Rozprawy doktorskie na temat „Sodium sulfonates”

An experimental investigation of the high pressure synthesis of water soluble, self doping conducting polymers is presented. 2- And 3-aminobenzenesulfonic acid and the respective sodium sulfonates have been polymerised. Optimal polymerisation conditions have been determined with respect to yield, conductivity and molecular weight. Reaction parameters such as oxidant, pressure, catalysts, reaction time and temperature and the use of additives were investigated. The minimum pressure required for polymerisation was 7 kbar. An increase in pressure had a negligible effect on polymer characteristics. The polymers were generated in aqueous, non-acidic media, to ensure they were selfdoping when characterised. Conductivities of between 10-6 Scm-1 and 10-3 Scm-1 were measured. The sulfonate salts reacted faster than the sulfonic acids and for both a longer reaction time resulted in higher yields and conductivities. These polymers were completely water soluble, of high molecular weight and able to be cast as thin films. The arylamines 5- and 8-aminonaphthalene-2-sulfonic acid and their respective sodium sulfonates were polymerised at elevated pressure. The naphthalene sulfonate salts polymerised at atmospheric pressure, but displayed a higher molecular weight when reacted under pressure. Generally the naphthalene monomers reacted similarly to the benzene monomers, although there were some differences. Conductivity and yield decreased with increased reaction times and the use of 0.1M equivalents of ferrous sulfate had an negligible effect on the polymers. The polynaphthalenes were highly water soluble, self doping and had conductivities in the order 10-5 to 10-3 Scm-1. A measurement of the activation volume for the polymerisation of 2-methoxyaniline and sodium 8-aminonaphthalene-2-sulfonate was performed. These were determined to be -44 ± 3 cm3mol-1 and -62 ± 10 cm3mol-1 respectively. These large negative values are consistent with rate limiting monomer oxidation.

An experimental investigation of the high pressure synthesis of water soluble, self doping conducting polymers is presented. 2- And 3-aminobenzenesulfonic acid and the respective sodium sulfonates have been polymerised. Optimal polymerisation conditions have been determined with respect to yield, conductivity and molecular weight. Reaction parameters such as oxidant, pressure, catalysts, reaction time and temperature and the use of additives were investigated. The minimum pressure required for polymerisation was 7 kbar. An increase in pressure had a negligible effect on polymer characteristics. The polymers were generated in aqueous, non-acidic media, to ensure they were selfdoping when characterised. Conductivities of between 10-6 Scm-1 and 10-3 Scm-1 were measured. The sulfonate salts reacted faster than the sulfonic acids and for both a longer reaction time resulted in higher yields and conductivities. These polymers were completely water soluble, of high molecular weight and able to be cast as thin films. The arylamines 5- and 8-aminonaphthalene-2-sulfonic acid and their respective sodium sulfonates were polymerised at elevated pressure. The naphthalene sulfonate salts polymerised at atmospheric pressure, but displayed a higher molecular weight when reacted under pressure. Generally the naphthalene monomers reacted similarly to the benzene monomers, although there were some differences. Conductivity and yield decreased with increased reaction times and the use of 0.1M equivalents of ferrous sulfate had an negligible effect on the polymers. The polynaphthalenes were highly water soluble, self doping and had conductivities in the order 10-5 to 10-3 Scm-1. A measurement of the activation volume for the polymerisation of 2-methoxyaniline and sodium 8-aminonaphthalene-2-sulfonate was performed. These were determined to be -44 ± 3 cm3mol-1 and -62 ± 10 cm3mol-1 respectively. These large negative values are consistent with rate limiting monomer oxidation.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
School of Science
Full Text

Polymers containing less than 10 mol % of ions (ionomers) have been studied in depth for their potential in producing polymers with tailored properties for specific applications. A small molar percentage of ions can be incorporated into a polymer to drastically enhance the properties of the polymer. An ionomer that has been studied is that of isoprene copolymerized with sodium styrene sulfonate (poly(I-co-NaSS)). Research has been performed relating to the synthesis and chemical characterization of the copolymers. However, an in depth study of the way the physical properties are affected by a change in ion concentration has not been presented. Thus, it is the goal of this thesis to synthesize a series of poly(I-co-NaSS) copolymers with varying levels of sulfonated styrene and characterize their physical properties. The poly(I-co-NaSS) polymers, containing a range of 1.15 to 4.74 mol % NaSS, were polymerized using free radical emulsion polymerization. The copolymer compositions were confirmed using combustion sulfur analysis. Dynamic light scattering indicated that large aggregates were present in solution. These aggregates were large enough that capillary intrinsic viscosities could not be measured. Small angle x-ray scattering (SAXS) and thermal analysis showed little change as the ion concentration was increased, while tensile, stress relaxation and adhesion properties were improved. The absence of changes in the SAXS patterns indicated that there was an absence of a well-defined ionic aggregate, while the mechanical properties showed evidence of electrostatic interactions. This can be at least partially attributed to ionic interactions on a smaller scale (doublets, triplets).
Master of Science

