I denna kandidatuppsats avlägsnas organiska föroreningar från vatten genom användning av textilier, vars yta belagts med nanopartiklar utav ämnet titandioxid. När titandioxid belyses med UV-strålning sker en fotokatalytisk reaktion, vilket i sin tur bryter ned bland annat bakterier och organiska färgämnen. I hopp om att finna ultimat vidhäftning mot textil passande titandioxid har olika typer av beläggningar studerats; akrylbaserade, sol-gel och slutligen en hybrid. Dessutom har fem olika konstruktioner av textila bindningar jämförts i syfte att undersöka dess påverkan på den fotokatalytiska effekten. Förorenade vatten är ett stort problem, både i utvecklingsländer och i industriella sammanhang. Att använda en textil fr att rena nedsmutsat vatten är en lockande tanke, speciellt attraktivt är förmågan att dra nytta av endast solenergi. En av fördelarna med textilier inom området är möjligheten att tillverka stora tygareor på ett enkelt och kostnadseffektivt vis.Elementär analys visade att TiO2-partikellager på textilierna fastande i olika grad beroende på beläggningsteknik. Avfärgning genom nedbrytning av metylenblått studerades under sollampa. Proverna utvärderades genom att vid bestämda tidpunkter avläsa kromavärdet på färglösningen. För att erhålla mer information om textilernas effekt gjordes även en bakterieanalys, samt bildtagning i ytterlig förstorning med SEM. Resultaten visade goda fotokatalytiska egenskaper för samtliga beläggningar, däribland är akryl- och hybridbeläggningarna mest lovande. Utöver det visade de textila bindningarna på substratens konstruktioner ha en påverkan på den vattenrenande effekten.In this bachelor essay work organic contaminants are removed from water using textiles, whose surface is coated with nanoparticles of titanium dioxide. When titanium dioxide is illuminated with UV radiation a photocatalytic reaction occurs, which in turn degrades substances such as bacteria and organic dyes. In hope of finding the ultimate adhesion for a textile coating suitable with titanium dioxide, various types of coatings are studies; acrylicbased, sol-gel and finally a hybrid coating. In addition, five different structures of textiles are compared in order to examine their different outcome in photocatalytic effect.Contaminated water is a major problem in both developing countries and industrial context. The use of a fabric to purify polluted water is an attractive idea, especially because the ability to exploit only solar energy. One of the benefits with use of fabric is the ability to producelarge areas of fabric, a process which is both simple and costeffective.Elemental analyses showed varying degree of fasten of the particle layer of TiO2 depending on the coating technology used. Decolorization by degradation of methylene blue was studied under a solar energy AM 1,5 lamp. The samples were evaluated by reading the chroma value of the color solution at specified moments. To obtain more information the coated textiles went through bacterial analysis, as well as picture shooting in extreme magnification with SEM. The results showed good photocatalytic properties for all coatings, among them were the acrylic coating and the hybrid most promising. In addition, results showed that depending on textile structures different effects in water purification was achieved. / Program: Textilingenjörsutbildningen

During this project, photocatalytic material, nano sized titanium dioxide, was introduced into poly (lactic acid) to produce functional surface capable of self-cleaning property. Samples containing 0%, 5%, 10%, 15% and 20% titanium dioxide were prepared and etched with proteinase K to expose the nano particles on the surface. It was shown that the nano titanium dioxide could dispersed in the polymer matrix pretty well, it was also found that the nano particles affected the thermal and mechanical properties of the polymer matrix differently , due to difference in concentrations of nano filler. The self-cleaning property was evaluated by decolouration of stains caused by coffee and red wine, also by detecting degradation of methylene blue via a UV-vis spectrophotometer. By measuring changes in absorbance of light at 664nm wavelength after a maximum of 24h UV irradiation, it was possible to measure the degradation property of the samples. / Program: Masterutbildning i textilteknik

