Quaternary ammonium lipids containing long hydrocarbon-chains can cause deleterious effects when administered to many types of microorganisms. Some compounds have potent activity against spermatozoa and the HIV virus. Consequently, quaternary ammonium lipids are key components in spermicidal and antiseptic formulations. Surface-active quaternary ammonium lipids, containing a hydrophobic and hydrophilic moiety, will aggregate into micelles when dissolved in water above a narrow concentration range, termed the critical micelle concentration (CMC). This project investigates how the CMC relates to spermicidal and microbicidal properties. The CMC’s of the AD-nX and AT-nX compounds [see documents for figures] were determined by conductivity measurements. Relationships among the CMC and factors such as alkyl-chain length, head-group size, counteranion, and biological activity are discussed. [See document for figures of ADn and ATn] / Master of Science

Two types of oily waste sludges generated by a railroad maintenance facility were studied to reduce the volume of hydrocarbon waste. The specific goals of this laboratory study were to evaluate rate and extent of microbial degradation, benefits of organism addition, role of biosurfactant, and dewatering properties. The oily waste sludges differed in characteristics and contained a mixture of water, motor oil, lubricating oil, and other petroleum products. Degradation was measured using COD, suspended solids, GC measurements of extractable material, and nonextractable material concentration. Biosurfactant production was characterized using surface tension and polysaccharide measurements. Degradation of ten percent waste oil showed that the removal in a 91 day experiment was 75 percent for COD and suspended solids, 98 percent for extractable oil, and negligible for non-extractable material. It was concluded that methylene chloride extraction could be used to estimate degradation potential of a hydrocarbon waste. Addition of organisms increased the rate and extent of degradation over 22 days, but did not provide any benefits over 91 days. Data suggested that microorganisms degraded simple compounds first, then produced biosurfactants. It was thought that the biosurfactants remained attached to the organism membrane and increased solubility, stimulating the degradation of difficult to degrade waste oil. After oil was degraded the biosurfactants became ineffective. The dewatering properties of 10 percent oily sludge deteriorated with the production of biosurfactant and improved after the surfactant was degraded due to changes in oil solubility. / Master of Science

[pt] O presente trabalho tem como principal objetivo compreender o mecanismo de estabilização de emulsões por cristais líquidos de estrutura lamelar. Emulsões são dispersões coloidais formadas por dois líquidos imiscíveis, como água e óleo. Para garantir a estabilidade das emulsões, é preciso adicionar emulsificantes, como surfactantes, por exemplo. Em alguns tipos de cosméticos é muito comum o uso de cristais líquidos, formados pela adição de álcoois graxos que atuam como co-surfactantes, levando à redução da curvatura das micelas e, consequentemente, à transição para uma fase de estrutura lamelar. Neste trabalho, para o preparo das amostras, foram empregadas substâncias comumente utilizadas como ingredientes de emulsões cosméticas estabilizadas por cristais líquidos: cloreto de cetrimônio, álcool cetílico, água e óleo mineral. Em seguida, diversas técnicas foram utilizadas para: caracterizar a estrutura em escala nanométrica por Espalhamento de Raios X a Baixos Ângulos, SAXS, analisar a viscosidade por curvas de fluxo e a viscoelasticidade por ensaios oscilatórios através da Reologia, determinar a distribuição de tamanho das gotas e acompanhar a estabilidade das emulsões, por Microscopia Óptica e Difração de Laser. Dessa forma, foi realizada uma análise sistemática, variando diversos parâmetros, como concentração dos componentes, método de preparo e energia de homogeneização, possibilitando determinar como estes parâmetros levam a diferentes mecanismos de estabilização de emulsões por cristais líquidos lamelares. Além de afetar o tamanho das gotas, a energia aplicada para homogeneização também determina o comportamento dos cristais líquidos lamelares no sistema. Dentre os diferentes comportamentos observados, vale ressaltar a formação de um recobrimento lamelar ao redor das gotas ou de uma rede lamelar espalhada pelo meio contínuo. A correlação desses fenômenos com propriedades macroscópicas, como reologia e estabilidade, permitirá um maior controle das propriedades finais em emulsões cosméticas e até mesmo em outras aplicações. / [en] The main goal of the present study is to understand the mechanism of stabilization of emulsions by lamellar liquid crystals. Emulsions are colloidal dispersions formed by two immiscible liquids, such as water and oil. To guarantee the stability of the emulsions, it is necessary