La rupture du ligament croisé antérieur du genou est une affection fréquente qui survient majoritairement chez des sujets jeunes et sportifs. Une fois rompu, en raison de sa localisation intra articulaire et de la pauvreté de sa vascularisation, ce ligament ne cicatrise pas spontanément. Le traitement chirurgical de référence, l’autogreffe, présente de nombreux inconvénients et les travaux de recherche se tournent vers le développement d’implants ligamentaires synthétiques. Dans ce contexte, l’objectif de la thèse était d’étudier la possibilité d’élaborer un nouveau ligament bioactif et biodégradable en polycaprolactone (PCL) greffé de poly(styrène sulfonate de sodium) (pNaSS). Les résultats présentés dans ce manuscrit décrivent toutes les étapes du choix initial de la PCL brute à sa caractérisation, sa fonctionnalisation, ses propriétés mécaniques après élaboration, au mécanisme de dégradation et à son impact biologique in vitro et in vivo. À l’interface des disciplines de l’ingénierie, de la chimie, de la mécanique et de la biologie, nous avons montré que : le greffage de pNaSS accélère la dégradation de la PCL tout en protégeant la surface durant les six premiers mois ; que les propriétés mécaniques de la PCL sont adaptées à une application ligamentaire ; que le greffage de pNaSS favorise in vitro la vitesse de croissance, la distribution, la densité et l’étalement cellulaires, la production de facteur de croissance et le maintien de l’expression génique ; et enfin que le greffage de pNaSS permet in vivo de diminuer l’inflammation articulaire et l’arthrose post-opératoire tout en favorisant la recolonisation tissulaire
The rupture of the anterior cruciate ligament of the knee is a common affection which mainly occurs in young and active population. Because of its joint location and its poor vascularization, this ligament does not heal spontaneously. The “gold-standard”, consisting of using autograft, has many disadvantages and the research focuses on the development of synthetic ligament implants. In this context, this thesis studies and evidences the possibility of a new ligament with bioactive and biodegradable features, made of polycaprolactone (PCL) grafted with poly(sodium styrene sulfonate) (pNaSS). The results presented in this manuscript evaluate the initial choice of raw PCL, its characterization, its functionalization, its mechanical properties after processing, its degradation mechanism and its in vitro and in vivo biological impact. At the interface of engineering, chemistry, mechanics and biology fields, we demonstrated that: the pNaSS grafting accelerates the PCL degradation while protecting the surface during the first six months; the mechanical properties of PCL are adapted to the ligament application; in vitro the pNaSS grafting promotes cell growth, cell distribution, cell density, cell spread, growth factor production, and maintenance of gene expression; and finally that in vivo the pNaSS grafting allows to reduce joint inflammation and postoperative osteoarthritis while promoting tissue recolonization

In the past three decades, a new group of concrete admixtures, termed &ldquo
superplasticizers&rdquo
, were introduced to the concrete industry. They have gained wide acceptance because of their many advantages. The addition of superplasticizers to concrete improves the workability and strength of concrete. In this study, the effect of the chemical structure of poly (4-styrenesulfonic acid-co-maleic acid) sodium salt (SSAMA), which contains both sulfonic and carboxylic acid groups, which is a new superplasticizer, was analyzed. Two different molecular weights of PEG (polyethylene glycol monomethyl ether) were grafted to this water-soluble copolymer at different weight compositions. The structures of synthesized copolymers were verified by FTIR and NMR analyses. The molecular weight difference of the grafted copolymers with different side chain lengths was determined by dilute solution viscosimetry. The effects of chemical structure of grafted copolymers on the fluidity of cement paste and the mechanical properties of the mortars were investigated. The zeta potential measurements revealed the interactions between the cement particles and polycarboxylate type superplasticizers. The maximum fluidity was achieved for the PEG grafted copolymer with the weight ratio 3:3. The mechanical properties of this copolymer showed the highest flexural and compressive strength compared to other copolymers. The addition of various Li salts to SSAMA affected the ionic medium, therefore, the dispersion performance of cement paste and the mechanical properties of the mortars improved. The mixture of LiCl: SSAMA in 1:1 mol ratio exhibited the maximum fluidity compared to other Li salts and their compositions. This mixture gave the highest flexural strength but the mixture of Li2CO3 in 1:1 composition gave the highest compressive strength in each salt mixtures.

