Made available in DSpace on 2014-12-17T15:41:49Z (GMT). No. of bitstreams: 1 ErileideCR_DISSERT.pdf: 2520187 bytes, checksum: cbaac2eaf2812c34709374f87564cb10 (MD5) Previous issue date: 2010-07-12 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Corrosion is an important phenomenon that frequently occurs in the oil industry, causing surface ablation, such as it happens on the internal surfaces of oil pipes. This work aims to obtain new systems to reduce this specific problem. The surfactants SDS, CTAB, and UNITOL L90 (in micellar and microemulsionated systems) were used as corrosion inhibitors. The systems were obtained using a C/S ratio of 2, butanol as cosorfactant, kerosene as oil phase and, as water phase, NaCl solutions of 0.5M with pH = 2, 4, and 7. Microemulsion regions were found both for direct and inverse micelles. SDS had the higher microemulsion region and the area was not dependent of pH. The study of micellization of these surfactans in the liquid-gas interface was carried out via the determination of CMC from surface tension measurements. Regarding microemulsionated systems, in the case of CTAB, CMC increased when pH was increased, being constant for SDS and UNITOL L90. Concerning micellar systems, increase in pH caused decrease and increase in CMC for SDC and CTAB, respectively. In the case of UNITOL L90, CMC was practically constant, but increased for pH = 4. The microemulsionated systems presented higher CMC values, except for UNITOL L90 L90. The negative values of free energy of micellization indicated that the process of adsorption was spontaneous. The results also indicated that, comparing microemulsionated to systems, adsorption was less spontaneous in the case of SDS and CTAB, while it did not change for UNITOL L90. SAXS experiments indicated that micelle geometry was spherical, existing also as halter and flat micelles, resuting in a better inght on the adsorption at the liquid-solid interface. Efficiency of corrosion inhibition as determined by electrochemical measurements, from corrosion currents calculated from Tafel extrapolation indicuting heat showed surfactants to be efficient even at low concentrations. Equilibrium isotherm data were fitted to the Freundlich model, indicating that surfactant adsorption occurs in the form of multilayers / A corros?o ? um fen?meno presente em diversos seguimentos da ind?stria do petr?leo, causando desgastes em superf?cies de equipamentos met?licas, como exemplo a corros?o interna nos oleodutos. Este trabalho visa obter novos sistemas qu?micos para diminuir tal problema. Os tensoativos utilizados como inibidores de corros?o foram o SDS, CTAB e UNITOL L90 em sistemas micelares e microemulsionados. Para obten??o dos sistemas microemulsionados utilizou-se uma raz?o C/T=2, butanol como cotensoativo, querosene como fase ?leo e como fase aquosa utilizou-se solu??es de NaCl 0,5M nos pH s 2, 4 e 7. As regi?es de microemuls?o encontradas para os tr?s tensoativos s?o formadas por micelas diretas e inversas. A ?rea se mant?m constante com a varia??o do pH, o SDS tem maior regi?o de microemuls?o. O estudo da miceliza??o destes tensoativos na interface l?quido-g?s foi realizado a partir de medidas de tens?o superficial obtendo os valores de c.m.c, os quais foram particamente constantes para os sistemas microemulsionados com os tensoativos SDS e UNITOL L90 L90, e aumentaram para o CTAB quando elevou-se o pH. Os valores de c.m.c para os sistemas micelares com os tensoativos SDS e CTAB diminu?ram e aumentaram, respectivamente, quando aumentou-se o pH. J? o UNITOL L90 apresentou valores praticamente constantes, por?m foi maior em pH 4. Os sistemas microemulsionados apresentaram valores de c.m.c maiores, exceto para o tensoativo UNITOL L90. Os valores negativos de energia livre de miceliza??o indicaram que o porcesso de adsor??o ? espont?neo. Os resultados mostraram que os sistemas microemulsionados para os tensoativos SDS e CTAB foram menos espont?neos comparados ao sistema micelar, enquanto o UNITOL L90 apresentou valores praticamente constantes. Experimentos com SAXS mostraram que as geometrias das micelas foram esf?ricas, existindo ainda na forma de halteres ou de micelas achatadas, o que facilitou a compreens?o do estudo de adsor??o na interface l?quido-s?lido. As efici?ncias de inibi??o ? corros?o foram determinadas mediante medidas eletroqu?micas, a partir das correntes de corros?o encontradas atrav?s da extrapola??o de Tafel. Os tensoativos estudados se mostraram eficientes mesmo em baixas concentra??es. Os dados experimentais de ajustaram ao modelo da isoterma de Freundlich, indicando que a adsor??o dos tensoativos ocorre em multicamadas