to add emulsifiers, such as surfactants, for example. In some types of cosmetics, it is very common to use liquid crystals, formed by the addition of fatty alcohols that act as co-surfactants, leading to the reduction of the curvature of the micelles and, consequently, to the transition to a phase of lamellar structure. In this work, for the preparation of the samples, substances often used as ingredients of cosmetic emulsions stabilized by liquid crystals were used: cetrimonium chloride, cetyl alcohol, water and mineral oil. Then, several techniques were used to: structural characterization at nanoscale by Small Angle X-Ray Scattering, SAXS, analysis of viscosity by flow curves and viscoelasticity by oscillatory tests using Rheology, determination of drops size distribution and monitoring emulsion stability by Optical Microscopy and Laser Diffraction. Thus, a systematic analysis was performed, varying several parameters, such as the concentration of components, preparation method and homogenization energy, allowing to determine how these parameters lead to different mechanisms of stabilization of emulsions by lamellar liquid crystals. In addition to affecting the droplet size, the energy applied for homogenization also determines the behavior of lamellar liquid crystals in the system. Among the different behaviors, it is worth mentioning the formation of a lamellar coating around the drops or a lamellar network spread over the continuous medium. The correlation of these phenomena with macroscopic properties, such as rheology and stability, will allow tuning the final properties in cosmetic emulsions, and even in other applications.

No / Incorporating edge activators (surfactants) into liposomes was shown previously to improve estradiol vesicular skin delivery; this phenomenon was concentration dependent with low or high concentrations being less effective. Replacing surfactants with limonene produced similar behaviour, but oleic acid effects were linear with concentration up to 16% (w/w), beyond which it was incompatible with the phospholipid. This present study thus employed high sensitivity differential scanning calorimetry to probe interactions of additives with dipalmitoylphosphatidylcholine (DPPC) membranes to explain such results. Cholesterol was included as an example of a membrane stabiliser that removed the DPPC pre-transition and produced vesicles with a higher transition temperature (Tm). Surfactants also removed the lipid pre-transition but reduced Tm and co-operativity of the main peak. At higher concentrations, surfactants also formed new species, possibly mixed micelles with a lower Tm. The formation of mixed micelles may explain reduced skin delivery from liposomes containing high concentrations of surfactants. Limonene did not remove the pre-transition but reduced Tm and co-operativity of the main peak, apparently forming new species at high concentrations, again correlating with vesicular delivery of estradiol. Oleic acid obliterated the pre-transition. The Tm and the co-operativity of the main peak were reduced with oleic acid concentrations up to 33.2 mol%, above which there was no further change. At higher concentrations, phase separation was evident, confirming previous skin transport findings.

Cette thèse présente une étude originale de l'effet d'un copolymère bloc de polyisobutylene - polydimethylsiloxane (PIB-PDMS) utilisé comme agent actif interfacial sur le comportement dynamique des gouttes Newtoniennes isolées suspendues dans une matrice Newtonienne de polyisobutylene (PIB). Le travail a été divisé en deux parties. La première partie présente des expériences sur des gouttes pures de polydimethylsiloxane (PDMS), et également sur des gouttes PDMS modifiées à 2wt% de copolymère bloc. Les gouttes expérimentées ont été à cinq différentes masses moléculaires. La tension interfaciale des gouttes a été mesurée avec et sans ajout de copolymère bloc. Les gouttes modifiées ont montré une tension interfaciale inférieure à celle des gouttes pures. La présence du compatibilisateur (PIB-PDMS) a altéré le mode de déformation et de rupture des gouttes compatibilisées, ainsi que la puissance du champ d'écoulement nécessaire pour les déformer et pour les rompre en les comparants avec des gouttes de PDMS pures. Toutefois, les mesures de déformations dans les deux régimes; équilibre et transitoire ont augmenté. Les gouttes pures ont suivi le mode de rupture classique qui se caractérise par une déformation symétrique ellipsoïdale de la goutte suivi par une forme cylindrique et enfin rupture en deux gouttelettes majeures de même taille et quelques gouttelettes de petites tailles. La deuxième partie de cette thèse a été consacrée à l'évaluation des effets de la concentration du compatibilisateur (par l'ajout de 0.5, 2 et 10 wt% dans la goutte de PDMS) sur le comportement dynamique des gouttes. Les gouttes choisies ont été de type PDMS ayant deux rapports de viscosité, p =0.036 et p =1.13. Dont le