Le Laboratoire de Biomatériaux et Polymères de Spécialité a développé des copolymères solubles composés d'acide métacrylique et de styrène sulfonate de sodium. Ces copolymères ont une activité antitumorale et antiangiogénique in vitro. Ils inhibent l'adhérence cellulaire à la matrice extracellulaire médiée par les intégrines. Les capacités inhibitrices des copolymères ont été montrées sur une lignée cancéreuse mammaire et sur des cellules endothéliales primaires. Le manque d'adhérence empêche le recrutement du cytosquelette d'actine et provoque l'inhibition de la prolifération cellulaire dès les premiers jours d'incubation. La migration et la différentiation des cellules endothéliales sont également ce qui entraîne une diminution de la densité de formations pseudovasculaires. L'efficacité des copolymères est fonction du type cellulaire considéré et de leur composition en MA et NaSS. Le copolymère composé de 30% de MA et à 70% de NaSS semble être le plus actif. Par ailleurs, les copolymères MA/NaSS induisent l'anoïkis de manière importante chez les cellules endothéliales sans montrer de cytotoxicité. Les copolymères MA/NaSS représentent surtout une stratégie intéressante dans la lutte contre l'angiogénèse pathologique. Ils continuent à faire l'objet d'étude pour élucider de façon complète leur mécanisme d'action et, à plus long terme, évaluer leur efficacité in vivo sur des modèles animaux
The Laboratoire de Biomatériaux et Polymères de Spécialité has developped soluble copolymers composed of methacrylic acid and sodium styrene sulfonate. These copolymers have antiangiogenic and antitumor activities in vitro. They inhibit cell adhesion to the extracellular matrix mediated by integrins. We have shown this activity on a breast cancer cell line and on primary cultured endothelial cells. The lack of adhesion prevents the recruitment of actin cytoskeleton and induces the inhibition of cell proliferation. Cell migration ans differentiation are also inhibited and the density of microtubules decreased. The efficacy of copolymers depends o their composition and on cell type. The copolymer composed of 30% methacrylic acid and of 70% sodium styrene sulfonate seems to be the most efficient. The copolymers induce anoïkis in endothelial cells without any toxicity. These new copolymers are an interesting strategy in antiangiogenic therapies. We continue to study them to better know their mechanism of action and to evaluate their in vivo efficiency

Le mécanisme et la stabilité d’auto-assemblage de deux polyélectrolytes (PAH et PSS) en vue de la nano-encapsulation ont été essentiellement étudiés par réflectométrie laser à angle fixe. Cette technique se révèle très utile pour quantifier la masse de polymère adsorbé en fonction du temps sur un substrat. Dans un premier temps, plusieurs méthodes, de conversion du signal réflectométrique en quantité adsorbée, ont été présentées. Ainsi, ans le cas de film monocouche, une nouvelle approche de conversion des signaux est nécessaire afin de prendre en compte un fort changement d’indice de la solution dû à des concentrations de polymères importantes. Dans le cas de films auto-assemblés, le modèle consiste à considérer une couche adsorbée d’épaisseur et d’indice variant après chaque injection. La deuxième partie, a permis de proposer un mécanisme d’auto-assemblage de ces deux polyélectrolytes. Cette étude réalisée sur substrat plan, à l’aide de la réflectométrie et de l’AFM, met en évidence des différences de comportement de chaque polyélectrolyte. On a aussi eu recours à une étude sur colloïde pour montrer le rôle important des ions, le changement d’ionisation des polymères et le nombre de couches nécessaire à une couverture complète du substrat. Enfin, cette partie s’est terminée par l’étude de films très épais, constitués d’un nombre de couches allant jusqu’à 320, et nécessitant l’utilisation de techniques nouvelles dans ce domaine, le faisceau d’ions focalisé et la spectroscopie à décharge luminescente. La dernière partie a traité de la stabilité du film auto-assemblé lors de son rinçage dans des conditions différentes ou non de celles de la construction. Le dernier polyélectrolyte adsorbé et le nombre de couches déposées influent le comportement des films. Ces résultats permettent de prévoir les conditions de conservation de ces films ainsi que celles de déconstruction partielle ou totale en vue du relargage du principe actif contenu dans les capsules
The growth mechanism and the stability of polyelectolyte films elaborated by multi-steps self association were investigated using principally fixed angle laser reflectometry. The first part of the investigation addressed the conversion of the reflectometric output into the deposited weight of polymer. In the case of a monolayer we have established the range of validity of a linear relationship between the deposited weight and the reflectometric output. In the case of a multilayer film we have used and explored a new approach developed in the laboratory allowing the determination of the stepwise change of the refractive index and the film thickness, leading eventually to the deposited weight. The second part of the work is dedicated to the experimental elaboration of films with the polyelectrolytes poly(allylamine,HCl) and poly(styrene sulfonate). The influence of the principal operational parameters was screened (pH, ionic strength, type of electrolytes, molecular weight of polymers, washing between deposition steps, etc). The charge balance and the incorporation of small ions were determined step by step. The elaboration of films on the flat silica substrate in the reflectometric cell was compared with that on colloidal silica. Complementary characterization of the polymer films were made with AFM and Focused ion beam imaging (FIB-SIM), which allowed the determination of the films morphology and roughness. Very thick films were constructed. A growth mechanism was proposed to explain the transition between an early stage (first steps), influenced by the property of the surface and later steps where the growth only depends on the interaction between the two polymers. Finally the stability of 1 to 5 bilayers films was examined upon change of the pH of the solution

