using four-wave mixing, pump-probe and photoluminescence techniques. Using time-resolved up-conversion photoluminescence, we investigate the relaxation dynamics and state filling effect in InGaAs self-assembled quantum dots with different doping, and the implantation effect in InGaAs/InP quantum wells. Finally, we study the optical properties of silicon quantum dots using time-resolved photoluminescence and photon echo spectroscopy on various time scales, ranging from microseconds to femtoseconds.

Increased demand of power, limited fuel resources and environmental concerns have recently prompted a huge thrust on research areas of alternative energy and photovoltaics have been hailed as energy source for future. Particularly, third generation solar cell configurations like dye-sensitized solar cells and quantum dot Schottky barrier solar cells have drawn more attention because of their ease of processability, cheap cost with decent performance, low payback time and portability. Quantum dots are very attractive materials as sensitizers because of their size dependent bandgap tunability, increased oscillator strength and hence higher absorption coefficient, possibility of multiple exciton generation and photochemical robustness. Hence syntheses of quantum dot based hybrid nanostructures have received huge attention among researchers for using it quantum dot sensitized solar cell configuration. This dissertation can be divided in two parts. In the first part two different methods have been reported to prepare interconnected mesoporous nanostructures of wide band gap semiconductors like TiO2 and ZnO which is very important in providing high surface area for absorption or attachment of the sensitizers. In the second part, methods have been developed to establish direct contacts between quantum dots and wide bandgap substrates without molecular linkers which are expected to increase the electron injection rate from quantum dots to TiO2/ZnO. The entire thesis based on the results and findings obtained from the present investigation is organised as follows: Chapter-I provides a general introduction on the working principle of different type of solar cells and then gives a detailed description of the structure and electronic process of dye sensitised solar cells. Then, benefits of quantum dots as sensitizer over dye molecules has been discussed followed by the modification needed in case of quantum dot sensitized solar cells. Chapter-II deals with the materials and methods which essentially gives the information about the materials used for the synthesis and the techniques utilized to characterize the materials chosen for the investigation. Chapter-III describes a hybrid sol-gel combustion technique to synthesize large quantities of highly crystalline and phase-pure anatase powder in a single step. Titanium isopropoxide reacts with oleic acid to form a viscous liquid (oxocarboxoalkoxide) which undergoes non-hydrolytic polycondensation to form TiO2 during combustion. Oleylamine takes part in formation of reverse micelle which expands during combustion giving rise to porous interconnected membrane like microstructure of pore size ~5 nm, BET surface area of ~100 m2/g and porosity of ~ 48%. More importantly, this porous powder having a pre-existing network can be used to form thicker film by doctor blade technique from its paste and at the same time is expected to have better transport properties due to its less particulate nature. Chapter-IV presents a general method to prepare mesoporous structure from rod-like morphologies by partial sintering of a green pellet. Material having inherent anisotropy in their crystal structure tends to grow in a particular direction rather undergoing equiaxial growth. For instance, hexagonal ZnO and tetragonal rutile usually grow as rod-shaped particles. A loose compact of these nanorods give nanoporous morphology upon heating. Advantage of this method is the tunability of pore size by tuning the aspect ratio of the nanorods. Preparation of porous TiO2, ZnO and hydroxyapatite has been demonstrated from their corresponding nanorods. Chapter-V deals with a solvothermal based technique that has been developed for in-situ deposition of nanoparticles on any plane or curved surfaces conformally. This has been demonstrated for nanoparticles of FeCo, Au, Co, CdS on substrates like glass, mica, Si, NaCl, Al2O3 M-plane and also conformal coating of Au nanoparticles on polystyrene latex spheres. CdSe on rutile nanorods, ZnO nanorods and CNTs are promising hybrid nanostructures for third generation photovoltaics and their successful preparation has been detailed in the chapter. The mechanism proposed is based on dominant attractive sphere-plate interaction under high temperature and high autogeneous pressure condition which at reduced density and surface tension of the solvent reduces the dispersibility of the nanoparticle and allow effective spreading of the nanoparticles on the substrate. This method is also advantageous for coating of complicated geometry like inner walls of porous structures. Chapter-VI presents a method to coat chalcogenide nanoparticles on mesoporous TiO2 without any molecular linker which can enhance the electron injection rate from the chalcogenide quantum dots to TiO2. CdS, PbS can be easily synthesized through aqueous chemistry. For deposition of these sulfides, the ion layer gas absorption and reaction (IGLAR) method was modified to form uniform dense nanoparticles on anatase and ZnO surfaces. Nitrate salts of corresponding metal ions are dried directly on the semiconductor surface and instead of exposing it to H2S gas, it was treated with a concentrated sulfide solution. This introduces two competitive process i) dissolution of nitrate salt ii) formation of the metal sulfide. This dissolution step was absent when treated with H2S gas (IGLAR) and hence lead to a continuous coating. We have successfully produced CdS-TiO2 and PbS-TiO2 composites using this approach. Photoelectrochemical measurements on CdSTiO2 composites show an overall efficiency of 2.8% which is among the highest values obtained for this system demonstrating the applicability of the method to engineer interfaces to achieve high efficiency solar cells. Chapter-VI explores the combination of strategies of nanocrystal conversion chemistry with previously described sol-gel combustion technique to create dense and uniformly coated QD sensitized TiO2 electrode without compromising heat-treatment routines which is essential for better adhesion and to enhance performance with reduced leakage. Intimate biphasic oxide mixtures of PbO and CdO with TiO2 are first synthesized by nonhydrolytic solgel process with is followed by combustion to produce porous morphology. This powder can be coated as electrode and can sustain high temperature heat treatment routines and finally can be selectively converted to sulfides with Na2S treatment as TiO2 is immune to sulfidation under this condition. Materials at different stages are characterised by XRD, TEM, EDS, UV-Vis and XPS.