but de faire une comparaison, la même expérience a été également réalisée sur les gouttes de PDMS pures. Les gouttes compatibilisées ayant deux rapports de viscosité, p =0.036 et p =1.13, ont montré une déformation plus élevée en comparaison avec les gouttes de PDMS pures. Les concentrations choisies, à savoir 0.5, 2, 10wt%, sont respectivement inférieures, égales et supérieures à la concentration critique, 0.5% < Cs = 2% < 10%. La concentration critique, Cs, de copolymère bloc sur la surface des gouttes de PDMS a permis d'expliquer les résultats des étapes initiales (au taux de cisaillement faible) de déformation des gouttes de PDMS ayant deux rapports de viscosité cités ci-dessus. Au taux de cisaillement plus élevé, la déformation des gouttes modifiées ayant un rapport de viscosité plus bas a été déterminée par une extension des bouts (tip-stretching), la distribution non-uniforme du bloc copolymère (PIB-PDMS) sur la surface de la goutte de PDMS et l'effet de dilution sur la surface de la goutte. Toutefois, pour les gouttes ayant un rapport de viscosité plus élevé, des paramètres comme la viscosité de la goutte, l'absence de circulation interne du fluide et la difficulté de la mobilité des blocs de copolymère dans les phases similaires ont déterminé le comportement de déformation et de rupture des gouttes.

La génération des fréquences somme (SFG), une technique spectroscopique spécifique aux interfaces, a été utilisée pour caractériser les changements de la structure macromoléculaire du surfactant cationique chlorure de dodécyltriméthylammonium (DTAC) à l’interface silice/eau dans une plage de pH variant entre 3 et 11. Les conditions expérimentales ont été choisies pour imiter les conditions les plus communes trouvées pendant les opérations de récupération assistée du pétrole. Particulièrement, la silice a été étudiée, car elle est un des composantes des surfaces minérales des réservoirs de grès, et l’adsorption du surfactant a été étudiée avec une force ionique pertinente pour les fluides de la fracturation hydraulique. Les spectres SFG ont présenté des pics détectables avec une amplitude croissante dans la région des étirements des groupes méthylène et méthyle lorsque le pH est diminué jusqu’à 3 ou augmenté jusqu’à 11, ce qui suggère des changements de la structure des agrégats de surfactant à l’interface silice/eau à une concentration de DTAC au-delà de la concentration micellaire critique. De plus, des changements dans l’intensité SFG ont été observés pour le spectre de l’eau quand la concentration de DTAC augmente de 0,2 à 50 mM dans les conditions acide, neutre et alcaline. À pH 3, près du point de charge zéro de la surface de silice, l’excès de charge positive en raison de l’adsorption du surfactant cationique crée un champ électrostatique qui oriente les molécules d’eau à l’interface. À pH 7 et 11, ce qui sont des valeurs au-dessus du point de charge zéro de la surface de silice, le champ électrostatique négatif à l’interface silice/eau diminue par un ordre de grandeur avec l’adsorption du surfactant comme résultat de la compensation de la charge négative à la surface par la charge positive du DTAC. Les résultats SFG ont été corrélés avec des mesures de l’angle de contact et de la tension interfaciale à pH 3, 7 et 11. / Sum Frequency Generation (SFG), an interface specific spectroscopic technique, was used to characterize the changes in the macromolecular structure of the cationic surfactant dodecyltrimethylammonium chloride (DTAC) at the silica/water interface at pH values ranging from 3 to 11. The experimental conditions were selected to mimic conditions common during enhanced oil recovery operations. In particular, silica was studied since it is one of the most abundant mineral components of sandstone reservoirs, and surfactant adsorption was studied at an ionic strength (100 mM NaCl) relevant to hydraulic fracturing fluids. SFG spectra showed detectable peaks with increasing amplitude in the methylene and methyl stretching region when the pH was lowered to 3 or increased to 11, suggesting changes in the surfactant aggregate structure at the silica/water interface at a DTAC concentration above the critical micelle concentration. In addition, changes in the SFG intensity were observed for the water spectrum when increasing the DTAC concentration from 0.2 to 50 mM under acidic, neutral or alkaline conditions. At pH 3, near the point of zero charge of the silica surface, the excess positive charge due to adsorption of the cationic surfactant creates an electrostatic field that orients water molecules at the interface. At pH 7 and 11, which are above the point of zero charge of the silica surface, the negative electrostatic field at the silica/water interface decreases in magnitude with surfactant adsorption due to compensation of the negative surface charge by the positively charged DTAC. The SFG results were correlated with contact angle and interfacial tension measurements at pH 3, 7 and 11.