Que ce soit à des fins de contrôle qualité ou de veille concurentielle, la déformulation (action d'identifier et de quantifier les constituants d'un produit) représente aujourd'hui un véritable challenge analytique dans de nombreux domaines industriels tels que les cosmétiques, la santé, les matériaux... Dans ce contexte, nous nous sommes intéressés aux mélanges complexes que sont les produits détergents tels que les lessives qui représentent un marché en constante croissance et en perpétuelle évolution. Dans ce secteur, en effet, les réglementations sont de plus en plus drastiques et les consommateurs plus exigeants ce qui entraine le développement de nouveaux produits plus respectueux de l'environnement et de la santé intégrant des tensioactifs bio-sourcés et des enzymes. Les lessives pouvant contenir jusqu'à 25 composés différents, nous nous sommes focalisés sur l'analyse de leurs composés majoritaires que sont les tensioactifs et les enzymes. Après avoir élaboré une échantillothèque exhaustive de ces produits, la RMN du proton et la spectrométrie Raman ont été utilisées pour identifier et quantifier les tensioactifs et la spectrométrie de masse des rapports isotopiques (IRMS) pour l'évaluation de leur origine bio-sourcée. Les résultats obtenus ont montré l'intérêt du couplage de la spectroscopie Raman avec des méthodes chimiométriques d'extraction du signal comme l'ICA et la MCR-ALS pour identifier et quantifier les tensioactifs. L'IRMS a permis d'identifier les tensioactifs d'origine bio-sourcée ainsi que le type de plantes (C3 ou C4) utilisé comme matière première pour leur synthèse. Les enzymes utilisées dans la formulation d'une lessive commerciale ont pu être identifiées et quantifiées grâce à l'association d'une méthode de précipitation des protéines avec une analyse par LC-MS/MS. Ces développements analytiques contribuent à la mise en place d'une méthodologie de la déformulation des produits détergents / Deformulation of complex mixtures requires analytical methods for compound identification and quantification. It still represents a real analytical challenge in various industrial fields, such as cosmetics, health, food, materials. In this context, we studied complex mixtures such as detergents and especially, laundry detergents, that represent a constantly growing market. Regulations becoming stricter and consumers requiring more eco-friendly products, manufacturers constantly innove detergent formulations by using bio-based surfactants or enzymes. Laundry detergents containing up to 25 compounds, we focused on the analysis of their major components, i.e. surfactants and enzymes. After developing a comprehensive sample library of such raw materials, 1H NMR and Raman spectrometry were used for surfactant identification and quantification while Isotope Ratio Mass Spectrometry (IRMS) was tested to evaluate their bio-sourced origin. Raman spectrometry combined with chemometric tools such as signal extraction methods was useful for surfactant identification and quantification. Enzymes were identified and quantified using protein precipitation before analyses by LCMS/ MS. All these analytical developments contribute to the establishment of a deformulation strategy for detergent products

