Orientador: Watson Loh / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-19T04:42:09Z (GMT). No. of bitstreams: 1 Brinatti_Cesar_M.pdf: 6269984 bytes, checksum: 65e7cdbf89a7e16102822d62f57e20e9 (MD5) Previous issue date: 2011 / Resumo: As sulfobetaínas (SB) são uma classe de surfatantes zwitteriônicos. A presença de grupos carregados tanto positiva quanto negativamente na mesma molécula concede à sua cabeça polar uma hidrofilicidade intermediária entre surfatantes iônicos e não-iônicos. O estudo termodinâmico de associação da série homóloga de sulfobetaínas, bem como sua interação com polímeros iônicos e não-iônicos, foi feito utilizando a técnica de titulação calorimétrica isotérmica (ITC), em diferentes temperaturas. O aumento da temperatura leva a um valor mais negativo de energia livre de Gibbs de micelização DmicG, o que favorece a micelização. O termo entrópico TDmicS, embora sempre positivo, é o responsável pela micelização em baixas temperaturas. No entanto, com o aumento da temperatura este termo perde sua intensidade, enquanto o termo entálpico DmicHinverte seu sinal, de positivo para negativo, superando em intensidade o termo entrópico, sendo então o responsável pela micelização em temperaturas elevadas. No estudo de interação com polímeros não-iônicos, o poli (ácido acrílico), PAA, induziu a formação de agregados de unímeros de surfatantes em concentrações abaixo de sua cmc, enquanto o poli (óxido de propileno), PPO, foi incorporado às micelas. Em relação aos polímeros iônicos, o polímero catiônico cloreto de poli (dialildimetilamônio), PDADMAC, e o polímero aniônico poli (acrilato de sódio), PAA, não apresentaram interação alguma com a sulfobetaína. Apenas o polímero aniônico poli (4-estireno sulfonato de sódio), PSS, induziu a formação de agregados de unímeros de surfatante em concentrações muito abaixo da cmc. Esta indução deve-se à interação eletrostática entre o grupo sulfonato (-SO3) do PSS e o grupo amônio ( RNMe2X ) da SB, auxiliada pela presença do grupo hidrofóbico estireno do polímero, que é incorporado às micelas / Abstract: Sulfobetaines (SB) are a class of zwitterionic surfactants. The presence of groups both positively and negatively charged in the same molecule renders an intermediate hydrophilicity between ionic and nonionic surfactants. The self-assembly thermodynamic study of a homologous series of sulfobetaines, as well as its interaction with ionic and nonionic polymers, was performed by isothermal titration calorimetry (ITC), in different temperatures. The increase in temperature leads to a more negative value of the Gibbs free energy of micellization DmicG, which favors micellization. The entropic term TDmicS, although always positive, is the responsible for the micellization in lower temperatures. However, with the increase in temperature this term loses its intensity, while the enthalpic term DmicH changes its sign, from positive to negative, overcoming the entropic term in intensity, and therefore being the responsible for the micellization in higer temperatures. In the study of interaction with nonionic polymers, poly (acrylic acid), PAA, induced the formation of aggregates of surfactant monomers in concentrations below its cmc, while poly (propylene oxide), PPO, was incorporated to the micelles. Regarding ionic polymers, the cationic poly(diallyldimethylammonium chloride), PDADMAC, and the anionic polymer poly (sodium acrylate), PAA, didn't show any interaction with the sulfobetaine. Only the anionic polymer poly(sodium 4-styrenesulfonate), PSS, induced the formation of aggregates of surfactant monomers in concentrations well below its cmc. This induction is due to the electrostatic interaction between the sulfonate group (-SO3) from the PSS and the ammonium group (RNMe2X) from the SB, aided by the presence of the hydrophobic group styrene in the polymer, which is incorporated into the micelles / Mestrado / Físico-Química / Mestre em Química

Orientador: Watson Loh / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-04T17:10:15Z (GMT). No. of bitstreams: 1 Silva_RodrigoCardosoda_D.pdf: 8247158 bytes, checksum: 473fe7463d68c6d0e0bc41282c54596d (MD5) Previous issue date: 2002 / Doutorado / Físico-Química / Doutor em Ciências