Os mecanismos endógenos de proteção frente aos danos promovidos pelas radiações solares são insuficientes, tornando importante a utilização de formulações fotoprotetoras, corporais e labiais, para reduzir as lesões promovidas por tais radiações. Protetores labiais são preparações que protegem os lábios de fatores ambientais adversos e evitam o ressecamento. Citam-se, como exemplos, os fotoprotetores labiais, que protegem a mucosa labial das radiações ultravioleta A e B. Estes são compostos por filtros solares (compostos ativos), aditivos e agentes graxos, dentre outros, os quais podem exercer influência na eficácia fotoprotetora da preparação. Deste modo, estudar a influência da alteração quali e quantitativa de determinados componentes da fórmula na fotoproteção conferida pelo produto final é de grande valia para a melhoria da eficácia do fotoprotetor labial. Portanto, este trabalho objetivou o desenvolvimento de fotoprotetores labiais contendo manteiga de karitê (butyrospermum parkii) como composto bioativo, ethylhexyl methoxicinnamate como filtro solar orgânico e titanium dioxide como filtro solar inorgânico; a avaliação da estabilidade das preparações por meio da Avaliação Preliminar da Estabilidade; a caracterização organoléptica e física das preparações; e a determinação da eficácia fotoprotetora in vitro por espectrofotometria de refletância difusa com esfera de integração. Todas as balas foram consideradas estáveis. Dentre as variáveis estudadas, o titanium dioxide exerceu influência na maioria das respostas avaliadas (ponto de fusão por equipamento de ponto de fusão; valor de L*; valor de b*; distância máxima no teste de dureza; força máxima no cantilever test; valor de slope no cantilever test; razão UVA/UVB; fator de proteção solar; e porcentagem de transmitância). A manteiga de karitê exerceu influência nas respostas: distância máxima no teste de dureza; força máxima no cantilever test; e valor de slope no cantilever test (apenas a 25°C). O ethylhexyl methoxicinnamate influenciou nas respostas: distância máxima no teste de dureza; força máxima no cantilever test; valor de slope no cantilever test (apenas a 25°C); razão UVA/UVB; fator de proteção solar; e porcentagem de transmitância. Nenhuma das variáveis influenciou as respostas: valor de ponto de gota, DSC e a distância máxima no cantilever test. / The endogenous protection mechanisms against the damages promoted by solar radiations are insufficient. Therefore, the use of photoprotective formulations both corporal and labial, become important for the minimization of the lesions caused by these radiations. Lip protectors are preparations that protect the lips against adverse environmental conditions and avoid their dehydration. Photoprotective lipsticks may be cited as examples. These formulations protect the mucosa against ultraviolet A and B radiations. They are composed by solar filters (active compounds), addictives and fatty agents, amongst others, which may exert influence on the formulation\'s photoprotective efficacy. Therefore, the study of the influence of qualitative and quantitative alterations of certain components of the formula on the photoprotection supplied by the final product is greatly valuable for the efficacy improvement of a photoprotective lipstick. Hence, this research work aimed at the development of photoprotective lipsticks containing shea butter (butyrospermum parkii) as bioactive compound, ethylhexyl methoxicinnamate as organic filter and titanium dioxide as inorganic filter; the evaluation of formulations\' stability through the Preliminary Stability Test; physical and organoleptical characterization of the formulation; and the determination of the in vitro photoprotective efficacy by diffuse reflectance spectroscopy with integration sphere. All formulations were considered stable. Amongst the studied variables, titanium dioxide influenced the majority of the evaluated responses (melting point using melting point equipment; L* value; b* value; maximum distance on the hardness test; maximum strength on cantilever test; slope value on cantilever test; UVA/UVB ratio; sun protection factor; and transmittance percentage). Shea butter influenced: maximum distance on the hardness test; maximum strength on cantilever test; and slope value on cantilever test (only at 25°C). Ethylhexyl methoxicinnamate influenced: maximum distance on the hardness test; maximum strength on cantilever test; slope value on cantilever test (only at 25°C); UVA/UVB ratio; sun protection factor and transmittance percentage. None of the variables influenced drop point, DSC and maximum distance on the cantilever test.

O aumento da concentração de gases de efeito estufa (GEE) de fontes antropogênicas tem sido visto como uma das principais contribuições para o aquecimento global, ameaçando a vida no planeta. O dióxido de carbono (CO2) é um dos principais GEE e suas fontes geradoras estão relacionadas a processos essenciais à sociedade, como a produção de energia, produtos diversos e transporte. A conversão do CO2 parece ser uma alternativa promissora para reduzir a emissão deste gás na atmosfera. De particular interesse para este estudo, a fotorredução do CO2 a metanol pode contribuir para mitigar o problema dos GEE, gerando um importante insumo da indústria química. Assim, este estudo tem por objetivo utilizar cálculos quanto-mecânicos, como a Teoria do Funcional Densidade, para investigar um caminho para a reação de redução do CO2. A reação de redução do CO2 à ácido fórmico, formaldeído e metanol foi estudada sem a interação com o catalisador e na presença de dióxido de titânio como catalisador. Foi realizada uma comparação de cálculos em diferentes níveis teóricos e diferentes bases, com dados experimentais. Para os cálculos envolvendo o TiO2, foi utilizado o nível B3LYP/6-31G(d,p). Frequências vibracionais também foram calculadas para cada etapa, permitindo a identificação de possíveis estados de transição e estimativa de barreiras de reação (energia potencial). Cálculos de coordenada intrínseca de reação (IRC) foram empregados para confirmar que os estados de transição encontrados, estão relacionados a cada etapa estudada. A comparação da redução do dióxido de carbono a ácido fórmico, com e sem catalisador, mostrou que a presença do dióxido de titânio reduziu em mais de 25,0% a barreira reacional desta etapa

