Um sistema de análises químicas por injeção em fluxo foi desenvolvido e aplicado à determinação espectrofotométrica de baixas concentrações de sulfato em águas de chuva. O método explora a reação de deslocamento entre o ânion sulfato e o complexo dimetilsulfonazo (III) de bário, Ba-DMSA, com consequente formação do sal pouco solúvel BaSO4. A solução com o complexo Ba-DMSA apresenta alta absortividade molar a 656 nm, e uma diminuição pronunciada na absorbância ocorre na presença de sulfato. Desta forma, o sinal analítico é registrado como pico invertido proporcional à concentração de sulfato na amostra. A presença de altas concentrações de dimetilsulfóxido, DMSO, no reagente favorece a intensidade do sinal analítico, por coordenar as moléculas de água, melhorando a sensibilidade do método. A utilização do tensoativo dodecilsulfato de sódio, SDS, determina também uma melhoria considerável na sensibilidade analítica, pois sua presença no ambiente reacional altera as condições de supersaturação. A sensibilidade e seletividade do procedimento são melhoradas incluindo-se uma etapa de troca iônica em linha, com resina aniônica Dowex 1-X8, para concentração do sulfato e separação dos íons interferentes em potencial. O sistema proposto é robusto e fornece resultados precisos (d.p.r. < 0,01) com frequência analítica de 30 determinações por hora. O consumo de DMSA é de 0,17 \'mü\'mol por determinação. A curva analítica se apresenta linear até 2,0 mg L-1 SO42- e os limites de detecção e de quantificação foram estimados em 0,01 mg L-1 SO42- e 0,04 mg L-1 SO42-. / A flow injection system was developed and applied to the spectrophotometric determination of low concentrations of sulphate in rain waters. The method exploits the displacement reaction involving the sulphate anion and the barium dimethylsulfonazo (III) complex, Ba-DMSA, with consequent formation of the slightly soluble BaSO4 salt. As the Ba-DMSA solution is characterized by a high molar absorptivity at 656 nm, a pronounced absorbance lessening is observed in the presence of sulphate. The analytical signal is then recorded as an inverted peak proportional to the sulphate content in the sample. Presence of dimethylsulphoxide, DMSO, at high concentrations in the reaction medium leads to an enhancement of the analytical signals, coordinating water molecules, thus improving the sensitivity of the method. Addition of the surfactant sodium dodecylsulphate, SDS, results also in a pronounced improvement in sensitivity, as its presence in the reaction medium alters the supersaturation conditions. The sensitivity and selectivity of the method were improved by including an in-line ion exchange mini-column with the anionic resin Dowex 1-X8 into the manifold, for sulphate concentration and separation from potential interfering ions. The proposed system is robust and provides accurate results (R.S.D. <0.01) at an analytical frequency of 30 determinations per hour. About 0.17 \'mü\'mol DMSA are consumed per determination. The analytical curve is linear up to 2.0 mg L-1 SO42- and the detection and quantification limits were estimated as 0.01 mg L-1 SO42- and 0.04 mg L-1 SO42-.