There is a demand for new straightforward approaches for stabilization and solubilization of various nanoparticulate materials in their colloidal form, that pave way for fabrication of materials possessing compatibility with wide range of dispersing media. Therefore in this thesis a new general method to form stable nanocrystals in water and organics using amphiphilic polymers generated through simple and low cost techniques is presented and discussed. Amphiphilic coating agents are formed using thiolated or carboxylated polyethylene glycol methyl ether (mPEG-SH) as a starting material. These materials are available with a wide variety of chain lengths. The method of obtaining of amphiphilic NPs is quite general and applicable for semiconductor CdTe nanocrystals as well as nanoscale noble metal (Au) and magnetic (Fe3O4) particles. This approach is based on anchoring PEG segment to the surface of a nanoparticle to form an amphiphilic palisade. Anchoring is realized via interaction of –SH (for CdTe and Au) or –COOH (in the case of magnetite) functional groups with particle’s surface. The resulting amphiphilicity of the nanocrystals is an inherent property of their surface and it is preserved also after careful washing out of solution of any excess of the ligand. The nanocrystals reversibly transfer between different phases spontaneously, i.e. without any adjustment of ionic strength, pH or composition of the phases. Such reversible and spontaneous phase transfer of nanocrystals between solvents of different chemical nature has a great potential for many applications as it constitutes a large degree of control of nanocrystals compatibility with technological processes or with bio-environments such as water, various buffers and cell media as well as their assembly and self-assembly capabilities.

This dissertation presents a new class of cancer diagnostic agents composed of quantum dots, magnetic nanoparticles, and amphiphilic polymers. The central hypothesis is that biocompatible, amphiphilic block copolymers can be used to create multinanoparticle micellar probes with imaging capabilities and surface properties optimized for applications in cancer diagnostics. To test this hypothesis, we investigated a number of different block copolymer structures and synthetic procedures. We found that use of a poly(methyl methacrylate)-poly(ethylene oxide) polymer in conjunction with a dialysis-based procedure produced uniform probes with excellent imaging properties. We also found that the probes formed using these materials and methods were surprisingly stable, even after incubation in whole human blood for 24 hrs at 37oC. As a corollary, we hypothesized that modified polymer structures could be used to introduce functional groups for use in linking the micellar probes to biological molecules. To test this hypothesis, we used a modified version of our synthetic procedure and utilized a novel method for studying nanoparticle binding to biological molecules in real time. We found that active amine groups could be added to the polymer shell using these methods, and that surface plasmon resonance could be used for studying nanoparticle binding. In sum, this dissertation makes several contributions to the field of cancer nanotechnology. First, we provide a new encapsulation procedure and nanostructure that has promising physical and biological properties. Secondly, we provide general strategies that can be used for future nanoprobe development. Finally, we demonstrate the capability of a new method for quantitative study of probe binding characteristics. Together, these contributions drive the field of cancer nanotechnology forward by providing a deeper understanding of the relationship between surface design and behavior in biological systems.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Textile dyes and other commercial dyestuffs have become a focus of environmental remediation efforts in the last few years. Considerable attention has been expended recently on the photocatalytic oxidative degradation of colored contaminants in waste water over semiconductor surfaces. In this work, we evaluated the photocatalytic activities of nanocomposites based on cadmium sulfide (CdS) quantum dots anchored on (mercaptopropyl)silica (MPS) monitoring the photodegradation of methylene blue and rhodamine 6G aqueous solutions under sunlight irradiation. Herein, MPS was selected as the stabilizing agent to prepare the CdS and CdS doped with Cu2+ Qdots by the chemical reaction of cadmium acetate and thiourea in dimethylformamide Abstract|viii (DMF) by a rather simple one-step method. The quantum size effect has been monitored by UV visible spectroscopy, which showed a blue shift of about 16 48 nm relative to bulk CdS in the range 442-474 nm. Particle sizes calculated