"Neste trabalho, propõe-se o desenvolvimento de instrumentação e procedimentos analíticos automáticos para a determinação de tensoativos em águas empregando o conceito de multicomutação em fluxo. Visando a miniaturização do sistema, a minimização do consumo de reagentes, e da geração de efluentes foram utilizadas mini-bombas solenóide para a propulsão dos fluidos e válvulas solenóide de estrangulamento para controlar a manipulação das soluções. Estes dispositivos foram controlados por um microcomputador equipado com uma interface eletrônica baseada no circuito integrado ULN2803A a qual foi acoplada à saída da impressora. Como sistema de detecção foram empregados um espectrofotômetro HP8452A, um espectrofotômetro multicanal com arranjo linear de fotodetectores do tipo CCD e um fotômetro baseado em dois LEDs (azul e vermelho) como fonte de radiação e um fotodiodo de silício (IPL10530DAL) como detector. A aquisição dos dados do fotômetro foi realizada com um multímetro digital com saída serial RS232, empregando um programa escrito em linguagem VISUAL BASIC 3.0. No mesmo programa foram incluídas rotinas para controle do módulo de análise. Primeiramente, foram desenvolvidos a instrumentação e os procedimentos analíticos para a determinação independente de tensoativos aniônicos e catiônicos em águas. O mesmo módulo de análises foi utilizado para os dois tensoativos e foi constituído de quatro mini-bombas solenóide. O procedimento proposto para a determinação de tensoativos aniônicos foi baseado na substituição do reagente cromogênico alaranjado de metila (MO) pelo tensoativo aniônico dodecilbenzeno sulfonato de sódio (DBS), formando o par-iônico com o tensoativo catiônico cloreto de cetilpiridino (CPC) em pH 5,0. A instrumentação proposta possibilitou a obtenção de resposta linear entre 1,4 x 10-6 mol L-1 e 1,4 x 10-5 mol L-1 (0,5 - 5 mg L-1) (R = 0,997, n = 7), limite de detecção de 9,8 x 10-8 mol L-1 (0,034 mg L-1), e freqüência de amostragem de 60 determinações por hora. O desvio padrão relativo foi estimado em 0,8 % (n = 11) usando uma solução de referência contendo 5,7 x 10-6 mol L-1 (2 mg L-1) de DBS. Os resultados obtidos pelo método proposto processando amostras de efluentes domésticos e industriais foram comparados com os obtidos empregando-se o método de referência, e não foi observada diferença significativa em nível de confiança de 95 %. Para a determinação de tensoativos catiônicos em águas foi desenvolvido um procedimento baseado na formação do complexo ternário entre tensoativo catiônico CPC, Fe (III) e cromazurol S (CAS) em pH 4,5. Com o sistema proposto, utilizando-se uma cela de detecção de 40 mm de comprimento, obteve-se resposta linear entre 0,1 x 10-5 mol L-1 e 3,0 x 10-5 mol L-1 (0,34 - 10,2 mg L-1) (R = 0,999, n = 9), limite de detecção estimado em 1,0 x 10-7 mol L-1 (0,035 mg L-1), desvio padrão relativo de 0,6 % (n = 11) empregando uma solução de referência contendo 1,0 x 10-5 mol L-1 (3,4 mg L-1) de CPC, e freqüência de amostragem de 72 determinações por hora. O procedimento foi aplicado em amostras de águas coletadas no rio Piracicaba. Empregando-se teste de adição e recuperação foi observada recuperação entre 91 % e 106 %. O módulo de análise para a determinação seqüencial de tensoativos aniônicos e catiônicos foi constituído de duas mini-bombas solenóide e seis válvulas solenóide de estrangulamento. Com o sistema proposto, as características analíticas para os tensoativos aniônicos foram: resposta linear entre 0,1 x 10-5 mol L-1 e 3,0 x 10-5 mol L-1 (0,35 - 10,5 mg L-1) (R = 0,9992, n = 7); limite de detecção estimado em 1,6 x 10-7 mol L-1 (0,056 mg L-1); desvio padrão relativo de 0,6 % (n = 11) usando uma solução de referência contendo 1,0 x 10-5 mol L-1 (3,5 mg L-1) de DBS. Para os tensoativos catiônicos obteve-se resposta linear entre 0,1 x 10-5 mol L-1 e 3,0 x 10?5 mol L-1 (0,34 - 10,2 mg L-1) (R = 0,9992, n = 7); limite de detecção estimado em 1,4 x 10-7 mol L-1 (0,05 mg L-1); desvio padrão relativo de 0,5 % (n = 11) usando uma solução de referência contendo 1,0 x 10-5 mol L-1 (3,4 mg L-1) de CPC. O consumo das soluções de reagentes e de amostra foram de 400 mL e 200 mL, respectivamente, e freqüência de amostragem de 60 determinações por hora, para ambos tensoativos. O sistema foi aplicado em amostras de águas coletadas no rio Corumbataí, e os resultados obtidos com testes de adição e recuperação variaram entre 91 % e 105 %. Aplicando-se teste-t entre os resultados obtidos pelo procedimento proposto e pelos métodos de referência (aniônicos) e de validação (catiônicos), os resultados foram concordantes em nível de 95 % de confiança." / "In this work, development of the instrumentation and automatic analytical procedures for spectrophotometric determination of surfactants in waters employing the multicommutation concept were proposed. Aiming to