Le détachement d'une goutte est un phénomène que nous observons quotidiennement. Il résulte de la rupture de l'interface entre le fluide dispersé en goutte et le fluide environnant. Cette rupture a fait l'objet de nombreuses études. Il est bien établi que sa dynamique est régie par une compétition entre la capillarité, l'inertie, et la viscosité du fluide. Ce manuscrit décrit l'influence sur la dynamique de rupture d'une modification des propriétés de l'interface entre deux fluides à l'aide d'agents de surface. Lorsque l'agent de surface est un surfactant (SDS), la dynamique d'amincissement peut se faire selon deux modes. Deux régimes linéaires en temps constituent le premier mode. Le second mode comporte trois régimes linéaires. Dans les deux cas, l'aminicissement commence par un premier régime, suivi d'un deuxième régime de pente plus forte. Lorsque le troisième régime existe, sa pente est inférieure à celle du second régime. La variation des pentes des régimes linéaires témoigne du comportement dynamique du surfactant à l'interface. La valeur de la tension interfaciale $\gamma$ extraite du premier régime linéaire correspond à la valeur à l'équilibre de la tension interfaciale du système, $\gamma_{eq}$. La vitesse d'amincissement plus élevée au cours du second régime est reliée à une dépletion partielle en surfactant de la zone d'amincissement maximal. Le ralentissement constaté pendant le troisième régime est lié au déplacement de cette zone vers une région plus riche en surfactant, où la tension $\gamma$ est plus faible. La dynamique d'amincissement du cou est très différente lorsque des polymères de poids moléculaire intermédiaire ($\sim$ 100 kDa) sont présents simultanément avec du SDS dans la phase continue. Lorsque $C_{SDS}$ est supérieure à 0,15 fois la concentration micellaire critique (CMC), le comportement est identique à celui observé en présence de surfactant seul. En dessous de 0,15 CMC, l'amincissement ralentit exponentiellement à l'approche de la rupture, et un phénomène de beads-on-a-string apparaît. Ces constatations sont analogues à celles faites lorsqu'une solution de polymères est menée à la rupture. Dans notre cas, les polymères sont uniquement à la surface du jet et non dans son volume! Une analyse des profils du cou au cours du temps démontre l'existence d'une auto-similarité à l'approche de la rupture. Bien que les systèmes étudiés soient plus complexes, ils présentent des caractéristiques qualitativement analogues à celles observées dans des systèmes de fluides simples. Toutefois, il existe une grande différence quantitative. / Droplet detachment is ubiquitous in everyday life. It results from the rupture of an interface separating two fluids. This rupture has been widely studied. It is now well established that it relies on a competition between capillary, inertial and viscous phenomena. In this manuscript, we report on the influence on the breakup dynamics of the presence of surface agents at the interface. When SDS is used as a surface agent, thinning can proceed in two ways. In the first mode, the dynamics of thinning are characterized by two linear-in-time regimes. The second mode is made of three linear-in-time regimes. In both cases, thinning starts with a first regime, followed by a steeper second regime. When a third regime exists, its slope is softer. Slope variation bears witness to a dynamical behaviour of the surfactants at the interface. The value for the interfacial tension $\gamma$ calculated from the slope of the first linear regime is in agreement with the equilibrium interfacial tension of the system, $\gamma_{eq}$. The higher thinning speed during the second regime is linked to a partial depletion in surfactant of the maximal thinning zone. The slowdown in the tihrd regime is related to a displacement of the thinning zone in a region of higher surfactant concentration, where $\gamma$ is lower. The thinning dynamics is very different when polymers are added to the surfactant solution. If $C_{SDS}$ is higher than 0.15 times the critical micellar concentration (CMC), a behaviour similar to the pure-surfactant case is observed. Below 0.15 CMC, an exponential slowdown is observed in the last instants, as well as a "`beads-on-a-string"' phenomenon. These observations are analogous to what is seen when a solution of polymers is led to breakup. In our case, polymers are not in the bulk; they are at the interface of the two fluids! Analysis of the profiles of the neck in both cases showed that profiles are self-similar. Qualitatively, they share features with profiles observed in the case of breakup of interfaces between simple fluids. Quantitatively, slopes and angles are different.