from Brus s model were found to be dependent on the MPS amount. These results evidenced that as-prepared CdS nanocrystals behave as Qdots. Additionally, XRD mensurements and HRTEM images indicated CdS cubic structure for the nanocrystals, which also exhibited an increment in the fluorescence intensity with decreasing particle size. UV absorption spectra for Cu-doped CdS are essentially similar to that of the undoped Qdots, but the luminescence properties are quite different from those of the undoped samples. Moreover, these materials could effectively degrade the organic dyes under sunlight irradiation by pseudo-first-order kinetics. This suggested that the CdS Qdots prepared in this work can be used as the potential photocatalyst to effectively treat the organic pollutants under sunlight irradiation. / Indústrias têxteis produzem elevado volume de efluentes ricos em corantes tóxicos e não-biodegradáveis. A degradação fotocatalítica de poluentes aquosos usando nanocristais semicondutores é uma área emergente na remediação ambiental. Neste trabalho, a atividade fotocatalítica de quantum dots (Qdots) de sulfeto de cádmio (CdS) ancorados em (mercaptopropil)sílica (MPS) foi investigada a partir da degradação dos corantes azul de metileno (AM) e rodamina 6G (R6G). Nanocristais de CdS e CdS dopado com íons Cu2+ foram preparados pela reação química de acetato de cádmio e tiouréia em presença da matriz de sílica organofuncionalizada, por um método bastante simples e de uma única etapa. Pelos espectros eletrônicos, foi possível notar um Resumo|vi deslocamento para o azul com o aumento da quantidade de MPS e band gaps mais largos do que o bulk de CdS. Os diâmetros das nanopartículas, estimados a partir do modelo de Brus, são dependentes da quantidade da matriz. Estes resultados sugerem que as partículas se comportam como Qdots. Fases cúbicas dos nanocristais são estabelecidas de acordo com dados de DRX e HRTEM e os espectros de emissão corroboram a presença de Qdots no material formado. A dopagem do nanocompósito com íons Cu2+ propiciou mudanças na recombinação elétron-buraco das nanopartículas de CdS, o que foi observado pelos espectros de absorção no UV-vis e de emissão. Avaliação temporal no espectro de absorção no UV-vis dos corantes AM e R6G em contato com CdS/MPS e CdS:Cu/MPS durante irradiação com luz solar mostrou uma pronunciada diminuição da intensidade de absorbância e um deslocamento do máximo de absorção para menores comprimentos de onda, em resposta à formação de subprodutos de degradação.

Neste trabalho utilizamos o método k.p na aproximação de função envelope, que é uma ferramenta muito útil para a solução de problemas relacionados a heteroestruturas em geral. Apresentamos a análise de heteroestruturas semicondutoras com confinamento espacial nas três direções de crescimentos {Quantum Dots}, utilizando o Hamiltoniano de Kane (8x8) em sua forma generalizada para descrever os estados do elétrons na banda de condução e na banda valência. Fazendo uso dessa ferramenta foram realizadas simulações de estruturas de banda em sistemas quase zero-dimensionais de InAs em matrizes de GaAs, em vários formatos e dimensões e sob diferentes estados de tensionamento. Um estudo sistemático de como as propriedades geométricas e as dimensões de um dado sistema podem influenciar os estados eletrônicos do mesmo foi também realizado, onde puderam ser confirmadas a presença de estados localizados e a sensibilidade do comportamento dos estados eletrônicos a estas propriedades. Pudemos observar um deslocamento para o vermelho no espectro de fotoluminescência com o aumento das dimensões do sistemas estudados. Foram ainda realizados cálculos de {Quantum Dots} de InN em matriz de GaN, que permitem explorar outras regiões do espectro eletromagnético e observamos o comportamento dos mesmos sob estados de tensionamentos diferentes. Com base nos autoestados do sistema foram calculados espectros de fotoluminescência para as heteroestruturas aqui estudadas, permitindo uma comparação direta com resultados experimentais. Como pode-se verificar o strain exerce importância primordial na determinação dos estados eletrônicos dos sistemas estudados e na presença do hidrostático pode-se verificar mudanças apreciáveis na resposta óptica do material, onde pode ser observado um deslocamento para o azul quando levado em consideração a presença de um hidrostático. / In this work, we use the k.p method in the approximation of the envelope function, that is a very useful tool, to the solution of heterostructure related problems. We present a semiconductor heterostructure analysis with confinement on the three directions (Quantum Dots), using the Kane Hamiltonian (8x8) on its generalized form to describe electron eigenstates on the conduction and valence bands. Using this tool, we