system miniaturization, reduction of reagents consumption and effluents generation, solenoids micro-pump and solenoids pinch valves were used for the fluids propulsion and for solutions management, respectively. These devices were controlled by a microcomputer equipped with an electronic interface based on the integrate circuit ULN2803A that was coupled to the printer output. As system detection was employed an spectrophotometer model HP8452A, a multichannel spectrophotometer with CCD array linear arrangement of photodetectors and a homemade LED based photometer comprising two LEDs (blue and red) as radiation source and a photodiode (IPL10530DAL) as detector. In this case, the data acquisition was accomplished with a digital multimeter with serial out put RS232 employing a software wrote in VISUAL BASIC 3.0. The software comprised also routines to control the analysis module. Firstly, instrumentation and analytical procedures for independent determination of anionic and cationic surfactants in waters were developed. The same flow system comprised of four solenoid micro-pumps and it was employed for both surfactants. The procedure proposed for the determination of anionic surfactant was based on the substitution reaction of orange methyl (MO) by anionic surfactant (sodium dodecylbenzene sulfonate - DBS) to form an ion-pair with the cetyl pyridine (CPC) at pH 5.0. The proposed instrumentation allowed the achievement of a lineal response range between 1.4 x 10-6 mol L-1 and 1.4 x 10-5 mol L-1 (0.5 – 5.0 mg L-1) (R = 0.997, n = 7), a detection limit of 9.8 x 10-8 mol L-1 (0.034 mg L-1), a relative standard deviation of 0.8% (n = 11) for a reference solution containing 5.7 x 10-6 mol L-1 (2.0 mg L-1) DBS and sampling throughput of 60 determinations per hour. Results obtained applying the proposed procedure for domestic and industrial effluent samples were compared with those obtained using reference method and no significant differences at the 95 % confidence level was observed. For the determination of cationic surfactant in waters the procedure was developed based on the ternary complex formation between CPC, Fe (III) and chromazurol S at pH 4.5. The proposed system comprised a flow cell device with 40 mm optical path-length presented the following features: a linear response range between 0.1 x 10-5 mol L-1 e 3.0 x 10-5 mol L-1 (0.34 – 10.2 mg L-1) (R = 0.999, n = 9); a detection limit of 1.0 x 10-7 mol L-1 (0.035 mg L-1); a relative standard deviation of 0.6 % (n = 11) for a reference solution containing 1.0 x 10-5 mol L-1 (3.4 mg L-1) CPC; and a sampling throughput of 72 determinations per hour. The procedure was applied to samples waters collected in the Piracicaba River. Using standard addition test recoveries between 91 % and 106 % were observed. The flow network for the sequential determination of anionic and cationic surfactants comprised two solenoid micro-pumps and six solenoid pinch valves. Employing the system proposed for the determination of anionic surfactants the folowing analytical characteristics: linear response range between 0.1 x 10-5 mol L-1 e 3.0 x 10-5 mol L-1 (0.35 – 10.5 mg L-1) (R = 0.9992, n = 7); a detection limit of 1.6 x 10-7 mol L-1 (0.056 mg L-1); a relative standard deviation of 0.6 % (n = 11) for a reference solution containing 1.0 x 10-5 mol L-1 (3.5 mg L-1) DBS were observed. For cationic surfactants a linear response range between 0.1 x 10-5 mol L-1 e 3.0 x 10?5 mol L-1 (0.34 - 10.2 mg L-1) (R = 0.9992, n = 7), a detection limit of 1.4 x 10-7 mol L-1 (0.05 mg L-1), a relative standard deviation of 0.5 % (n = 11) for a reference solution containing 1.0 x 10-5 mol L-1 (3.4 mg L-1) CPC were observed. In both cases, the reagents and sample consumption were 400 mL and 200 mL, respectively. The sampling throughput of 60 determinations per hour was achieved for both surfactants. The system was applied to waters samples from the Corumbataí River. The results obtained using the standard addition test presented recoveries between 91 % and 105 %. Applying t-test between the results obtained by the proposed procedures and those obtained using reference procedures showed that for anionic and cationic surfactants, the results were concordant at 95% confidence level."