Neste trabalho estudou-se o comportamento de soluções dos hidrótropos toluenossulfonato de sódio (TSS) e n-butilbenzeno sulfonato de sódio (NBBSNa) quanto a suas características de agregação/associação por Ressonância Magnética Nuclear 1H (RMN 1H), espalhamento de raios-X à baixo ângulo (SAXS), espalhamento de luz estático (SLS) e espalhamento de luz a médios ângulos (WAXS). Medidas realizadas com outros hidrótropos tais como estirenossulfonato de sódio (ESS), salicilato de sódio (SalS) e benzoato de sódio (BS) foram realizadas para comparação dos resultados. O NBBSNa foi sintetizado, purificado e caracterizado. Os experimentos de RMN revelam mudanças no deslocamento químico com a concentração, indicando mudança de ambiente a que as moléculas estão submetidas. Pela técnica de SLS pode-se avaliar o segundo coeficiente do virial das soluções de TSS com e sem a adição de um soluto. Pelas análises de SAXS determinou-se o tamanho do agregado de NBBSNa utilizando ajustes pelo programa SASfit, sendo o resultado comparado com um surfactante clássico dodecilbenzenossulfonato de sódio (DBSNa). O NBBSNa é um sistema de três densidades eletrônicas e esférico. Os demais hidrótropos estudados apresentam comportamento de líquido, sendo observado a correlação das moléculas a curta distância nos experimentos de WAXS.
In this work the behavior of solutions of the hydrotropes sodium toluene sulfonate (TSS) and sodium n-butylbenzene sulfonate (NBBSNa) was studied, concerning the aggregation/association characteristics of this molecules by the use of Nuclear Magnetic Resonance (NMR 1H), small angle x ray scattering (SAXS), static light scattering (SLS) and wide angle x ray scattering (WAXS). Measurements with other hydrotropic molecules like sodium styrene sulfonate (ESS), sodium salicylate (SalS), sodium benzoate (BS) were realized in order to discuss the results. The NBBSNa molecule was synthesized, purified and characterized. The experiments of NMR revealed changes in the chemical shift with the concentration, indicating the changes of the surround environment in what molecules are embedded. For the technique of SLS, the second virial coefficient of the solutions of TSS could be evaluated with and without the addition of a solute. By the SAXS data the size of the aggregate of NBBSNa was determined using the SASfit software. The result was compared with a classic surfactant sodium dodecylbenzene sulfonate (DBSNa). NBBSNa is a spherical system of three electronic densities. All the other hydrotropes studied shows a liquid scattering behavior. By WAXS experiments a correlation of the molecules at short distance was observed.

This work is focused on physical interactions of negatively charged polymers with small ionogenic fluorescent molecules. Trying to verify the presence of these interactions using fluorescence correlation spectroscopy (FCS) and provides a comprehensive view of the problem. The aim of this work is to observe the effect of concentration on the diffusion properties. P/D ratio, where P represents number of polymer binding sites and D number of dye binding sites, was chosen for this issue. Hyaluronate, sodium chondroitin sulfate and sodium polystyrene sulfonace were used as polymers and Acridine Orange, and Rhodamine 6G were chosen as fluorescent probes. The reason why this experiment uses these probes, was the assumption, that the positive charge occuring on the fluorescent probe will lead to the electrostatic interaction with the negatively charged polymer. As a result, the bond between acridine orange and polyelectrolyte was not clearly demonstrated, but the interaction with Rhodamine 6G have been proved.