Foi estudado o comportamento eletroquímico de interfases Cu/H2SO4 0,5 mol L-1 na ausência e presença de compostos triazólicos - benzotriazol (BTAH) e tolitriazol (TTAH) e de surfactantes: dodecilsulfato de sódio (SDS aniônico) e cloreto de dodecilamônio (DAC catiônico) a 25ºC, empregando eletrodo parado e de disco rotativo (EDR). Foram empregadas como técnicas medidas de potencial de circuito aberto, polarização potenciostática e potenciodinâmica, cronoamperometria, espectroscopia de impedância eletroquímica e microscopia óptica. As características inibidoras do filme formado dependem da natureza dos aditivos e das condições hidrodinâmicas. As interfases contendo BTAH, TTAH, BTAH + TTAH, BTAH + SDS e TTAH + SDS apresentaram uma faixa ampla de potencial em que o cobre se mostrou passivado, chegando a 200 mV para a mistura BTAH + SDS empregando EDR. Densidades de corrente de passivação tão baixas quanto 2&#181;A cm-2 foram observadas com EDR na presença de BTAH + TTAH. As misturas composto triazólico - surfactante mostraram filmes menos resistentes. Os surfactantes isolados não produzem faixa passiva e antecipam o potencial de oxidação do cobre com eletrodo parado. As misturas triazol - DAC só produzem faixa passiva com EDR. Todos os aditivos se mostraram inibidores para a reação H+/H2, destacando-se, com eletrodo parado, BTAH, TTAH e BTAH + TTAH. / The electrochemical behavior of 0.5 mol.L-1 Cu/H2SO4 interphases has been studied in the presence and in the absence of triazolic compounds-benzotriazole (BTAH) and tolitriazole (TTAH) and of surfactants - sodium dodecylsulphate (anionic, SDS) and dodecylammonium chloride (cationic, DAC) at 25ºC, using non-stirred electrode and rotating disc electrode (RDE). Open circuit potential, potentiostatic and potenctiodinamic polarization, chronoamperometry, electrochemical impedance spectroscopy, and optical microscopy were used as techniques. The inhibitive features of the formed film depend on both the nature of the additives and on the hydrodynamic conditions. The interphases containing BTAH, TTAH, BTAH + TTAH, BTAH + SDS e TTAH + SDS presented a wide potential range where the copper is passivated, reaching to 200 mV for BTAH + SDS mixture using RDE. Low passivating current densities (2&#181;A cm-2) were observed with RDE in the presence of BTAH + TTAH. Triazolic compound?surfactant mixtures have originated less resistant films. Isolated surfactants do not originate passive ranges and anticipate the oxidation potential of copper under non stationary conditions. The mixtures triazole-DAC only produce passive range at stationary conditions. All the additives have shown to be inhibitors for the H+/H2 reaction, specially BTAH, TTAH e BTAH + TTAH using non stirred conditions.