Les mousses sont des assemblées de bulles de gaz dans une matrice liquide et sont utilisées dans plusieurs applications telles que par exemple l'isolation thermique et phonique, le forage pétrolier. Cependant, elles sont instables et tendent donc à disparaître. Les mécanismes qui gouvernent la stabilité d'une mousse et son effondrement restent encore incompris au niveau fondamental. Ce travail de thèse vise à étudier le couplage physico-chimique et rhéologique au sein d'une mousse par des simulations numériques, au niveau d'un amas de bulles cisaillées, afin de mieux comprendre l'origine de cette instabilité / Foams are gaz bubbles assemblies in a liquid matrix and are used in several applications such as for example the thermal and phonic insulating, ore drilling. However, they are instables and trend to disappear. the mechanisms that gouverns the foam stability and its collapse are still not well understood from a fundamental point of vue. The goal of this thesis work is to study the physico-chemical and rheological coupling in a foam, by numerical simulations of a cluster of sheared bubbles, in order to better understand the origin of this foam instability

A la lumière de la bioaccumulation potentielle relative à la longueur de la chaîne fluorocarbonée, la duplication en chaines courtes constitue une technique intéressante dans la conception de nouveaux matériaux à très faible potentiel de biopersistance. Ainsi, nous avons utilisé cette méthode pour préparer de nouveaux matériaux tensioactifs et polymères conçus avec des chaînes courtes fluorées et évaluer l’influence des paramètres structuraux sur les propriétés physico chimiques de ces composés. L’évaluation des propriétés de surface des tensioactifs ont donné d’intéressantes valeurs aussi bien pour la tension de surface !!!! que pour la concentration micellaire critique (CMC) et la densité moléculaire adsorbée (Amin). La comparaison des propriétés de surface a permis de montrer, que les tensioactifs bicaténaires avec deux chaînes courtes fluorées C4F9 ou C6F13 peuvent égaler, voire dépasser les performances d’un monocaténaire à chaîne longue C8F17 réputé bioaccumulant. Deux populations d’agrégats ont été mises en évidence par la technique de la diffusion de la lumière en mode dynamique (DLS) et par microscopie électronique à transmission (TEM). Des monomères contenant deux segments fluorés ont été synthétisés. Les polymères correspondants ont ensuite été déposés par électropolymérisation et les propriétés de surface des films ont été étudiées. Des films superhydrophobes et oléophobes ont été obtenus avec le polymère PEDOT-2C4,4 à chaînes courtes du fait de nanoparticules uniformément réparties à la surface. Les performances des matériaux conçus avec deux chaînes courtes fluorées ouvrent des perspectives dans la lutte contre la bioaccumulation avérée des longues chaînes perfluorées. / In the light of the potential bioaccumulation relative to the length of the fluorocarbon chain, duplication short chains is an interesting technique in the design of new materials with very low biopersistance. Thus, we used this method to prepare novel surfactants and polymeric materials designed with fluorinated short chains and assess the influence of structural parameters on the physicochemical properties of these compounds. The evaluation of surface properties of surfactants gave interesting values for both surface tension !!!!, critical micelle concentration (CMC) and the molecular density adsorbed (Amin). Comparison of surface properties have shown that double-tailed short chains surfactants with two fluorinated C4F9 or C6F13 can match or exceed the performance of a single-tailed long chain C8F17 deemed bioaccumulant. These surfactants gave two aggregate populations identified by the technique of dynamic light scattering (DLS) and TEM images (transmission electron microscopy). Fluorinated monomers containing two segments were synthesized. The corresponding polymers were then deposited by electropolymerization and the films were studied. Oleophobic and superhydrophobic films were obtained with the PEDOT-2C4,4 polymer short chains because nanoparticles uniformly distributed on its surface. Performance materials designed with two short chain fluorinated open perspectives in the context of the fight against bioaccumulation proven long perfluorinated chains.