Submitted by Marilene Donadel (marilene.donadel@unioeste.br) on 2018-08-14T17:49:42Z No. of bitstreams: 1 Mateus_Sausen_2017.pdf: 2943768 bytes, checksum: a2c72e2a3998357e8a9b3be38176720d (MD5) / Made available in DSpace on 2018-08-14T17:49:42Z (GMT). No. of bitstreams: 1 Mateus_Sausen_2017.pdf: 2943768 bytes, checksum: a2c72e2a3998357e8a9b3be38176720d (MD5) Previous issue date: 2017-03-10 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The incidence of new diseases demands the fabrication of highly resistant and efficient pharmaceutical compounds for human and animal health. This aspect, along with the inadequate treatment of wastes generated by this activity, damages the environment and may consequently affect the population. In this sense, the objective of this study was to evaluate the removal of ciprofloxacin drug (CIP) of aqueous solutions by using the cationic resin SupergelTM SGC650H packed in a fixed bed column. Therefore, the characterization of the resin was performed by techniques of gas helium pycnometer, nitrogen physisorption, X-ray sedimentometry, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and point of zero charge (pHPZC). Initially, closed system and batch experiments were conducted to evaluate the effect of solution pHinitial. Afterwards, equilibrium experiments were performed. Finally, it was obtained the breakthrough curves in fixed bed in different volumetric flow rates and heights of the bed, defined by a central composite experimental design (CCD) and by using phenomenological mathematical modeling. The characterization demonstrated a low amount of pores on the structure of the resin and the analysis of pHPZC indicated that the point of zero charge of the resin was 2.68. The pH tests showed that the higher CIP removal capacity was achieved at pH values below 6. In the analysis of the equilibrium results, it was verified that the Langmuir model showed the best fit to the experimental data obtained in a closed and batch system, providing the values of 510.64 mg g-1 and 1.93 L mg-1 to qmáx and bL estimated parameters, respectively. In the fixed bed column tests, the maximum efficiency of the column as a function of the studied operational variables was obtained for volumetric flow rate of 3.8 cm3 min-1 and bed height of 15.2 cm (81,5%). In addition, it was observed that the kinetic model that considers the adsorption step on the surface (AS) as rate-limiting step of the process satisfactorily described the results obtained in column. In general, the work was able to identify a high removal capacity the ciprofloxacin drug by using the SGC650H resin. Finally, the study presented satisfactory results in the prediction of column efficiency from the phenomenological mathematical modeling used. With this, a new perspective is observed in the treatment of this drug compound and the possible application of the large-scale method. / A incidência de novas doenças necessita a fabricação de compostos farmacêuticos altamente resistentes e eficazes para a saúde animal e humana. Esse aspecto, aliado ao tratamento inadequado dos resíduos gerados por essa atividade, prejudica o meio ambiente e pode afetar, consequentemente, a população. Nesse contexto, o objetivo deste trabalho foi avaliar a remoção do fármaco ciprofloxacina (CIP) de soluções aquosas utilizando a resina catiônica SupergelTM SGC650H empacotada em coluna de leito fixo. Para tanto, a caracterização da resina foi realizada pelas técnicas de picnometria a gás hélio, fisissorção de nitrogênio, sedimentometria de raios X, microscopia eletrônica de varredura (MEV), espectroscopia de energia dispersiva de raios X (EDX) e ponto de carga zero (pHPCZ). Inicialmente, foram realizados experimentos em sistema fechado e batelada para avaliar o efeito do pHinicial da solução. Após isso, realizaram-se os experimentos de equilíbrio. Por fim, foram obtidas as curvas de ruptura em leito fixo sob diferentes vazões volumétricas e alturas do leito, definidas a partir de um planejamento experimental do tipo delineamento composto central rotacional (DCCR) e utilizando modelagem matemática fenomenológica. A caracterização apresentou baixa quantidade de poros na estrutura da resina e a análise do pHPCZ indicou que o ponto de carga zero da resina foi 2,68. Os testes de pH mostraram que a maior capacidade de remoção da CIP foi alcançada para valores de pH abaixo de 6. Na análise dos resultados de equilíbrio, foi possível verificar que o modelo de Langmuir foi o que melhor se ajustou aos dados experimentais obtidos em sistema fechado e batelada, fornecendo os valores de 510,64 mg g-1 e 1,93 L mg-1 para os parâmetros qmáx e bL, respectivamente. Nos ensaios em coluna de leito fixo, a maximização da eficiência da coluna em função de suas variáveis testadas, foi obtida para vazão volumétrica de 3,8 cm3 min-1 e altura do leito de 15,2 cm (81,5%). Paralelamente, notou-se que o modelo cinético que considera a etapa de adsorção na superfície (AS) como limitante do processo, conseguiu descrever de forma satisfatória os resultados obtidos em coluna. De forma geral, o trabalho conseguiu identificar uma alta capacidade de remoção do fármaco ciprofloxacina com a utilização da resina SGC650H. Além disso, apresentou resultados satisfatórios na previsão da eficiência da coluna a partir da modelagem matemática fenomenológica utilizada. Com isso, observa-se uma nova perspectiva no tratamento deste composto fármaco e a possível aplicação do método em larga escala.