Os mecanismos endógenos de proteção frente aos danos promovidos pelas radiações solares são insuficientes, tornando importante a utilização de formulações fotoprotetoras, corporais e labiais, para reduzir as lesões promovidas por tais radiações. Protetores labiais são preparações que protegem os lábios de fatores ambientais adversos e evitam o ressecamento. Citam-se, como exemplos, os fotoprotetores labiais, que protegem a mucosa labial das radiações ultravioleta A e B. Estes são compostos por filtros solares (compostos ativos), aditivos e agentes graxos, dentre outros, os quais podem exercer influência na eficácia fotoprotetora da preparação. Deste modo, estudar a influência da alteração quali e quantitativa de determinados componentes da fórmula na fotoproteção conferida pelo produto final é de grande valia para a melhoria da eficácia do fotoprotetor labial. Portanto, este trabalho objetivou o desenvolvimento de fotoprotetores labiais contendo manteiga de karitê (butyrospermum parkii) como composto bioativo, ethylhexyl methoxicinnamate como filtro solar orgânico e titanium dioxide como filtro solar inorgânico; a avaliação da estabilidade das preparações por meio da Avaliação Preliminar da Estabilidade; a caracterização organoléptica e física das preparações; e a determinação da eficácia fotoprotetora in vitro por espectrofotometria de refletância difusa com esfera de integração. Todas as balas foram consideradas estáveis. Dentre as variáveis estudadas, o titanium dioxide exerceu influência na maioria das respostas avaliadas (ponto de fusão por equipamento de ponto de fusão; valor de L*; valor de b*; distância máxima no teste de dureza; força máxima no cantilever test; valor de slope no cantilever test; razão UVA/UVB; fator de proteção solar; e porcentagem de transmitância). A manteiga de karitê exerceu influência nas respostas: distância máxima no teste de dureza; força máxima no cantilever test; e valor de slope no cantilever test (apenas a 25°C). O ethylhexyl methoxicinnamate influenciou nas respostas: distância máxima no teste de dureza; força máxima no cantilever test; valor de slope no cantilever test (apenas a 25°C); razão UVA/UVB; fator de proteção solar; e porcentagem de transmitância. Nenhuma das variáveis influenciou as respostas: valor de ponto de gota, DSC e a distância máxima no cantilever test. / The endogenous protection mechanisms against the damages promoted by solar radiations are insufficient. Therefore, the use of photoprotective formulations both corporal and labial, become important for the minimization of the lesions caused by these radiations. Lip protectors are preparations that protect the lips against adverse environmental conditions and avoid their dehydration. Photoprotective lipsticks may be cited as examples. These formulations protect the mucosa against ultraviolet A and B radiations. They are composed by solar filters (active compounds), addictives and fatty agents, amongst others, which may exert influence on the formulation\'s photoprotective efficacy. Therefore, the study of the influence of qualitative and quantitative alterations of certain components of the formula on the photoprotection supplied by the final product is greatly valuable for the efficacy improvement of a photoprotective lipstick. Hence, this research work aimed at the development of photoprotective lipsticks containing shea butter (butyrospermum parkii) as bioactive compound, ethylhexyl methoxicinnamate as organic filter and titanium dioxide as inorganic filter; the evaluation of formulations\' stability through the Preliminary Stability Test; physical and organoleptical characterization of the formulation; and the determination of the in vitro photoprotective efficacy by diffuse reflectance spectroscopy with integration sphere. All formulations were considered stable. Amongst the studied variables, titanium dioxide influenced the majority of the evaluated responses (melting point using melting point equipment; L* value; b* value; maximum distance on the hardness test; maximum strength on cantilever test; slope value on cantilever test; UVA/UVB ratio; sun protection factor; and transmittance percentage). Shea butter influenced: maximum distance on the hardness test; maximum strength on cantilever test; and slope value on cantilever test (only at 25°C). Ethylhexyl methoxicinnamate influenced: maximum distance on the hardness test; maximum strength on cantilever test; slope value on cantilever test (only at 25°C); UVA/UVB ratio; sun protection factor and transmittance percentage. None of the variables influenced drop point, DSC and maximum distance on the cantilever test.