Uma nova série de porfirinas catiônicas e seus respectivos metalocomplexos de Zn(II) e Cu(II) foi sintetizada. Esta nova série apresenta resíduos benzílicos substituídos ligados aos grupos piridínicos presentes nas posições meso do anel porfirínico. Estes compostos foram caracterizados e investigados utilizando várias técnicas, tais como: espectroscopia eletrônica de absorção e de emissão, RMN-1H, espectroscopia vibracional IR e raman ressonante, voltametria cíclica, espectroeletroquímica e fotólise por pulso de laser. Não foram observadas evidências de auto-agregação destes compostos em água, entretanto, estes apresentam agregação diferenciada em função da força iônica do meio, do ânion do eletrólito utilizado e do tamanho do substituinte periférico. Os potenciais de redução apresentam dependência ao caráter aceptor/doador de elétrons dos substituintes benzílicos. As porfirinas desta série apresentam parâmetros fotofísicos da mesma ordem de grandeza e comparáveis ao composto modelo 5, 10, 15,20-tetrakis(1-metilpiridínio-4-il)-porfirina (H2TMPyP) e seus metaloderivados em meio homogêneo. Em meio microhetrogêneo são observadas alterações nestes parâmetros fotofísicos, existindo um comportamento diferenciado em relação à H2TMPyP. Uma análise global dos resultados evidência que estes derivados são promissores fotossensibilizadores em sistemas de terapia fotodinâmica. / A new series of cationic porphyrins and metalloporphyrins derivatives of Cu(II) and Zn(II) has been synthesized. These compounds show substituted benzylic residues attached to the piridil groups at the meso porphyrin ring positions. All porphyrins and metalloporphyrin have been fully characterized and investigated, employing approaches such as elemental analysis, electronic, vibrational and proton NMR spectroscopy, flash photolysis, and cyclic voltammetry. There is no evidence of self-aggregation of the porphyrin derivatives in pure water, however the addition of inorganic electrolytes to water solution induces aggregation in different extension, which depends on the nature of the electrolyte, the total ionic strength, and the benzylic substituent. Studies of cyclic voltammetry show that the reduction potentials are directly dependent on the electron donor/acceptor characteristics of the benzylic substituent and of the coordinated metal ion. All photophysical parameters investigated in homogeneous media are very similar through porphyrins and metalloporphyrins studied and are comparable to the model compound, the 5, 10, 15, 20-tetrakis(1-methylpyridinium-4-yl)porphyrin (H2TMPyP). Therefore, in micro-heterogeneous media, the new series of porphyrins presents some differences in the photophysical parameters, when compared to the model compound. In conclusion, the present results reveal that these new cationic porphyrins can be useful as photosensitizers in photodynamic therapy.

Atualmente, decorrente da cultura estética onde há o culto aos corpos esbeltos com aparência saudável e pele lisa, macia e viçosa, a hidrolipodistrofia ginóide, conhecida como celulite, tem sido um dos desafios para os dermatologistas e cirurgiões plásticos. Assim, temse testado diferentes formas de tratamentos entre as quais estão aplicações de cremes à base de xantinas visando a atenuação dos sintomas. O conhecimento das propriedades físicoquímicas de tais formulações é essencial para otimizar as condições de produção e liberação do ativo na pele, além de prover elegância cosmética do produto desenvolvido. Os objetivos desse trabalho foram obter e avaliar a estabilidade de emulsões O/A contendo fase líquida cristalina, adicionada de cafeína, para aplicação no tratamento da hidrolipodistrofia ginóide, bem como avaliar o perfil de liberação da substância ativa in vitro com intuito de determinar sua disponibilidade. A emulsão O/A contendo como fase oleosa, óleos vegetais naturais (óleo de urucum, de café e de melaleuca) foi desenvolvida através da utilização do Sistema Equilíbrio Hidrófilo- Lipófilo (EHL). Utilizando os tensoativos não-iônicos Ceteareth 5 e Steareth 2 nas concentrações de 10,0 e 15,0% foi possível obter fases líquidas cristalinas lamelares. A adição de cafeína a 1,0% foi conseguida em emulsão contendo 15,0% da mistura de tensoativos e com auxílio na solubilização através do uso de benzoato de sódio na mesma concentração (1,0%). As emulsões foram consideradas estáveis segundo as condições experimentais e parâmetros analisados. O perfil de liberação da substância ativa apresentou fase inicial de liberação mais rápida seguida de outra mais lenta. A eletroforese capilar mostrou-se ferramenta mais adequada para quantificação do ativo. Os resultados sugerem que os cristais líquidos lamelares estejam atuando provavelmente como veículo de liberação lenta. / Nowadays, due to aesthetic culture that there is the cult to slim body with health appearance and smooth, vigorous skin, the gynoid hydrolipodystrophy, known as cellulite, has been one of the challenges for dermatologists and plastic surgeons. Thus, different kinds of treatments have been tested, and among them, the application of xantines-based creams in order to attenuate the symptoms. The knowledge of the physicochemical properties of such formulations is essential to optimize the production conditions and active skin delivery, besides promoting cosmetic elegance of the developed product. The aims of this research were to attain and to evaluate the stability of O/W emulsions containing liquid crystalline phase, with the addition of caffeine, to be used on the gynoid hydrolipodystrophy treatment, as well as evaluate the release profile of the active in vitro in order to determine its availability. The O/W emulsion containing natural vegetable oils (annatto oil, coffee oil and tea tree oil) as oily phase was developed through the utilization of Hydrophilic Lipophilic Balance System (HLB). When using the non-ionic surfactants Ceteareth 5 and Steareth 2 in the 10.0 and 15.0% concentrations it was possible to obtain lamellar liquid crystalline phases. The addition of caffeine 1.0% was attained in emulsion containing 15.0% of the surfactant mixture and its solubility was improved through the sodium benzoate use in the same concentration. The emulsions were considered stable according to the experimental conditions and evaluated parameters. The release profile of the active agent presented a faster initial phase followed by a slower one. The capillary electrophoresis showed a more suitable tool to quantify the active. The results suggest that the lamellar liquid crystals are probably acting as slow delivery vehicle.