O objetivo deste estudo foi avaliar o efeito da temperatura de troca iônica (TI) nas propriedades mecânicas da porcelana Ultrapaline ST e o efeito da TI nos parâmetros de crescimento subcrítico de trincas (SCG) (coeficiente de SCG - n, parâmetro escalar - ?f0), de Weibull (resistência característica - ?0, módulo de Weibull - m) e no comportamento de curva R desta porcelana. 250 discos (12 mm diâmetro x 1 mm espessura) foram fabricados de acordo com as instruções do fabricante, usinados em retificadora plana e polidos até 1 ?m. Para determinar o efeito da temperatura de TI na resistência à flexão biaxial (?), dureza (H) e tenacidade à fratura (KIc), 40 discos foram divididos em 4 grupos (n=10): GI (controle) - sem TI; e GII, GIII e GIV submetidos a TI com KNO3 por 15 min a 450°C; 470°C e 490°C, respectivamente. A ? foi determinada por \"pistão sobre três esferas\" em saliva artificial a 37°C a 10 MPa/s. Para dureza e tenacidade à fratura, foram feitas 3 indentações Vickers em cada espécime (2kg, 30s) e as diagonais e trincas radiais foram medidas e os valores de H e KIc calculados. As médias e desvios-padrão para ? (MPa), H (GPa) e KIc (MPa.m1/2) foram: GI: 57,95 ± 8.97, 7,24 ± 0,79 e 1,14 ± 0,14; GII: 125,04 ± 23,58, 5,80 ± 0,14, 2,62 ± 0,14; GIII: 133,00 ± 11,00, 5,88 ± 0,45, 2,54 ± 0,22; GIV: 137,67 ± 12,05, 5,88 ± 0,17, 2,57 ± 0,10, respectivamente. Para determinação dos parâmetros de SCG e de Weibull, 140 espécimes foram divididos em 2 grupos: GC (controle) e GT (submetidos à TI por 15 min a 470°C). Para determinação de n e de ?f0, 50 espécimes de cada grupo foram testados em saliva artificial a 37°C em flexão biaxial em uma das seguintes taxas de tensão: 10-2, 10-1, 100, 101 e 102 MPa/s. Para determinação dos parâmetros de Weibull, mais 20 espécimes de cada grupo foram ensaiados na taxa de 100 MPa/s. Os valores de n, ?f0, m e ?0 foram, respectivamente (valores entre parênteses representam intervalos de confiança de 95%): 24,1 ± 2,5; 58,1 ± 0,01; 13,8 (10,0 a 18,8) e 60,4 (62,2 a 58,5) para GC e 36,7 ± 7,3; 127,9 ± 0,01; 7,4 (5,3 a 10,1) e 136,8 (129,1 a 144,7) para GT. Para determinação do efeito da TI no curva R, 7 espécimes de cada grupo receberam uma indentação Vickers em uma das seguintes cargas de indentação (kg): 0,18; 0,32; 0,56; 1,0; 3,2. Após armazenados ao ar por 24 h os espécimes foram ensaiados a 10 MPa/s em saliva artificial a 37°C. Os parâmetros ?, ?, q foram, respectivamente: 62,57; 0,12 e 0,2857 para GC e 161,50; 0,34 e -0,0074 para GT. Os valores de k variaram de 0,371 a 0,515 para GC e de 1,240 a 0,804 para GT. Não houve diferença nas propriedades mecânicas entre as três temperaturas de TI testadas. A TI promoveu aumento significativo do valor de n, ?f0 e ?0, entretanto resultou em diminuição do valor de m e também suprimiu o comportamento de curva R, presente no material antes da realização da TI. / The objectives of this study were to determine the influence of different ion exchange (IE) temperatures on mechanical properties of a dental porcelain Ultrapaline ST and the effect of IE on slow crack growth (SCG) (coefficient of SCG - n, scale parameter - ?f0) and Weibull parameters (characteristic strength - ?0; Weibull modulus - m) and R-curve behavior of this porcelain. 