La mise en forme de matériaux fonctionnels et leur texturation contrôlée à toutes les échelles sont des conditions sine qua non pour l’amélioration des systèmes existants. Ce projet de thèse consiste en la création de structures solides complexes en utilisant des méthodes interdisciplinaires telles que la chimie sol-gel et la physique des fluides complexes. Ainsi, il est possible d’obtenir des fibres ou des films de dioxyde de Titane poreux présentant des pores de différentes tailles organisés hiérarchiquement. Cette organisation texturale optimise le transport de matière (gaz / liquides) pour des applications telles que la dépollution d’air (photocatalyse) ou les cellules solaires à colorant. Par ailleurs, nous avons contrôlé l’alignement de nano-bâtonnets d’oxyde de Zinc au sein d’une fibre macroscopique générant ainsi des propriétés collectives d’émission de lumière (photoluminescence)anisotrope, spécificité d’utilité pour l’électronique à permutation. Enfin, nous avons synthétisé des nano objets anisotropiques et des nano-lamelles de polypyrrole afin de générer des films minces lisses avec des propriétés électriques permettant leur utilisation comme électrode ou électrolyte solide dans des cellules solaires à colorant. / The shaping of functional materials and the control of their texture at all length scales are sine qua non conditions for the improvement of current systems. This PhD project consists in creating complex solid architectures using interdisciplinary methods such as sol-gel chemistry or complex fluids physics. Therefore, it is possible to synthesize Titanium Dioxide macroscopic fibers orfilms which possess a hierarchical porosity. This organization allows the optimization of the matter transport (liquid/gaz) for air depollution application (photocatalysis) or dye-sensitizedsolar cells. In another project, we were able to control the alignment of zinc oxide nanorods within a macroscopic fiber. This alignment provides to the fiber an anisotropic photoluminescence behavior which can be useful for switching devices application. Finally, we synthesized anisotropic particles and nano-sheets of polypyrrole (conducting polymer) in order to obtain smooth thin films presenting interesting electrical properties. The objective was to use them as electrolyte and/or electrode in dye-sensitized solar cells.

Des substrats SERS, élaborés selon une approche simple et à moindre coût, ont été étudiéspour la détection sans marqueurs d’ADN en vue d’applications dans le domaine du diagnostic médical.Un protocole de réduction photocatalytique assistée chimiquement conduisant à des hétérostructuresAg°/TiO2 a été optimisé. Nohttp://star.theses.fr/editeur.jsp?tefId=58411&action=save#droitsus avons montré en quoi l’utilisation d’un agent encapsulant et d’uneprocédure de nucléation-croissance permettent de contrôler la formation et l’agrégation de NPs Ag° à lasurface de couches minces TiO2. L’agrégation contrôlée des NPs conduit à des points chauds induisantune très forte amplification de l’effet SERS. Les performances des substrats SERS ont tout d’abord étévalidées par détection Raman de la molécule modèle R6G. Des études de fond, portant sur la détectionde polybases dérivées des quatre nucléobases constituant la structure de l’ADN, adénine, cytosine,guanine et thymine, ont ensuite été réalisées. Le potentiel de détection des hétérostructures Ag°/TiO2 apermis l’indexation quasi-intégrale des bandes Raman des quatre polybases étudiées, modifiées ou nonavec des groupements NH2, et nous a permis de discuter des effets d’accrochage, d’orientation etd’agencement des molécules d’ADN sur les substrats SERS. Des études complémentaires ont finalementconfirmé le potentiel de nos hétérostructures en fournissant différents aperçus sur l’hybridation despolybases et l’association de différentes polybases sur un même substrat SERS. / SERS substrates, elaborated through a simple and low-cost procedure, have been studied forthe label-free detection of DNA in the view of applications in the medical diagnostic field. A chemicallyassisted photocatalytic reduction protocol leading to an Ag°/TiO2 heterostructure has been optimized.We have shown how the use of an encapsulating agent and a nucleation-growth procedure enable tocontrol the formation and aggregation of Ag° NPs at the surface of TiO2 thin films. The controlledaggregation of NPs leads to hot points inducing a very strong amplification of the SERS effect.Performances of the SERS substrate have first been evaluated through the Raman detection of the R6Gmodel molecule. Thorough studies dealing with the detection of polybases derived from the fournucleobases constituting the DNA structure, adenine, cytosine, guanine, and thymine, have then beenconducted. The detection potential of the Ag°/TiO2 heterostructure enabled a nearly exhaustiveindexation of the Raman bands for the four studied polybases, modified or not with NH2 groups, and todiscuss on binding, orientation, and ordering effects of the DNA molecules on the SERS substrate.Complementary studies finally enabled us to confirm the potential of our heterostructure by providingdifferent insights on the polybase hybridization and the association of different polybases on a sameSERS substrate.