Ce travail a été entrepris en vue d'une étude approfondie des phénomènes de relaxation croisée dans un système de deux spins 1/2. Nous avons été amenés à développer des logiciels qui couvrent toutes les phases du traitement de données de RMN : analyse des signaux de précession libre (RMNY), traitement des données de relaxation (TFIT) en termes de paramètres dynamiques et interprétation de ces derniers en termes de mouvements moléculaires (TWOSTEG). Ces logiciels sont écrits en turbo pascal et fonctionnent sur tout micro-ordinateur compatible PC. L'étude de la relaxation croisée a été réalisée sur deux tensio-actifs micellisés comportant un cycle benzénique avec la tête polaire et la chaîne aliphatique en position para. Ce sont l'obs (octyl-benzène sulfonate du sodium) et le 4-DBS (4-dodecyl-benzène sulfonate du sodium) étudiés dans les mêmes conditions (0. 3M dans D20 à 50#O). Nous avons élaboré de nouvelles méthodes aussi bien sur le plan expérimental que sur le plan du traitement pour : 1) Détermination précise des termes de relaxation croisée, en fonction de la fréquence de mesure, dans des systèmes homo et hétéronucléaires de deux spins 1/2 ; 2) détermination précise des termes d'interférence entre l'intéraction dipolaire carbone-proton et l'anisotropie de déplacement chimique du carbone ou du proton ; 3) Étude d'un système de deux spins 1/2 couplés en présence d'un champ radio-fréquence (relaxation et transferts de type hartmann-hahn)

Ce travail concerne l'etude des proprietes des solutions de polyacrylonitrile (pan) et des copolymeres d'acrylonitrile et de methallylsulfonate de sodium observees a l'equilibre ou hors equilibre thermodynamique. Utilisees dans la fabrication de membranes de dialyse renale, ces solutions ont ete explorees par rmn a une echelle d'espace caracteristique des processus physiques (cristallisation, demixtion) responsable des proprietes de permeabilite de ces membranes. Le pan et son copolymere presentent en solution un diagramme de phases typiques d'un polymere semi-cristallin; les conditions d'etablissement de la transition de phase solide-liquide et de la transition liquide-liquide ont ete precisees pour des solutions en solvant binaire dmf-eau equimolaire. La presence de charges ioniques sur la chaine polymere provoque un elargissement du domaine de la demixtion; cet effet a ete modelise dans le cadre de description des solutions proposees par flory. La cinetique de mise en ordre de ces polymeres en solution peut etre decrite comme un processus gouverne par une nucleation heterogene et sporadique, sans etape de croissance; cette cristallisation conduit a la formation de domaines ordonnes dont la taille moyenne a ete evaluee a l'aide de donnees thermodynamiques. Les membranes de dialyse renale realisees a partir de ces solutions peuvent etre decrites comme des gels physiques composes de domaines ordonnes interconnectes par des chaines polymeres a l'etat amorphe. La presence de ces domaines gouverne les proprietes de permeabilite et de selectivite de ces membranes