Keratins are important structural components of hair and skin. There has been extensive study of keratins from the health and medical perspectives, although little work has been done to date to investigate their basic physicochemical properties in the form of biomaterials. The work presented in this thesis aimed to study surface and interfacial adsorption and solution aggregation of water soluble keratin polypeptides (made available by previous work within the research group). A range of physical techniques were employed including spectroscopic ellipsometry (SE), neutron reflection (NR), dual polarisation interferometry (DPI), quartz crystal microbalance with dissipation (QCM-D), dynamic light scattering (DLS) and small-angle neutron scattering (SANS).A major technical advantage of the neutron techniques is the use of hydrogen/deuterium substitution to enhance structural resolution. This approach was explored to study the interaction of keratins with both conventional surfactants and novel biosurfactants. The work presented comprises four results chapters. The first examines and compares four widely used interfacial techniques, SE, DPI, QCM-D and NR, by studying the adsorption of C12E6 at the silicon oxide/water interface. Whilst the data exhibits a large degree of consistency in the interfacially adsorbed amount, each technique helped reveal unique structural information with a high degree of complementarity. The second results chapter reports on findings regarding the properties of keratin polypeptides in surface adsorption and solution aggregation. It was found that the keratins adsorbed strongly on the surface of water, and formed rugby-shaped nanoaggregates in solution, the size and shape of which responded to salt concentration. The third results chapter reports on the interfacial behaviour of keratin/surfactants complexes in bulk solution, with cationic DTAB and anionic SDS as model conventional surfactants. It was found that both the electrostatic and hydrophobic forces contributed strongly to the surface adsorption processes. The final results chapter reports on interactions of a coated keratin film with novel biosurfactants including rhamnolipids (R1 and R2 with 1 and 2 sugar head(s), respectively) and Mel-C. The keratin films formed were found to be exceptionally stable and reproducible below pH 8, and these films could be widely used as model keratin substrates for screening their binding with surfactants and bioactive molecules. Both rhamnolipids and Mel-C exhibited strong adsorption onto the keratin substrate and interestingly, whilst R1 exhibited a completely reversible adsorption, R2 showed only a partially reversible adsorption. Mel-C showed some degree of irreversible adsorption similar to R2 and exhibited the strongest adsorption at around pH 4-5. These results show mild interactions with the keratin substrate, but indicate that the extent of adsorption and desorption could be manipulated by surfactant structure or solution conditions. The findings presented in this thesis are fundamental in aiding the development of the use of keratin polypeptides as biomaterials, in applications such as personal care. The work is also highly relevant to the understanding of the interactions between surfactants and keratin molecules at interfaces and in solution.