250 specimens (12 mm diameter x 1 mm height) were fabricated according to the manufacturer\'s instructions, grounded with a surface-grinding device and polished up to 1?m. To determine the effect of IE temperature on biaxial flexural strength (?), hardness (H) and fracture toughness (KIc), 40 specimens were divided in four groups (n=10) as follow: GI - control (no ion exchange); GII, GIII and GIV submitted to IE with KNO3 for 15 min at 450°C; 470°C e 490°C, respectively. The ? was determined using a piston-on-three-balls device, in artificial saliva at 37°C and constant loading rate of 10 MPa/s. For hardness and fracture toughness, 3 Vickers indentations (2kg, 30s) were made on each specimen. The diagonals and radial cracks were measured in order to calculate H and KIc. Mean and standard deviations values of ? (MPa), H (GPa) and KIc (MPa.m1/2) were: I: 57.95 ± 8.97; 7.24 ± 0.79; 1.14 ± 0.14; II: 125.04 ± 23.58; 5.80 ± 0.14; 2.62 ± 0.14; III: 133.00 ± 11.00; 5.88 ± 0.45; 2.54 ± 0.22; IV: 137.67 ± 12.05; 5.88 ± 0.17; 2.57 ± 0.10, respectively. To determine the effect of IE on SCG and Weibull parameters, 140 specimens were divided in 2 groups: GC (control) and GIE (submitted to IE at 470°C for 15 min). To determine the SCG parameters, 10 specimens of each group were tested in biaxial flexural strength in each one of five constant stress rates: 10-2, 10-1, 100, 101 e 102 MPa/s. To determine the Weibull parameters, 20 specimens of each group were tested in the stress rate of 100 MPa/s. The n, ?f0, m and ?0 (values in parenthesis represent the confidence interval) were: 24.1 ± 2.5; 58.1 ± 0.01; 13.8 (10.0 to 18.8) and 60.4 (62.2 to 58.5) for GC and: 36.7 ± 7.3; 127.9 ± 0.01; 7.4 (5.3 to 10.1) and 136.8 (129.1 to 144.7) for GIE, respectively. To determine the effect of IE on R-curve behavior, 7 specimens of each group received a Vickers indentation in one of the following indentation loads (kg): 0.18; 0.32; 0.56; 1.0; 3.2. After stored on air for 24 h, the specimens were tested biaxial flexure strength in artificial saliva at 37°C in a stress rate of 10 MPa/s. The ?, ?, q parameters were, respectively: 62.57; 0.12 and 0.2857 for GC and 161.50; 0.34 and -0.0074 for GIE. The values of k varied from 0.371 to 0.515 for GC and from 0.34 to 0.0074 for GIE. There are no differences on mechanical properties among the three IE temperatures tested. The IE promoted significantly increase of n, ?f0 and ?0 however, decreased the m value and suppressed the R-curve behavior originally present on material before the IE.