A influência dos tensoativos lauril sulfato de sódio, cloreto de cetil trimetil amônio e álcool láurico etoxilado com 12 moles de óxido de etileno sobre o stratum corneum da pele de muda das cobras Bothrops jararaca e Spilotis pullatus foi avaliada através das técnicas biofísicas de PAS-FTIR, FT-Raman e DSC. Foram utilizadas soluções dos tensoativos em concentrações acima e abaixo da cmc e tratamentos por 4 e 8 horas (stratum corneum íntegro) e por 12 horas (stratum corneum após a remoção mecânica das camadas superficiais de células com fita adesiva). A presença do lauril sulfato de sódio e do cloreto de cetil trimetilamônio no stratum corneum foi detectada e a principal alteração observada para ambos foi o aumento do conteúdo hídrico do tecido; o álcool láurico etoxilado com 12 moles de óxido de etileno não promoveu aumento do conteúdo hídrico, apresentando ação de extração de lipídeos. A remoção mecânica das camadas superficiais de células com fita adesiva mostrou ser um procedimento útil para tratamento do stratum corneum da pele de muda de cobra, tornando a membrana mais adequada para estudos da ação de promotores de permeação. / The influence of the surfactants sodium lauryl sulfate, cetyl trimethyl ammonium chloride and lauryl alcohol ethoxylate (12 moles ethylene oxide) was evaluated on the stratum corneum of shed snake skin (Bothrops jararaca and Spilotis pullatus) through the biophysical techniques PAS-FTIR, FT-Raman and DSC. The surfactants were used in solutions above and below the cmc and the stratum corneum samples were pre-treated for periods of 4 and 8 hours (whole stratum corneum) and for 12 hours (stratum corneum after tape stripping procedure). The presence of the surfactants sodium lauryl sulfate and cetyl trimetyl ammonium chloride could be detected in the stratum corneum and the main change promoted by both was the increase of the water content of the membrane; the lauryl alcohol ethoxylate (12 moles ethylene oxide) did not promote increase in the hydration but showed some action as far as lipid extraction. The tape stripping procedure showed to be useful for the treatment of the stratum corneum of shed snake skin, making the membrane more adequate than the whole stratum corneum for the studies of the action of permeation enhancers.

Silica gels containing incorporated heteropolyacids (HPAs) were synthesized in acidic media by co-condensation of tetraethoxysilane (TEOS) with phosphotungstic or phosphomolybdic acids using sol-gel technique. Effect of the synthesis conditions on their structure and morphology was studied. Yields of modified materials were some lower as compared to non-modified silica gels. All materials were mesoporous but contained micropores in their structures. Presence of bands of Keggin’s structures in FT-IR spectra along with absence of XRD patterns of crystalline HPAs confirmed their fine incorporation into silica network. Particle sizes of modified materials were 800-1100 nm excepting for W-containing sample obtained with trimethylstearylammonium chloride. This unusual effect was attributed to stabilization of primary silica nanoparticles by interaction between surfactant and HPA. High ratio HPA/TEOS resulted in partial loss of porosity. Obtained results might be used for optimization of synthesis of effective catalysts and adsorbents containing HPAs in mesoporous structure.