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The main anionic surfactants world widely used are the sodium dodecyl benzene sulfonate (LAS) and sodium dodecyl sulfate (DSS), which are mainly used in the manufacturing of domestic and personal hygiene products. As a consequence of the great and increasing consumption of LAS and DSS there is an increasing wareness regarding the adverse effects of these compounds to the organisms and environment. The present study aimed to evaluate the acute and chronic toxicity of the compounds LAS and DSS to the cladocerans Daphnia similis, Ceriodaphnia dubia and Ceriodaphnia silvestrii. It was also evaluated the toxicity of the water and sediments of four reservoirs and one stream of São Paulo State Analyses of LAS concentrations in the water of these reservoirs were also performed by Liquid chromatography. Acute toxicity tests indicated a value of CE(I)50;48h for LAS of 14.17 mg L-1 to D. similis, 11.84 mg L-1 to C. dubia and 13.51 mg L-1 to C. silvestrii. Significant changes in the viability of the cladoceran offsprings were observed for C. dubia and C. silvestrii exposed to the LAS, with values of CENO equal to 1.0 mg L-1 to C. dubia and 2.5 mg L-1 to C. silvestrii. It was concluded that the maximum permissible concentration of 0.5 mg L-1 surfactants as established by the resolution CONAMA nº. 357/2005 (Brazilian Ministry of Environment) in order to protect aquatic communities is adequate, considering the sensitivity of the native species C. silvestrii. The results of the acute toxicity tests with DSS indicated a CE(I)50;48h value of 12.82; 4.37 and 5.42 mg L-1, for D. similis, C. dubia and C. silvestrii, respectively. A CENO value of 2.0 mg L-1 was obtained in the chronic toxicity tests for C. silvestrii. The surfactant LAS was detected in all the water samples collected in the Lobo (Broa), Lagoa Dourada and Fazzari reservoirs, but at concentrations lower than 5 mg L-1 (the method limit of detection). The toxicity tests with environmental samples revealed that there is no toxicity in the water of the Lobo and Lagoa Dourada sampled, however the water of Monjolinho Reservoir was toxic to D. similis and Fazzari stream was toxic to D. similis and C. dubia. Only the sediment of Monjolinho Reservoir was not toxic to cladocerans.
Os principais surfactantes aniônicos disponíveis no mercado mundial são o dodecil benzeno sulfonato de sódio (LAS) e o dodecil sulfato de sódio (DSS), utilizados principalmente em produtos de limpeza doméstica e de higiene pessoal. Devido ao grande consumo mundial de LAS e de DSS há uma crescente preocupação sobre os efeitos adversos destes compostos no ambiente e aos organismos. Este trabalho teve por objetivo avaliar a toxicidade aguda e crônica do LAS e do DSS aos organismos-teste Daphnia similis, Ceriodaphnia dubia e Ceriodaphnia silvestrii. Foi também avaliada a toxicidade da água e dos sedimentos em quatro reservatórios e um riacho do estado de São Paulo por meio de testes de toxicidade aguda e da análise quantitativa do surfactante LAS. Os testes de toxicidade aguda indicaram uma CE(I)50;48h do LAS de 14,17 mg L-1 para D. similis, 11,84 mg L-1 para C. dubia e 13,51 mg L-1 para C. silvestrii. Nos testes crônicos realizados foi observada significativa alteração viabilidade da progênie de C. dubia e C. silvestrii exposta ao LAS, com valores de CENO igual a 1,0 mg L-1 para C. dubia e 2,5 mg L-1 para C. silvestrii. Pode-se concluir que o valor máximo permissível de surfactantes de 0,5 mg L-1, estabelecido pela Resolução CONAMA nº. 357/2005 em águas destinadas à proteção das comunidades aquáticas, é adequado para a espécie nativa C. silvestrii. Nos testes de toxicidade aguda de DSS foram obtidos valores de CE(I)50;48h de 12,82; 4,37 e 5,42 mg L-1, para D. similis, C. dubia e C. silvestrii, respectivamente. No ensaio de toxicidade crônica obteve-se valor de CENO igual a 2,0 mg L-1 para C. silvestrii. O surfactante LAS foi detectado nas amostras de água dos Reservatórios do Lobo (Broa), Lagoa Dourada e Represa do Monjolinho em concentração inferior a 5 mg L-1. Os testes revelaram que não há toxicidade aguda aos cladóceros da água da Lagoa Dourada e do Reservatório do Lobo, havendo, contudo, toxicidade da água da Represa do Monjolinho para D. similis e da água do Córrego do Fazzari para os cladóceros D. similis e C. dubia. Somente a amostra de sedimento da Represa do Monjolinho não causou toxicidade aos cladóceros.

Nous avons étudié les interactions de deux copolymères de l'acrylamide et du 2-acrylamido-2-méthyl propane sulfonate de sodium, l'AM-AMPS-20 (20% en moles) et l'AM-AMPS-5, avec les bromures de : -tetramethylammonium (TMAB),- décaméthylène bis-trimethylammonium (10(TA)2B2), -dodecylbenzyldimethylammonium (12FDAB). Les isothermes de complexation, les mesures rhéologiques, électrophorétiques et conductimétriques montrent que, contrairement au TMA+, le 12FDA+ et le 10(TA)2++ s'apparient avec les sulfonates des copolymères. Les associations de polyions complexés sont appréhendées par diffusion quasi-élastique de la lumière. La formation de micelles sur les polyions est décelée par spectroscopie de fluorescence du pyrène. L'adsorption de l'AM-AMPS-5 sur la silice en présence du 12FDAB est établie par l'isotherme d'adsorption mixte et visualisée par microscopie électronique à transmission
We have studied the interactions of two copolymers of acrylamide and sodium acrylamido-2-methyl propane sulfonate, AM-AMPS-20 (20% in moles) and AM-AMPS-5, with the bromides of : -tetramethylammonium (TMAB), -decamethylene bis-trimethylammonium (10(TA)2B2), and -dodecylbenzyldimethylammonium (12FDAB). The complexation isotherms determined by selective permeation of a hollow fiber membrane, rheology, laser Doppler electrophoresis and conductivity measurements show that, in opposition to TMA+, 12FDA+ and 10(TA)2++ cations complex with sulfonates of both copolymers. Associations of polyions-12FDAB complexes are disclosed by dynamic light scattering. The onset of micelle formation on polyions is determined by pyrene fluorescence spectroscopy. Adsorption of AM-AMPS-5 onto colloidal silica in presence of 12FDAB is established through individual adsorption isotherms and visualised by transmission electron microscopy

In this diploma thesis, the interactions between polyelectrolyte and surfactant at low and also at high concentration were studied. There was used pyrene as fluorescent probe during the fluorescence spectroscopy measurement, a cationic surfactant cetyltrimethylammonium bromide and as a main polyelectolyte has been chosen sodium polystyrene sulfonate at 1 MDa molecular size. In the medium containing 0.15 M NaCl we could observed a creation of the complexes – precipitates in the surrounding of CMC concentration and behind of this concentration. In the mixtures containing sodium polystyrene sulfonate and hyaluronan together, there was stronger tend to keep aggregation properties of sodium polystyrene sulfonate during difference concentration ratios. Beyond CMC concentration, hyaluronan starts to influence the aggregation properties of the system as well.