Les résines échangeuses d’ions (REI) sont largement utilisées dans l’industrie nucléaire pour décontaminer certains effluents radioactifs. Après utilisation, elles sont généralement enrobées dans des matériaux cimentaires. Cependant, leur cimentation est compliquée par la forte expansion de certains enrobés de résines. L’origine de cette expansion reste mal connue, de même que les conditions qui la favorisent. Au cours de ce travail, les interactions entre des résines échangeuses d’ions cationiques sous forme Na+ ou Ca2+ et du silicate tricalcique (C3S), du ciment Portland (CEM I) ou du ciment au laitier (CEM III/C) ont été étudiées au jeune âge afin d’améliorer la compréhension de cette instabilité dimensionnelle.Les résultats montrent que lors de l’hydratation d’une pâte de C3S ou de CEM I incorporant des REI sous forme Na+, celles-ci subissent transitoirement une phase d’expansion par suite de la diminution de la pression osmotique de la solution interstitielle. Cette expansion de faible amplitude qui se produit juste après la prise est suffisante pour dégrader l’enrobé par ailleurs fragilisé par un ensemble de processus : faible degré d’avancement de l’hydratation, précipitation de C-S-H moins cohésifs car fortement enrichis en sodium, microstructure hétérogène avec des zones de forte porosité et la précipitation de gros cristaux de portlandite facilement clivables à l’interface REI/matrice.Cette expansion peut être empêchée en réalisant un prétraitement calcique des résines ou en les enrobant avec un ciment au laitier dont la cinétique d’hydratation est plus lente que celle du ciment Portland. / Ion exchange resins (IERs) are widely used by the nuclear industry to decontaminate radioactive effluents. After use they are usually encapsulated in cementitious materials. However, the solidified waste forms can exhibit a strong expansion, possibly leading to cracking. Its origin is not well understood as well as the conditions when it occurs.In this work, the interactions between cationic resins in the Na+ or Ca2+ form and tricalcium silicate (C3S), Portland cement (CEM I) or Blastfurnace slag cement (CEM III/C) are investigated at an early age in order to gain a better understanding of the expansion process.The results show that during the hydration of a paste of C3S or CEM I containing IERs in the Na+ form, the resins exhibit a transient expansion of small magnitude due to the decrease in the osmotic pressure of the interstitial solution. This expansion, which occurs just after cement setting, is sufficient to damage the material which is poorly consolidated for several reasons: small hydration degree, precipitation of less cohesive sodium bearing C-S-H, heterogeneous microstructure with highly porous zones and lastly clivable crystals of portlandite at the interface between resins and paste.This expansion can be prevented by performing a calcium pretreatment of the resins or by using a CEM III/C cement with a slower rate of hydration than that of Portland cement.

La recherche vise à proposer des membranes pour des dispositifs électrochimiques capables d'atteindre le bon compromis en terme de conduction ionique, de stabilité et de longue durée de vie pour une haute efficacité.Nous avons réalisé des membranes échangeuses des protons, d'anions ou amphotères à base de polymères aromatiques stables fonctionnalisés. Des groupes sulfonique on été introduit sur la squelette du PEEK, des groupes d'ammonium sur le PEEK et le PSU ou le deux au même temps pour échanger ensemble des protons et des anions.L'optimisation continue des paramètres de synthèse, le choix des différents polymères et/ou des groupes de fonctionnalisation et l'amélioration des procédures et des traitements des membranes coulée, a conduit à de bons résultats en termes de conductivité ionique, sélectivité et stabilité.L'étude des principaux paramètres des membranes démontre une stabilité thermique entre 140 et 200 ° C selon la membrane sélectionnée, un comportement mécanique caractérisé par une résistance à la traction et un module d'élasticité élevée et un relativement faible ductilité, influencé par le niveau d’ hydratation de la membrane ou l éventuelle présence de cross-link. En optimisant le degré de fonctionnalisation et les types de groupes de fonctionnalisation, nous avons obtenu une accordable absorption d'eau, une conductivité ionique élevé pour différent ions (jusqu'à ≃ 3 mS / cm pour le polymère conducteurs des anions) et une perméabilité aux ions vanadium très faible (applications dans RFB) jusqu'à ≃ 10-10 cm2/min, ce qui est bien au-dessous des données typiques de la littérature et un paramètre très important pour applications technologiques. / The research aims to propose membranes for electrochemical devices alternative to the commercial ones able to reach the right compromise in term of good ionic conduction, stability and long life time for an high efficiency. We realized proton exchange, anion exchange and amphoteric membranes based on stable functionalized aromatic polymers (PEEK, PSU). We thus introduced sulfonic groups on a PEEK backbone to exchange protons or ammonium groups on PEEK and PSU to exchange anions. We also realized amphoteric membranes able to exchange at the same time both kinds of ions. The continuous optimization of synthesis parameters, the choice of different polymers and/or functionalization groups and the improvement of casting procedures and treatments of membranes, led to good results in terms of ionic conductivity, selectivity and stability.The study of the main parameters of the synthesized membranes demonstrates a thermal stability between 140 and 200°C depending on the selected membrane, a mechanical behavior characterized by a high elastic modulus and tensile strength and a relatively low ductility strongly influenced on the degree of hydration of the membrane as well as the eventual presence of cross-linking. Working on the degree of functionalization and the type of functionalizing groups, we obtained a tunable water uptake, an elevated ionic conductivity for different ions (up to ≃ 3 mS/cm for anionic conducting polymers) and a very low ion permeability (vanadium ions for RFB applications) down to ≃ 10-10 cm2/min, which is much below typical literature data for cation- and anion separation membranes and a challenge parameters for technological applications.