‘Soft condensed matter’ is a newly-emerged sub-discipline of physics concerned with the study of systems that are mechanically soft such as colloids, emulsions, surfactants, polymers, liquid crystals, granular media and various biomaterials including DNA and proteins. These materials display a broad range of interesting microstructures and phase behaviours and have a myriad of applications in the materials, food, paint and cosmetic industries as well as medical technologies. Soft condensed matter physics presents new opportunities and challenges for the development of new ideas and concepts in experimental and theoretical physics alike. Because the field overlaps with many different disciplines, the study of soft matter also offers promising developments to other fields of science including chemistry, chemical engineering, materials science, biology, and environmental science. The behaviour of these systems is dominated by one simple fact: they contain mesoscopic structures in the size range 10 nm to 1 µm that are held together by weak entropic forces. The elastic constants of these materials are 109 times smaller than the conventional atomic materials and hence are easily deformable by external stresses, electric or magnetic fields, or even by thermal fluctuations. We have studied two important classes of soft matter systems in this thesis -colloidal suspensions and surfactant systems. The thesis is divided into two main themes: (a) Effects of electric field on the colloidal suspensions, and (b) Effects of shear on surfactant solutions. Motions of colloidal particles under the influence of applied electric field were observed under a microscope and were studied using image analysis and particle tracking. We have also used tracking of thermal fluctuations of colloidal particles embedded in surfactant gels to study microrheology of surfactant solutions. Linear and non-linear rheology of aqueous solutions of cationic cetyltrimethyl ammonium bromide (CTAB) and anionic sodium-3-hydroxynapthalene-2-carboxylate (SHNC) were studied using bulk rheology in a commercial rheometer. Rheological studies of an anionic surfactant sodium dodecyl sulphate (SDS) in the presence of strongly binding counterion p-toluidine hydrochloride (PTHC) has also been done. Chapter 1 starts with a general introduction to soft condensed matter systems and then we proceed to describe two specific class of soft condensed materials which we have studied in this thesis -colloidal suspensions and surfactant/water systems. After describing different types of colloids, we discuss why colloids are suitable as model systems in condensed matter physics. This is followed by a discussion on the chemical structure, phase behaviour and self assembling properties of surfactant molecules in water. We then discuss the inter-macromolecular forces such as van der Waals interaction, the screened Coulomb repulsion, hydrogen bond, hydrophobic and hydration forces and steric repulsion which are the major players in the interaction in soft condensed matter systems. The systems that have been the subject of our experimental studies, viz. polystyrene colloidal suspensions, CTAB+SHNC, SDS+PTHC and CTAT have also been discussed in detail. Then we have given an overview of effects of electric field on the colloidal suspensions. Two types of geometries have been discussed: one in which the field is parallel to the plates and another when the field is perpendicular to the electrodes. Application of colloidal particles in diagnostic tests (Latex Agglutination Tests) has been discussed after this. Some methods used to enhance the sensitivity of LATs have also been reviewed. This is followed by a theoretical background of linear and non-linear rheology. We have also given an introduction to digital video microscopy, its advantages and discussed few quantities like pair correlation function, structure factor which can be extracted using digital video microscopy and particle tracking. The concluding part of this chapter describes the organization of this thesis. Chapter 2 discusses the experimental apparatus and techniques used in our studies. We describe our setup for applying the electric field to the colloidal particles and imaging and tracking their motion. We also discuss the image processing and analyzing methods for extracting the useful quantities from the digitized images. We have described the various components of the MCR-300 stress-controlled rheometer (Paar Physica, Germany) and the AR-1000N stress-controlled rheometer (T. A. Instruments, U. K.) followed by different experimental geometries that we have used for our experiments. Next we have described the various experiments that can be done using a commercial rheometer. Calculation of surface charge of colloidal particles using a conductivity meter has been demonstrated for our colloidal particle suspensions. We also describe the sample preparation methods employed in different experiments. In Chapter 3, we have discussed our study of clustering of colloidal particles under the influence of an ac electric field as a function of frequency. The field was applied in a direction perpendicular to the confining walls. Two regimes are observed, a low frequency regime where the clusters are isotropic with a local triangular order and a new high-frequency regime where the clusters are highly elongated (anisotropic) with no local order. The crossover from one regime to the other occurs at a critical frequency, fc. The formation of elongated clusters seen at high frequencies is explained in terms of rotation of particles due to a phase lag between the polarization of the