Dans ce manuscrit, une voie atome économique d'un robuste amphiphile polyols à base de alkyle chaîne liée à liaison C-C ont été développés, ce qui est plus stable pour des applications plus larges. Ce processus implique l'utilisation de matières premières renouvelables et relativement peu coûteuses. Des cétoses tels que la 1,3-dihydroxyacétone et le D-fructose ont été utilisés comme substrats avec des aldéhydes comme agents d'alkylation sans aucune étape de protection-déprotection. La synthèse a été divisée en deux étapes, dans la première étape, les cétoses déprotonées réagissent avec les électrophiles aldéhydes pour former les intermédiaires hydroxycétones. Ensuite, une seconde étape d'hydrogénation avec un catalyseur du ruthénium sur alumine sous pression d'hydrogène a donné accès aux polyols alkylés. Le rendement global de ce procédé en deux étapes est modéré compte tenu de la difficulté de faire réagir une partie fortement hydrophobe avec une partie fortement hydrophile. Ensuite, ces adduits de tétraols obtenus avec la 1,3-dihydroxyacétone ont également été évalués en tant que tensioactifs en effectuant des tests physico-chimiques (CMC, point Krafft et Phase Inverse Temperature). Les résultats ont montré que ces nouveaux agents tensioactifs liés à la liaison C-C sont aussi efficaces que d'autres agents tensioactifs disponibles dans le commerce en diminuant la tension de surface, ce qui est une propriété très attrayante pour des applications potentielles / In this manuscript, an atom economic route of C-C bond based surfactants has been developed. They are more stable for broader applications. This process involves the use of renewable and relatively low cost raw materials. Ketoses such as 1,3-dihydroxyacetone and D-fructose were used as substrates with aldehydes as alkylation agents without any protection-deprotection step. The synthesis has been divided into two steps, in the first step the deprotonated ketoses react with the aldehydes electrophiles to form the hydroxyketone intermediates. Then, a second step of hydrogenation with Ruthenium on alumina catalyst under hydrogen pressure gave access to the alkylated polyols. The overall yield of this two-step process is moderate considering the difficulty of reacting a highly hydrophobic part with a highly hydrophilic part. Then these tetraols adducts obtained with 1,3-dihydrdoxyacetone were also evaluated as surfactants by making physico-chemical tests (CMC, Krafft point and Phase Inverse Temperature). Results have exhibited this novel C-C bond connected surfactants perform as efficient as other commercially available surfactants in decreasing the surface tension which is a very attractive property for potential applications

Les interactions entre les interfaces liquide/liquide et liquide/solide interviennent dans de nombreux domaines et procédés industriels. Cependant, ces interactions ont été très peu étudiées par le passé. Nous nous concentrons ici sur le drainage spontané de solutions aqueuses de sel ou de tensio-actifs pressées entre une goutte d'huile et une surface en verre. Expérimentalement, une goutte d'huile est immergée dans de l'eau et approchée d'une surface solide ; le film d'eau pressé résultant draine et adopte une forme “dimple” due au gradient de pression. Par la suite, le film d'eau relaxe vers son épaisseur uniforme d'équilibre.Les profils d'épaisseur spatio-temporels du film sont mesurés par microscopie d'interférences en réflexion. Nous avons étudié la dynamique de drainage ainsi que l'état d'équilibre du système en présence de sel et/ou de tensio-actifs. Tout d'abord, nous réalisons une description quantitative de l'ensemble de la dynamique de drainage. Trois régimes sont identifiés pour une solution aqueuse d'électrolyte : un régime dominé par la pression capillaire, un second mixte décrit par les pressions capillaire et de disjonction, et un troisième dominé par la pression de disjonction. Ces régimes sont modélisés dans le cadre de l'approximation de lubrification. En particulier, le rôle de la pression de disjonction est étudié avec précision dans la limite de la portée des interactions électrostatiques. Nous déduisons des lois analytiques simples permettant de décrire la dynamique de drainage, découplant ainsi les effets des pressions des effets géométriques. Par ailleurs, nous montrons que l'ajout de tensio-actifs ne modifie pas qualitativement les régimes de drainage, à l'exception de concentrations supérieures à la concentration micellaire critique. En effet, à de très faibles épaisseurs, l'huile mouille alors partiellement le solide, ralentissant ainsi le drainage de l'eau piégée au centre du dimple.Nous mesurons la condition aux limites à l'interface eau/huile. Nous confirmons ainsi l'effet Marangoni, mentionné dans la littérature, résultant du gradient de concentration d'espèces (impuretés ou tensio-actifs) adsorbés à l'interface. Nous montrons que l'interface eau/huile est en général de type solide et donc que la vitesse tangentielle est nulle à l'interface. Cependant, pour des concentrations faibles en espèces adsorbées, nous mettons en évidence pour la première fois un contre-courant à l'interface eau/huile résultant de l'approche de la goutte et d'une cinétique lente d'adsorption des tensio-actifs.Par la suite, nous nous concentrons sur l'état d'équilibre du système, soit