Magister Scientiae - MSc / The objective of this study was to investigate the feasibility of the application of low cost high capacity inorganic ion exchange material, synthesized form collected fly ash and acid mine drainage solid residues, for the decontamination of secondary co-disposal process waters, with emphasis on investigating the processes governing the solid/solution interface. / South Africa

Doctor Educationis / The research focused on the synthesis, characterisation and activity of zeolite supported metal catalysts for the Friedel-Crafts alkylation of benzene with t-butyl chloride. Alkyl benzenes are traditionally produced via systems that employ the use of Lewis acids or strong mineral acids. There have been widespread concerns over these approaches based on their environmental impacts and separation difficulties. Recent approaches have endeavoured the much to use more environmentally eco-friendly systems and zeolites have proved to be versatile support materials. The use of zeolites has also shown to greatly improve product selectivity as well as easing separation constraints. However the adoption of zeolites on large scale Friedel-Crafts alkylation has been hampered by the high cost of zeolite production from commercial sources. On the other hand fly ash has been found to be a viable starting material for zeolite synthesis. Apart from that South Africa is faced with fly disposal challenges and there is continual accumulation of fly ash at the coal fired power stations, which provide about 77 % of the power produced in the country. In this light the use of fly ash will help to reduce the disposal constraints as well as providing a cheap starting material for zeolite synthesis. In this study the hierarchical Zeolite X has been successfully synthesised from fly ash via a hydrothermal treatment. The zeolite was then loaded with Fe/Mn via two approaches namely liquid phase ion exchange and incipient wetness impregnation. For comparison purposes seasoned commercial support materials namely HBEA and MCM- 41 were also loaded with the same metals and characterised with various techniques namely; HRSEM, EDS, HRTEM, XRD, SAED, ICP-OES and N2 adsorption analysis, It was found from the characterisation undertaken that the integrity of the respective supports was generally retained upon metal loading. Both the ICP-OES and the EDS proved that the desired metals were successfully introduced onto the zeolitic support materials. The calculated percentage metal loading for the catalysts prepared via incipient wetness impregnation was closely related to the actual values obtained from the ICP-OES analysis for both the monometallic and the bimetallic catalysts (Fe/Mn). It was observed that the amount of metal that can be introduced on a zeolite via liquid phase ion exchange is largely dependent on the cation exchange capacity of the zeolite Supported metal catalysts for FC alkylation Page v and of the catalysts prepared using 0.25 M Fe solution it was found that Zeolite X had the highest Fe wt% loading of 11.4 %, with the lowest loading of 2.2 % obtained with the MCM-41 supported catalyst. The XRD patterns for the both HBEA and the MCM-41 supported metal catalysts resembled the patterns of the respective prestine support materials except in the case of catalysts with anFe wt % of more than 10, which exhibited peaks due to the Fe2O3 crystallites. In the case of the hierarchical Zeolite X, the metal loaded support had a significant reduction in the XRD peak intensities. The prepared catalysts were tested for the alkylation of benzene with t-butyl chloride. The benzene was also used as the solvent. The alkylation reaction was carried out in a round bottomed flask under reflux conditions and stirring at a temperature of 45 oC over a period of 5 h. A total of 18 catalysts was tested and the highest percentage conversion of 100 % was obtained with the 10%FeH after a reaction time of 2 h. The general trend obtained with the majority of the catalysts was characterised with a rapid initial increase and then steady state was achieved. Generally after a reaction time of 3 h almost all the catalysts had reached steady state in terms of the percentage conversion obtained. The outcomes reflect that the inclusion of Mn does not enhance the conversion but rather decreases it. It was also found that the Mn was not active in the alkylation of benzene as shown by the inactivity of the 10%MnM, where 10% by weight Mn was loaded on MCM-41. However the other monometallic catalysts containing Mn supported on Zeolite X and HBEA were found to be active. The activity is attributed to the presence of Brønsted acid sites in these zeolites which are