electric double layer around a particle and the applied electric field that arises because of inhomogeneities of the conducting surface. We have also observed that the threshold field for the cluster formation, Eth, increases with frequency in both the regimes. We did these studies on two different sizes of particles and found that both Eth and fc were lower for the larger particles. Our model based on particle rotation was able to estimate the value of fc correctly for both the sizes of the particles. Chapter 4 describes a method employing an ac electric field applied perpendicular to the confining walls to increase the sensitivity of recognition of ligands by their corresponding receptors grafted on Brownian latex particles. Application of electric field assists the colloidal micro-particles grafted with receptors to come nearer due to electro-hydrodynamic drag. This increase in the local concentration of the latex particles results in improving the chances of ligand-receptor interaction leading to the aggregation of the latex particles. With this technique we have been able to increase the sensitivity of the ligand-receptor recognition by a factor as large as 50. We have demonstrated the utility of our method using streptavidin as the model receptor and biotinylated RNase A as the model ligand. We have also applied our technique to a commercially available kit for rheumatoid factor (RF) with successful results. The same method was also successfully applied for the detection of typhoid whose antibodies were purified and attached to polystyrene particles by our collaborators from DRDE Gwalior. In Chapter 5, we have studied the statics and dynamics of colloidal particles at different applied electric fields from zero to beyond the threshold field. We have taken a series of time-lapsed images and calculated out the pair-correlation function, mean squared displacement, structure factor, non-Gaussian parameter etc. We have studied both mono-dispersed colloidal system and binary colloidal system (mixture of two different sizes of particles). The aggregates formed in the two cases were analysed with the help of Voronoi polygons to quantify the microscopic structure. In mono-dispersed system, the aggregates formed were two-dimensional hexagonal crystals and we have used this system to study the freezing transition in 2-dimension. The properties of the system in the liquid and the crystalline state satisfy various criteria for the 2-d freezing transition. The first maximum of the structure factor at the voltage at which freezing occurs, is 5.5 as has been suggested for the 2-d freezing. This is reflected in the dynamics of the system also, where the ratio D/D0 falls below 10%, in accordance with the LPS (L¨owen, Palberg, Simon) criterion for freezing in 2-d colloidal systems [Phys. Rev. Lett. 70, 1557 (1993)]. However, in the binary colloidal system the clusters formed were not crystalline but more like 2-d dense liquids. A closer inspection of these clusters reveals that the motion of a smaller subset of particles is cooperative and follows string-like paths. The mean square displacement of such a system shows a plateau in the intermediate times which indicates the “caging” of particles by its neighbours. A peak in non-gaussian parameter indicates the presence of dynamical heterogeneities in the system. In Chapter 6, we have described the use of multiple particle tracking to study the microrheology of semidilute solutions of wormlike micelles and compared the results with those from macrorheology experiments done on the same samples. Two concentrations of CTAT (1.3% and 2%) were used. We observed that, in spite of the mesh size being much smaller than the size of the probe particles, the viscoelastic response function calculated using the one-point microrheology does not match with that measured from macrorheology. This can be attributed to the fact that there is another important length scale in the system, the mean micellar length, and it is comparable to the probe particle size. Two-point microrheology was successful in verifying the macrorheology results for CTAT 1.3% but it fails to do so for CTAT 2%. We attribute this to the fact that in a higher viscosity sample (2%), the hydrodynamic force propagate to a lesser distance, thereby limiting the measurable correlation between the particles and precluding the success of two-point microrheology. Chapter 7 describes a rheological study of aqueous solutions of varying concentration of cationic cetyltrimethyl ammonium bromide (CTAB) and anionic sodium-3-hydroxynapthalene-2-carboxylate (SHNC) kept at a fixed molar concentration ratio [CTAB]/[SHNC] = 2. At this molar ratio, the surfactants self-assemble into wormlike micelles which get entangled above the overlap concentration to form viscoelastic gel. The range of the total surfactant concentration φ varies from 1.17% to 5.16% by weight. We found that, plateau modulus, G0, shows a power law dependence on the surfactant concentration, φ, with an exponent 3, which is higher than the expected value of 2.25 observed for the one-component wormlike micelles. Zero shear viscosity, η0, and relaxation time, τR show a maximum at the surfactant concentration, φmax = 1.9% in contrast to a monotonic increase with φ. We propose that this non-monotonic behaviour is due to the unusual dependence of the average micellar length L ¯on φ, showing a maximum in average micellar length L at φmax. This argument provides a strong support to the model of micellar growth in the presence of electrostatic interactions developed by Mackintosh et. al [Europhys. Lett. 12, 697 (1990)]. The presence