Les matériaux à faible énergie de surface (LSEMs) sont conçus pour différentes applications. Parmi celle-ci, les applications sur un support solide pour l’élaboration de surfaces superhydro/oléophobes ainsi qu’à l'interface de 2 milieux distincts pour la synthèse de nouveaux tensioactifs éco-responsables. Actuellement, ces matériaux sont constitués essentiellement de composés fluorés pour leurs propriétés uniques leur conférant à la fois l’hydro- et oléo-phobie ainsi que pour leur stabilité thermique et chimique dans des milieux corrosifs. Ce projet montre que l’élaboration des surfaces superhydro/oléophobes peut être réalisée sans utiliser nécessairement des chaînes perfluorées. Deux approches sont adoptées dans ce processus. La première stratégie est d'étudier l'influence de la longueur de la chaîne fluorée sur la structuration et la mouillabilité de la surface des dérivés du ProDOT. La seconde est d'explorer l'influence d'une chaine hydrocarbonée incorporée au coeur des monomères et d'étudier l'effet du type et de la longueur de ces chaînes sur les propriétés de surface. Dans le cadre de l'application des LSEMs sur les ‘matériaux mous’, deux études ont été réalisées : la première se focalisant sur l'effet de la longueur des chaînes hydrocarbonées sur les tensioactifs hybrides à courte chaine fluorée et la deuxième étudiant l'effet de la tête polaire. Deux séries de sulfates et bisulfates hybrides ont donc été synthétisées et leurs propriétés physico-chimiques étudiées. Ce travail a abouti à des résultats intéressants. / Two types of Low surface energy materials LSEMs can be recognized; those which are firstly applied on solid surfaces to elaborate superhydro/oleophobic surfaces that are micro and nano structured, and secondly at the water/air interface to synthesize new ecofriendly surfactants. LSEMs are essentially made from fluorinated compounds due to their unique properties of being both hydro and oleophobic as well as, their thermal and chemical stability in corrosive media. This project shows that the creation of superhydrophobic materials with high oleophobic properties does not necessarily require the utilization of long and bioaccumulative perfluorocarbon chains. Two approaches were adopted in this field. The first strategy was to develop ProDOT derivatives bearing short fluorinated chains to study the influence of the fluorinated chain length on the surface wettability. The proceeding part was to explore the effect of the introduction of a hydrocarbon tail and study the effect of their type and chain length on the surface properties. Another important aspect of this research involves the application of LSEMs on soft materials like surfactants as alternatives to toxic perfluorinated homologues. This study was done to explore the effect of the variant hydrocarbon chains with a short fluorinated tail of hybrid surfactants as well as the effect of the polar head. In this area, two families of hybrid sulfate and bisulfates were synthesized. Their physico-chemical properties were investigated and interesting results were obtained.

Philosophy of Doctor - PHD / The aim of this study was to compare the water quality of raw wastewater and treated sewage effluents from three different sewage treatment plants in the Western Cape, South Africa. The treatment plants investigated are on the same river system. Sewage treatment plant 1 and 2 use older technologies, while sewage treatment plant 3 has been upgraded and new technologies (membrane bioreactor) were incorporated in the treatment processes. The first objective was to determine the occurrence of total coliforms, Escherichia coli (E. coli) and fluoroquinolone and sulfamethoxazole antibiotic residues in raw wastewater and treated sewage effluents. Bacteria in treated sewage effluents can result in diseases such as dysentery, gastroenteritis, and typhoid upon exposure. A chromogenic test was used to screen for coliforms and E. coli. Enzyme linked Immunosorbent Assays (ELISA) were used to quantitate antibiotic residues (fluoroquinolones and sulfamethoxazole) in raw wastewater and treated sewage effluents. This study showed that bacteria are present in raw wastewater and residual bacteria are released with treated sewage effluents from sewage treatment plants. / South Africa

Orientador: Watson Loh / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-27T11:59:07Z (GMT). No. of bitstreams: 1 Ferreira_GuilhermeAugusto_M.pdf: 3614152 bytes, checksum: 568d89fdf3adc43ec1f13c46bc935cad (MD5) Previous issue date: 2015 / Resumo: Surfactantes são moléculas anfifílicas que, em solução, se organizam dando origem a uma série de estruturas de associação, dentre as quais destacam-se os cristais líquidos. Especialmente os brometos de dialquildimetilamônio se associam formando principalmente estruturas líquido-cristalinas lamelares. Nesse trabalho, foram estudadas as propriedades estruturais de fases lamelares formadas pela auto-organização, em solução aquosa, de dois surfactantes dessa classe: o DDAB (brometo de didodecildimetilamônio) e o DODAB (brometo de dioctadecildimetilamônio). Através das técnicas de caracterização utilizadas, foi verificado que, nas condições de concentração e temperatura estudadas, ambos os surfactantes, DDAB e DODAB, se associam em duas fases lamelares, La e Lß, fases essas que diferem pela organização das cadeias carbônicas nas bicamadas e intumescimento. Além