not present in MCM-41. The selectivity studies reflect that the inclusion of Mn does slightly improve the selectivity towards the formation of the monoalkylated product (t-butyl benzene). The highest selectivity of 91.1 % was obtained with the 10%FeMnM after a reaction time of 4 h. MCM-41 supported catalysts had a relatively higher selectivity compared to the other supports. Considering the Fe monometallic catalysts tested it generally can be said that the yield were in the order HBEA > MCM-41 > Zeolite X. It however should be noted that the percentage yield is calculated from the conversion and selectivity percentages, this implies that the factors affecting these parameters will consequently affect the percentage yield obtained. Supported metal catalysts for FC alkylation Page vi The alkylation reaction was found to be characterised by the formation of two intermediate products which could not be identified. These products were formed during the transient start up stages of the reaction and would disappear from the reaction mixture with longer reaction times, and after 3 h in almost all the reactions studied the intermediates were not detected in the reaction mixture. The main products found were the monoalkylated product (desired product) and the para isomer (1,4-t-di-butyl benzene). There were no other dialkylated isomers or trialkylated products detected. The formation of the para isomer was usually after a reaction time of 2 h in most reactions. The research managed to show that the hierarchical Zeolites X can be synthesised from fly ash and ion exchange and incipient wetness impregnation are appropriate approaches that can be used to introduce Fe/Mn onto the support materials studied. The catalysts prepared were active to varying degrees in the Friedel-Crafts alkylation of benzene with t-butylchloride, with the exception of the 10%MnM which was found to be inactive.

Malgré le nombre croissant de capteurs dans les domaines de la chimie et la biologie, de nombreuses réactions n’ont pas encore été correctement identifiées et étudiées. C’est entre autres le cas des interactions intermoléculaires à l’interface liquide/solide trouvées dans les chimies de surface utilisées pour les méthodes de diagnostics médicaux et l’identification de divers processus biologiques. Afin de correctement comprendre les mécanismes en jeux, il est important de pouvoir croiser différentes méthodes de détection pour obtenir des informations complémentaires.MuLe principal objectif de cette étude est de dimensionner, fabriquer et caractériser un détecteur optique intégré sur verre basé sur la résonance plasmonique de surface, destiné à terme à être combiné avec d’autres techniques de détection. La résonance plasmonique de surface est une technique reconnue pour sa sensibilité adaptée à la détection de surface, qui a l’avantage d’être sans marquage et permet de fournir un suivi en temps réel de la cinétique d’une réaction. L’avantage principal de ce capteur est qu’il a été dimensionné pour une large gamme d’indice de réfraction de l’analyte, allant de 1,33 à 1,48. Ces valeurs correspondent à la plupart des entités biologiques associées à leurs couches d’accroche, particulièrement les matrices de polymères. Ces matrices sont de plus en plus utilisées non seulement pour leur capacité à augmenter la densité d’analytes présents à la surface du capteur, mais aussi pour leurs propriétés favorisant l’adsorption spécifique et leur utilisation comme élément actif de reconnaissance biologique.Étant donné que beaucoup d’études biologiques nécessitent la comparaison de la mesure à une référence ou à une autre mesure, le second objectif du projet est d’étudier le potentiel du système SPR intégré sur verre pour la détection multianalyte.MuLes trois premiers chapitres se concentrent sur l’objectif principal du projet. Le dimensionnement du dispositif suivant un cahier des charges préétabli est présenté, ainsi que les outils de simulation. Le procédé de fabrication de la puce optique sur verre est ensuite décrit, ainsi que les instruments et protocoles de caractérisation. Une comparaison est faite entre les simulations et les résultats expérimentaux, et les performances des outils numériques ainsi que celles du dispositif sont évaluées.Le dernier chapitre de la thèse présente l’étude de plusieurs techniques de multiplexage spectral adaptées à un système SPR intégré, exploitant en particulier la technologie sur verre. L’objectif est de fournir au moins deux détections simultanées. Dans ce cadre, plusieurs solutions sont proposées et les dispositifs associés sont dimensionnés, fabriqués et testés. / In spite of the growing number of available biosensors, many