of electrostatic interactions also appears in the behaviour of the plateau modulus G0 that exhibits a larger φ dependence than in highly screened micelles. In the non-linear flow experiments, a minimum observed in critical shear rate (the shear rate at which shear thinning starts), ˙γc, at φmax strengthens our arguments. In Chapter 8, we describe the phase behaviour and rheology of SDS+PTHC (sodium dodecyl sulphate + p-toluidine hydrochloride) micellar solutions at different molar ratios α=[PTHC]/[SDS]) of the two components. At low values of α, polarizing microscopy observations reveal a transition from an isotropic to a nematic phase of disk-like micelles, whereas a transition to a lamellar phase occurs at higher α values > 0.5, on increasing the surfactant content. Linear rheology of the isotropic micellar solution reveal a viscous behaviour over a large range of surfactant concentrations. Surprisingly, this also extends to the nematic phase of disk-like micelles observed at α =0.2 and φ =0.35. These systems also exhibit a viscoelastic behaviour over a narrow range of surfactant concentration as reported in earlier studies. The extent of the viscoelastic region of the isotropic micellar solution also decreases with increase in α. Frequency sweep curves in this region, scaled on to a master curve is reminiscent of dilute suspensions of hard spheres or rigid Brownian rods. Consistent with the results from oscillatory shear measurements, the f;ow behaviour examined under steady shear is Newtonian over a large range of surfactant content in the isotropic micellar solution. An interesting result in these studies is the non-monotonic behaviour of the viscosity with increase in surfactant concentration. It is likely that the sharp rise in viscosity arises from a jamming effect of the rigid rods. Dynamic light scattering studies suggest that the drop in viscosity is due to the decrease in the length of the micellar aggregates. This is followed by a change in the morphology of the micelles from rods to disks as indicated by the transition to a nematic phase of disk-like micelles or a lamellar phase. A change in the morphology of micellar aggregates with increase in α is expected in mixed surfactant systems with strongly binding counterions. However, the surprising result is the change in morphology of the micellar aggregates with surfactant content. Such a behaviour is seen in mixed surfactant systems for the first time. The thesis concludes with a summary of our main results and a brief discussion of the scope of future work in Chapter 9.

Thanks to their adaptability and high efficiency compared to traditional carbon based surfactants, silicone surfactants are a success in many different applications, from pesticides to cosmetics, polyurethane foam, textile and car care products. In spite of those numerous applications, no analytical method existed for their trace determination in environmental samples and no data have been available regarding their environmental occurrence and fate. An analytical method for the trace analysis of trisiloxane surfactants in the aqueous environment was developed and validated. The method, based on liquid-liquid extraction and HPLC-MS/MS, reaches limits of quantification in the ng L-1 range and allows an individual quantification of every homologue of the targeted trisiloxane surfactant. The newly developed analytical method was applied to analyze 40 river water samples. The targeted trisiloxane surfactant was detected in 14 samples, between 1 ng L-1 and 100 ng L-1. The results showed that the studied trisiloxane surfactant does not ubiquitously occur in the aquatic environment in measurable concentrations, but can reach surface waters on a local scale. In order to assess the persistence of the trisiloxane surfactant in surface waters, its hydrolysis was studied in the lab, under various conditions (temperature, pH, and concentration). The half-lifes at pH 7 and 2 mg L-1 were found to be between 29 days and 55 days at 25°C and between 151 days and 289 days at 12°C. Taking only into account the hydrolysis, these results indicate that the trisiloxane surfactant could persist several weeks in surface waters. A degradation product of the trisiloxane surfactant was tentatively identified by high resolution mass spectrometry. When used as agricultural adjuvants, trisiloxane surfactants may reach the soil compartment and might further leach to ground water. The behavior of the trisiloxane surfactant on soil was therefore investigated to assess the possibility to reach ground water. With a sorption batch equilibrium method, distribution coefficients between water and soil (Kd, Koc, and Kclay) were estimated for two standard soils (loam and sandy loam) and for every homologue of the trisiloxane surfactant. The obtained values for Kd were between 15 L kg-1 and 135 L kg-1, indicating that the trisiloxane surfactant is only slightly mobile in soil. To further investigate the possibility of leaching to ground water after application on agricultural fields, the leaching in soil was simulated in the lab in a soil column. The experimental settings were designed to simulate a worst case scenario where the application of the trisiloxane surfactant is done on quartz sand and is immediately followed by a heavy rainfall. Even in these conditions, less than 0.01 % of the initially applied trisiloxane surfactant leached through 20 cm of quartz sand. Based on the Kd values and the results of the leaching in soil column, the studied trisiloxane surfactant is considered to be unlikely to leach to ground water after application as an agricultural adjuvant.