de formarem diferentes fases lamelares, essas também apresentaram distintas propriedades estruturais, dependendo do surfactante utilizado. Estudos de calorimetria diferencial de varredura também permitiram acompanhar as transições entre as fases lamelares obtidas causadas por variação da temperatura. As bicamadas formadas pela auto-associação do surfactante DDAB apresentaram um intumescimento menor do que as formadas pelo análogo DODAB, porém, com esse último, houve a formação de bicamadas menos espessas. Misturas preparadas com ambos os surfactantes em diferentes proporções também indicaram a variação das propriedades investigadas, intumescimento e espessura das bicamadas, aumentando o teor de DODAB. A hipótese levantada é que as propriedades estruturais investigadas são fortemente influenciadas pelas forças eletrostáticas atuantes no sistema. A caracterização de amostras formuladas com os tensoativos acima da temperatura de transição para fase fluída e na presença de sal confirmou esta ideia. O maior intumescimento e a pequena espessura das bicamadas formadas pelo DODAB se devem, provavelmente, à interdigitação das cadeias carbônicas e ao efeito de correlação iônica, respectivamente, descritos em mais detalhes nessa dissertação / Abstract: Surfactants are amphiphilic molecules that self-assemble, in solution, giving rise to a number of association structures, among which the liquid crystals stand out. Particularly the dialkyldimethylammonium bromides associate to form mosty lamellar liquid crystalline structures. In this work, we studied the structural properties of lamellar phases formed by self-organization, in aqueous solution, of two surfactants from this class: DDAB (didodecyldimethylammonium bromide) and DODAB (dioctadecyldimethylammonium bromide). Through the used characterization techniques, we found that under the conditions of concentration and temperature studied, both surfactants, DDAB and DODAB are associated in two lamellar phases, La and Lß, phases that differ by the organization of the carbonic chains in bilayers and swelling degree. In addition to forming different lamellar phases, these also showed distinct structural properties, depending on the surfactant used. Studies with differential scanning calorimetry also allowed us to follow the transitions between the lamellar phases caused by temperature variation. The bilayers formed by self-association of DDAB showed a lower swelling degree than those formed by DODAB, however, with the later, there was the formation of thinner bilayers. Mixtures prepared with both surfactants in different proportions also indicated the variation of the investigated properties, swelling degree and bilayer thickness, upon increasing the DODAB content. We propose that the structural properties investigated are strongly influenced by electrostatic forces acting on the system. The characterization of samples formulated with surfactants above the transition temperature to the fluid phase and in the presence of salt confirmed this hypothesis / Mestrado / Físico-Química / Mestre em Química

Os líquidos iônicos, por geralmente apresentar, em sua estrutura, uma cadeia alquílica apolar e uma parte polar, como o cátion imidazólio, podem ser considerados estruturas anfifílicas, e apresentam semelhanças com os tensoativos. Tais estruturas, devido a este caráter anfifílico, podem interagir com estruturas do tipo Lipossomas ou até mesmo com biomoléculas, como a BSA. Neste trabalho, foram sintetizados três líquidos iônicos inéditos, com rendimentos de 52 a 66%, acoplados a sistemas quirais derivados de aminoácidos naturais e de fácil obtenção, como a L-Cisteína, a L-Serina e a L-Treonina. Estes foram caracterizados tanto do ponto de vista estrutural, quanto por suas propriedades fotofísicas. Como procedimento metodológico utilizou-se de ciclocondensação de aminoácidos, esterificação de Steglich e alquilação para inserção de cadeia carbônica ao anel metil-imidazol. Para investigação e confirmação dessas estruturas utilizou-se de estudos de Ressonância Magnética de 1H e de 13C, Infravermelho, além das espectroscopias de absorção na região do UV-Vis e de emissão de fluorescência. Por fim, estes novos líquidos iônicos foram testados com lipossomas e BSA, cujos resultados mostraram boa interação com essas biomoléculas. / Ionic liquids can be considered as amphiphilic structures and have similarities with the surfactants, once they generally have an apolar alkyl chain and a polar moiety, such as the imidazolium cation. Such structures, due to this amphiphilic character, may interact with liposome structures or even with biomolecules, such as BSA. In this work, three new ionic liquids containing chiral systems derived from naturally occurring amino acids, such as L-Cysteine, L-Serine and L-Threonine were synthesized, with yields ranging from 52 to 66%. They were fully characterized both from the structural point of view, and by its photophysical properties. As methodological procedures, amino acid cyclocondensation, Steglich esterification and alkylation were used. In order to investigate and confirm these structures, magnetic resonance studies of 1H and 13C, infrared, as well as absorption spectroscopies in the UV-Vis region and fluorescence emission were used. At last, these new ionic liquids were tested with liposomes and BSA, and the results showed good interaction with these biomolecules.