This diploma thesis studied the interaction of ionic and amphiphilic fluorescent probes with polyelectrolytes. The research of such colloidal system could be helpful in deeper understanding of interactions between polyelectrolytes and surfactants. The aim of this thesis was to determine whether ionic or amphiphilic probes are suitable for this research. Two polyelectrolytes, sodium polystyrene sulfonate and hyaluronan were used in this study. Interactions of polyelectrolytes with fluorescent probes (4-Di-2-Asp, methylene blue, dodecyl acridine orange, DiO and DiA) were studied in this work. Then cationic surfactant cetyltrimethylamonium bromide was added to this system. Samples were studied using fluorescence and UV/VIS spectroscopy. Emission and absorption spectra of these probes were recorded. This experiment was based on hypothesis that due to positive charge these probes will bind to the negatively charged polyelectrolyte. Formation of dimers or other aggegates was presumed for fluorescent probes dodecyl acridine orange and methylene blue. When 4-Di-2-Asp was used,changes in fluorescence intensity and absorption spectra in connection with possible formation of aggregates was supposed to be observed. It should be noted that formation of dimers for 4-Di-2-Asp is not described in literature. The formation of dimers wasn't clearly demonstrated during the measurement. Formation of dimers was observed only with dodecyl acridine orange. Probes DiO and DiA were used only in the study of the interaction with polyelectrolytes. These fluorescent probes showed up as inappropriate, because they adsorbed on tube walls. When cationic surfactant was added to hyaluronan-fluorescent probe system, surfactant pushed away fluorescent probe and bonded electrostatically to negatively charged groups of polyelectrolyte.