par mouillage de l'huile sur le solide, soit par formation d'un film d'eau homogène stable. Dans le cas d'un film d'eau stable, l'équilibre résulte d'une égalité entre la surpression dans la goutte et la pression de disjonction du film. En variant le rayon de la goutte, nous montrons qu'il est possible de mesurer l'évolution de la pression de disjonction avec l'épaisseur du film. Cette évolution peut être entièrement décrite par les interactions entre les interfacées chargées. Pour de grandes surpressions de goutte, ou de petites longueurs de Debye, l'huile mouille le solide. Nous montrons que la dynamique de mouillage dépend fortement de la concentration en tensio-actif lorsqu'elle est inférieure à la concentration micellaire critique. La vitesse de la triple ligne de contact peut varier de quatre décades. Nous attribuons ces comportements à l'adsorption du tensio-actif aux interfaces eau/huile et eau/verre, et en particulier à la possible formation de monocouches ou bicouches sur le solide. / The interactions between liquid/liquid and solid/liquid interfaces are involved in many industrial processes and fields. However, they have been poorly studied in the past. We focus here on the spontaneous drainage of aqueous solutions of salt or surfactants squeezed between an oil drop and a glass surface. Experimentally, an oil drop immersed in water is driven towards a solid surface; the resulting squeezed water film drains and adopts a dimple shape due to the pressure gradient, and further relaxes to its equilibrium uniform thickness. The thickness profile of the film is measured in space and time by reflection interference microscopy. We have studied both the drainage dynamics and the final equilibrium state reached by the system in presence of salt and/or surfactants. First, we quantify and provide a full description of the drainage dynamics. Three regimes are identified in an aqueous electrolyte: a capillary dominated regime, a mixed capillary and disjoining pressure regime, and a disjoining pressure dominated regime. These regimes are modeled within the lubrication approximation, and the role of the disjoining pressure is precisely investigated in the limit of thicknesses smaller than the range of electrostatic interactions. We derive simple analytical laws describing the drainage dynamics, thus providing tools to uncouple the effect of the film geometry from the effects of the disjoining or capillary pressures. We show that the addition of surfactants does not qualitatively modify the drainage regimes, except at concentrations larger than the critical micellar concentration and very small film thicknesses in which the oil can partially wet the solid, thus slowing down the drainage of the remaining trapped water. In addition, we provide measurements of the boundary condition at the oil/water interface. We confirm the role of Marangoni flows, suggested in the literature and resulting from concentration gradients of species (impurities or surfactants) adsorbed at the interface. We thus show that a solid-like, no-slip boundary condition is generally met at the oil/water interface. However, for low concentrations in adsorbed species, we evidence for the first time a reverse flow at the interface resulting from the approach of the drop and the slow adsorption kinetics of surfactants. In a second part, we focus on the equilibrium state reached by the water film, i.e. either wetting of the solid surface by the oil drop or formation of a stable water film between the drop and the solid. In the latter case, equilibrium results from the balance of the capillary pressure in the drop and the disjoining pressure. By varying the droplet radius, we show it is possible to measure the variations of the disjoining pressure with the film thickness, and that they can be fully described by taking into account the interactions between the charged interfaces. For large capillary pressures or short Debye lengths, the oil wets the solid surface and we show the wetting dynamics is strongly modified depending on surfactant concentration below the cmc: the velocity of the oil/water/solid triple line varied over four decades. We ascribe the observed behaviors to surfactant adsorption at the oil/water and solid/water interfaces, and in particular to the possible formation of surfactant mono or bi-layers on the solid.

L'ATPase-Ca2+ du réticulum sarcoplasmique est une protéine membranaire dont plusieurs conformations ont été résolues par cristallographie des rayons X. Ces structures ont été précieuses pour l'interprétation de nos études fonctionnelles sur le rôle du domaine A et de la boucle L6-7 de l'ATPase. Mais nous avons montré que les conditions de cristallisation aboutissent parfois à des structures paradoxales : la présence de concentrations importantes de Ca2+ pendant la cristallisation en présence d'AMPPCP conduit l'ATPase à adopter une conformation probablement différente de sa structure moyenne en solution; de même, dans les conformations de l'ATPase proches de l'état phosphorylé «E2P», les inhibiteurs généralement utilisés pour stabiliser l'ATPase bloquent de façon artéfactuelle l'ouverture des sites Ca2+ vers la lumière du réticulum. Nous avons tenté de comprendre les avantages et inconvénients de divers polymères amphiphiles conçus pour stabiliser en solution les protéines membranaires.