Source d'émerveillement et d'inspiration poétique, la beauté éphémère des films de savon recèle des questions scientifiques fondamentales, qui ont de nombreuses répercussions pour des applications allant de la formulation des shampoings à la récupération du pétrole. L'objectif de cette thèse est de comprendre comment la vie d'un film de savon, depuis sa génération jusqu'à sa rupture, dépend des propriétés physico-chimiques des tensioactifs qui le stabilisent.Dans une première partie, je m'intéresse à la génération de films savonneux verticaux, que je modélise à l'aide d'un modèle stationnaire supposant des tensioactifs insolubles. Je montre que l'épaisseur de tels films est gouvernée à la fois par la vitesse de génération et l'élasticité de surface du film. Le modèle décrit avec succès les données expérimentales pour des tensioactifs solubles, au moins dans le cas où l'adsorption est lente. Je présente également un dispositif expérimental original permettant de générer des films stabilisés par des tensioactifs insolubles, qui constituent un système modèle prometteur.Dans un second temps, j'étudie l'évolution temporelle – i.e. le drainage et la rupture – de films liquides minces en génération continue, en commençant par le cas simplifié des liquides purs. A l'aide d'une simulation non-stationnaire, je parviens à prédire le temps de vie de films d'huile silicone fonction de la vitesse de génération, qui se montre en accord quantitatif avec les expériences. Je caractérise ensuite expérimentalement le drainage des films savonneux en fonction de différents paramètres – position dans le film, vitesse de génération et humidité ambiante – et montre l'influence de la concentration en tensioactif dTAB et de l'humidité sur le temps de vie du film. Pour terminer, j'explore l'influence de la concentration en tensioactifs sur le drainage et la rupture de bulles hémisphériques flottant à la surface d'un bain savonneux, un système se rapprochant des mousses réelles. / The ephemeral beauty of soap films is not only a source of wonder and poetic inspiration, but also conceals fundamental scientific questions, which are at the heart of various applications, ranging from shampoo formulation to oil recovery. This work aims at understanding how the life of a soap film, from its generation until its rupture, is affected by the physical-chemical properties of the surfactants used to stabilise it.First, I present a stationary model describing the generation of vertical soap films, under the assumption of insoluble surfactants. I show that the film thickness is controlled by both the generation velocity and the film surface elasticity. The model successfully describes experimental data for soluble surfactants, at least when adsorption is slow. I also introduce an original experimental set up for the generation of liquid films stabilised by insoluble surfactants, which are certainly a promising model system. Secondly, I study the time evolution – i.e. the drainage and rupture – of thin films pulled from a liquid bath, starting with the simplified case of pure liquids. Implementing a non-stationary simulation, I am able to predict the lifetime of silicone oil thin films as a function of the generation velocity, which I find in quantitative agreement with experimental data. I then carry out systematic experiments to characterise the drainage of soap films for various generation velocities, environmental humidities and positions in the film. I also demonstrate the influence of dTAB concentration and humidity on film lifetime. Finally, I investigate how surfactant concentration affects the drainage and break-up dynamics of hemispherical soap bubbles at the surface of a liquid pool, which is a system somewhat closer to real foams.