biochemical reactions and biological components have not yet been studied in detail. Among them, some require the combination of several detection techniques in order to retrieve enough information to characterize them fully. An unknown reaction based, for example, on DNA hybridization could be characterized with an electrochemical sensor, a mechanical sensor and an optical sensor, each giving a different type of information.MuThe main objective of the work presented here is to design, fabricate and characterize a flexible integrated optical biosensor based on surface plasmon resonance, intended to be then combined with other detection techniques. Surface Plasmon Resonance (SPR) is well known to be a sensitive technique for surface-based biochemical detection. It has the advantage to be an unlabeled method and provides real time information on the kinetics of a reaction. The use of an integrated technology enables us to integrate several sensors on the same chip for the same sample, making them compact and low-cost. The flexibility of the proposed SPR biosensor comes from the fact that it is designed for a large range of analyte refractive indices, from 1.33 to 1.48 in the 600 nm-1000 nm wavelength range. These values are suitable for most biological entities and their ligand layers, and especially for hydrophilic polymer matrices used to trap DNA or protein entities. These biochemical matrices are used more and more for their ability to trap high densities of analyte, provide a strong binding and serve as an active detection medium with good anti-fouling properties.MuAs several biochemical studies require the simultaneous comparison of measurements to a reference or to another measurement, the second objective of this project is to study the potential of multianalyte detection in an integrated SPR device on glass.The first three chapters of the thesis are focused on the main objective. The design according to predefined specifications is presented, at the same time as the simulation tools. The fabrication process of the glass chip is introduced, as well as the characterization instruments and protocols. Simulation and experimental results are then compared, and the device performance is assessed.The last chapter describes the study of several spectral multiplexing techniques adapted to an integrated SPR system using the glass technology. The goal is to provide at least two simultaneous measurements. Several detection techniques are examined and the related devices are designed, fabricated and characterized.

Nous avons étudié les comportements dynamiques d'auto-assemblage des tensioactifs cationiques non-chiral en présence du contre-anion chiral.Lorsque le nucléotide anionique chiral est ajouté à des vésicules cationiques, la transition morphologique se produit et transforme in situ des vésicules sphériques en hélices micrométriques.D'autres types de Gemini tensioactifs cationiques forment des rubans nanométriques hélicoïdaux, en présence de tartrate contre-anions. La forme et l'hélicité de ces rubans peuvent être contrôlés in situ par la variation de l'excès énantiomérique.En outre, les nanohélices organiques peuvent être transcrite en nanohélices 3D de silice via une polycondensation sol-gel.Ces nanohélices de silice fonctionnalisées avec des groupes aminés peuvent interagir fortement avec des nanoparticules d'or (GNPs; 1 ~ 20 nm). Le réseau 3D de -nanohélices GNPs/silice sont potentiellement utilisables pour des applications de capteurs basée sur les SERS comme ceux chimiques et biologiques ultra-sensibles en phase liquide. / We have studied the dynamic self-assembly behaviors of non-chiral cationic surfactants in thepresence of chiral counter-anion.When the chiral anionic nucleotides are added to cationic vesicles, morphology transitionoccurs and spherical vesicles transform in situ to micrometric helices.Other types of cationic surfactant, gemini surfactants form nanometric helical ribbons in thepresence of tartrate counter-anion. The shape and helicity of these self-assembled structurescan be controlled in situ by the variation of enantiomeric excess.In both cases, they form gels in water by creating extended networks of nanometric tomicrometric chiral fibers.Additionally, the organic nanohelices can be transcribed to 3D silica nanostructures via solgelpolycondensation. These silica nanohelices functionalized with amino group can interactstrongly with gold nanoparticles (1 ~ 20 nm). The 3D network of GNPs/silica-nanohelices canpotentially be used for SERS-based sensing applications such as ultra-sensitive chemical andbiological sensors in liquid phase.

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