have made band structure simulations in quasi zero-dimensional systems of InAs in GaAs matrices, in diverse shapes and dimensions and on different tension states. A systematic study of how the geometrical properties and dimensions of a given system could influence the electronic states was also done. There can be confirmed the presence of localized states and the sensitivity of the electronic states to these properties.We could observe a deviation to the red on the photoluminescence spectrum with the increase of the system dimensions. There were also made calculations on InN dots in a GaN matrix, which allow to explore other electromagnetic spectral regions and we have studied their behavior under different tension states. From the system eigenvalues, we calculated the photoluminescence spectra from the heterostructures studied here, allowing a direct comparison with experimental results. It can be verified that the strain is is extremely important on the determination of the electronic states of the studied systems in the presence of an hydrostatic strain. We could observe important modifications on the optical responseof the material, where there is a deviation to the blue when it is considered the presence of the hydrostatic strain.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Textile dyes and other commercial dyestuffs have become a focus of environmental remediation efforts in the last few years. Considerable attention has been expended recently on the photocatalytic oxidative degradation of colored contaminants in waste water over semiconductor surfaces. In this work, we evaluated the photocatalytic activities of nanocomposites based on cadmium sulfide (CdS) quantum dots anchored on (mercaptopropyl)silica (MPS) monitoring the photodegradation of methylene blue and rhodamine 6G aqueous solutions under sunlight irradiation. Herein, MPS was selected as the stabilizing agent to prepare the CdS and CdS doped with Cu2+ Qdots by the chemical reaction of cadmium acetate and thiourea in dimethylformamide Abstract|viii (DMF) by a rather simple one-step method. The quantum size effect has been monitored by UV visible spectroscopy, which showed a blue shift of about 16 48 nm relative to bulk CdS in the range 442-474 nm. Particle sizes calculated from Brus s model were found to be dependent on the MPS amount. These results evidenced that as-prepared CdS nanocrystals behave as Qdots. Additionally, XRD mensurements and HRTEM images indicated CdS cubic structure for the nanocrystals, which also exhibited an increment in the fluorescence intensity with decreasing particle size. UV absorption spectra for Cu-doped CdS are essentially similar to that of the undoped Qdots, but the luminescence properties are quite different from those of the undoped samples. Moreover, these materials could effectively degrade the organic dyes under sunlight irradiation by pseudo-first-order kinetics. This suggested that the CdS Qdots prepared in this work can be used as the potential photocatalyst to effectively treat the organic pollutants under sunlight irradiation. / Indústrias têxteis produzem elevado volume de efluentes ricos em corantes tóxicos e não-biodegradáveis. A degradação fotocatalítica de poluentes aquosos usando nanocristais semicondutores é uma área emergente na remediação ambiental. Neste trabalho, a atividade fotocatalítica de quantum dots (Qdots) de sulfeto de cádmio (CdS) ancorados em (mercaptopropil)sílica (MPS) foi investigada a partir da degradação dos corantes azul de metileno (AM) e rodamina 6G (R6G). Nanocristais de CdS e CdS dopado com íons Cu2+ foram preparados pela reação química de acetato de cádmio e tiouréia em presença da matriz de sílica organofuncionalizada, por um método bastante simples e de uma única etapa. Pelos espectros eletrônicos, foi possível notar um Resumo|vi deslocamento para o azul com o aumento da quantidade de MPS e band gaps mais largos do que o bulk de CdS. Os diâmetros das nanopartículas, estimados a partir do modelo de Brus, são dependentes da quantidade da matriz. Estes resultados sugerem que as partículas se comportam como Qdots. Fases cúbicas dos nanocristais são estabelecidas de acordo com dados de DRX e HRTEM e os espectros de emissão corroboram a presença de Qdots no material formado. A dopagem do nanocompósito com íons Cu2+ propiciou mudanças na recombinação elétron-buraco das nanopartículas de CdS, o que foi observado pelos espectros de absorção no UV-vis e de emissão. Avaliação temporal no espectro de absorção no UV-vis dos corantes AM e R6G em contato com CdS/MPS e CdS:Cu/MPS durante irradiação com luz solar mostrou uma pronunciada diminuição da intensidade de absorbância e um deslocamento do máximo de absorção para menores comprimentos de onda, em resposta à formação de subprodutos de degradação.