<p>This thesis is based on experimental studies in chemical physics. Titanium dioxide (TiO₂) and phthalocyanine’s (Pc’s), interesting in many future perspectives, have been deposited as thin films and studied as follows. Information has been obtained on e.g. molecular orientation, crystal structure, depth profile of the chemical composition, electrochemical properties and electronic structure. This has been achieved by means of a combination of techniques: X-ray photoelectron spectroscopy (XPS), near edge x-ray absorption fine structure (NEXAFS), density functional theory calculations (DFT), UV-visible absorption spectroscopy (UVVIS) and cyclic voltammetry (CV).</p><p>Metal-free phthalcyanine (H₂Pc) has been shown to form films with different crystal structure and molecular orientation depending on deposition method, evaporation/sublimation or powder deposition, on commercial conducting glass (fluorine doped tin oxide, FTO), which is used e.g. in solar cells and organic light emitting devices (OLEDs). The unoccupied molecular orbitals are divided in x, y and z space coordinates of the molecule and also divided in inequivalent nitrogen components. </p><p>The electronic structure is also studied for a sublimated titanyl phthalocyanine (TiOPc) film and related to the metal-free phthalocyanine. The ligand field around the titanium atom in TiOPc is compared with that of TiO₂ to delineate the unoccupied levels recorded by means of x-ray absorption spectroscopy.</p><p>Nanostructured TiO₂ films were manufactured by screen printing/doctor blading on FTO. Such films were additionally covered with lutetium diphthalocyanine (LuPc₂) by means of surface assembly from solution. LuPc₂^-, LuPc₂⁺ and LuPc₂H were identified and the stability of the electrochromic reactions in this system was monitored.</p><p>Chemical vapor deposition (CVD) has been used to grow nanometer sized anatase TiO₂ crystals on pre-oxidized Si (111) without formation of interfacial carbon and with an interface layer of the size of 15- 25Å. The interface layer was found to be amorphous TiSi_xO_y with graded stoichiometry. </p>

<p>This work reports the chemical synthesis, characterisation and electrochemical application of titanium dioxide (TiO2) and iron oxide (Fe2O3) nanoparticles in the determination of phthalates. The other part of this work involved electrochemical polymerization of aniline doped with titanium and iron oxide nanoparticles for the sensor platform in the electrolytic determination of phthalates. The TiO2 and Fe2O3 nanoparticles were prepared by sol gel and hydrothermal methods respectively. Particle sizes of 20 nm (TiO2) and 50 nm (Fe2O3) were estimated from transmission electron microscopy (TEM) The other technical methods used in this study for the characterization of the TiO2 and iron oxide Fe2O3 NPs were SEM, XRD and UV- visible spectroscopy. Cyclic voltammetry, square wave voltammetry and electrochemical impedance spectroscopy (EIS) were used to study the electrochemical properties of the nanoparticles. These electrochemical studies of the nanoparticles were performed with a Fe2O3 or TiO2/nafion/glassy carbon membrane electrode in 0.1 M phosphate buffer (pH 7.0) and 0.1 M lithium perchlorate (pH 6.8) under an aerobic condition.</p>

<p>In this research project, nanostructured composites based on Tin dioxide (SnO2) and Titanium dioxide (TiO2) with poly-4-styrene sulfonic acid (PSSA) doped polyaniline (PANI) conducting polymer has been investigated based on their structural, electrical and electrochemical properties. The synthesis of conducting polymers and their metal oxide or composites have been carried out chemically or electrochemically according to methods modified from the literature. Layer-by-layer construction of nano-Metal Oxide/PSSA doped polyaniline composites were successfully constructed by electroanalytical methods on the surface of a glassy carbon working electrode (GCE).</p>