Coal seams are unconventional subsurface formations that host methane and are weaker (relative to conventional subsurface) formations. Coal seams are prone to coal fines generation within the fractured porous space throughout the life of the reservoir. These coal fines damage the permeability, deliverability and productivity of coal seams. Furthermore, the coal fines mobility/blockage in the hydraulically induced fractures and proppant packs negatively impacts the proppant conductivity. In this work, a comprehensive study has been conducted to augment the understanding of coal fines and their behaviour within porous and proppant pack systems. Systematic experiments were conducted to address the coal fines by developing various approaches presented in this work. The approaches adopted to achieve the study objectives were: i) streaming zeta potential on coal and sandstone, ii) nano-treated proppant surface modification for coal fines adsorption, and iii) coal fines mobility/attachment in the proppant packs. One of the electrokinetic parameters that is crucial in releasing/mobilising coal fines is coal’s zeta potential. The coal surface is generally hydrophobic and possesses negative zeta potential. Researchers have used the electrophoretic zeta potential technique to indicate charge identification of coal particles, denoting repulsion or attraction of the particle. In chapter 3, a robust study investigates streaming zeta potential measurements of an in-situ sub-bituminous coal core saturated with saline water of 0.1, 0.3 and 0.6 mol.dm-3 NaCl salinities. Thus, the novel study determines the charge carried by percolating fluid when passing through coal rock. The zeta potential is directly proportional to saline water salinity. The trends found in the research were consistent with reported zeta potential measured using other techniques, while the magnitude varied. The findings reported in the study apply to subsurface coal seams at salinity up to 0.6 mol.dm-3 NaCl. Coal seams are hydraulically fractured for commercial production, and sand-based proppants occupy the fractured space. Before understanding the electrokinetics of coal fines, the behaviour of these sand-based proppants should be determined. Sand-based proppants are predominantly silica, and so are sandstones. Furthermore, the selection of sandstone was further motivated by two reasons, i) for comparison and benchmarking, and ii) correlation with coals (as sandstone and coal both are negatively charged). The research presented in chapter 4 considered clay-rich (i.e. clay ≥ 5 wt.%) sandstones for the first time (as coal can have clay ingredients). Specifically, streaming potential measurements were conducted on Bandera Grey sandstone (clay-rich and -poor) saturated with saline water in pressurised environments. Additionally, the streaming potential was determined at identical conditions for the effect of two surfactants, sodium dodecylbenzene sulfonate (SDBS) and cetrimonium bromide (CTAB), at concentrations of 0.01 and 0.1 wt. % on the clay-poor sample. Moreover, a comparison of electrophoretic and streaming zeta potentials was conducted. Accordingly, the work analyses the effects of mineralogy and surfactants within this process. Clay-rich sandstone possessed lower zeta-potentials than clay-poor sandstone at the two tested salinities. SDBS reduced zeta-potential and yielded higher repulsive forces rendering the rock more hydrophilic. Additionally, electrophoretic zeta-potentials were higher when compared to streaming zeta-potentials. Mechanisms for the observed phenomena are also provided. Following the observations from the two studies, proppant column experiments with glass bead proppant and high volatile bituminous were conducted and are presented in chapter 5. One of the approaches to handling coal fines is its dispersal within the aqueous suspension. Proppant column experiments were conducted to test various schemes. It was found that coal zeta potential using SDBS reaches a maximum, and regardless of the pH, it effectively delivers the maximum output of coal fines in the effluent. Thus, a 0.001 wt.% SDBS could effectively disperse coal fines suspension through proppant packs. Nano-treated proppant surface modification was developed to investigate coal fines mobility/attachment within the proppant packs. Succinctly, four (alumina, magnesia, silica and zirconia) nanoparticles (NPs) were adsorbed onto synthetic porous media (glass bead) using a robust pseudo-continuous fixed-bed (PCFB) adsorption method in work presented in chapter 6. A wide range of salinity (0 to 10.5 wt.% NaCl), temperature (298.15 to 348.15 K), NPs loading (0.01 to 0.2 wt.%), and injection rate (1 to 50 mL.min-1) were tested. Results showed that PCFB adsorption of NPs with higher specific surface area resulted in faster adsorption (adsorbed in ~25 mins) with > 99% immobilisation of NPs on the proppant pack. Adsorption kinetics showed reasonable conformity with the pseudo-first-order model, where isothermal adsorption followed the Sips model. The adsorption capacity of magnesia NPs (specific surface area 50 to 80 m2.g-1, 7 wt.% NaCl) at 298.15 K was higher than silica NPs. Accordingly, the newly developed PCFB method can be used for onsite treatment of proppants with nanoparticles, which can then be injected into a fractured formation to achieve multiple objectives such as fines fixation, wettability alteration and sand control. In this work, another study explored the application of nano-treated proppant packs on the adsorption of coal fines, presented in chapter 7. In this study, the objective was to identify silica nano-formulations (0 – 0.1 wt.%), and coal fines concentration of 0.1 to 1 wt.% were examined to determine the fixation of coal fines within the glass bead synthetic proppant pack. The quantitative results showed that the proppant pack with nanoparticle treatment strongly affects the fixation ability of coal fines. The non-NP treated pack yielded 30% adsorption, whilst the NP treated pack yielded 74% adsorption. It was noted that greater adsorption is also related to the higher zeta potential of silica NPs (i.e. nearer to iso-electric point). A set of laboratory experiments on industrial-grade proppants was conducted as the definitive work, presented in chapter 8. The work involved sensitivity experiments as a function of coal rank, pH, salinity, and surfactants. These conductivity results were compared with established analytical models to interpret the mechanistic coal-proppant interaction in the presence of an electrolyte. It was found that fines dispersion and its mobility within the proppant pack is easier at high pH, low salinity, temperature, anionic surfactants, and lower concentration of coal fines. However, fines mobility is reduced at neutral pH, high salinity, temperature, and cationic surfactants.

碩士
中山醫學大學
醫學研究所
101
Background and Motivation: Since the 1960s, Adriamycin started as an anti-cancer drug. So far, despite the push into a new chemotherapy drugs, but either alone or in combination with other chemotherapy drugs, Anthrocycline -based chemotherapy remains an important cornerstone. Which Epirubicin is the most commonly used chemotherapy drug, but its unique heart toxicity affects its use, or even serious side effects affecting the survival of cancer patients. Epirubicin may damage by free radicals, iron ions involved in the redox reaction, a calcium ion concentration and starting a series of signal transduction induced apoptosis,then, cardiac toxicity resulting generation. There is still no definitive treatment for far advanced cardiotoxicity . Danshen (丹蔘) is a important traditional Chinese medicine used in gynecological and cardiovascular diseases. Modern research has found that the anti-oxidative stress effect, open a cardioprotective effect Danshen series of studies. Materials and Methods: In this study, by H9C2 rat embryonic heart cells, cell culture, MTT analysis, flow cytometry, and Western blotting experiments. Explore Epirubicin lead to heart toxicity mechanisms and Danshen derivative Sodium Tanshinon IIA sulfate (STS) intervention study. Results: study confirmed the heart of STS on Epirubicin induced toxicity does have a protective effect. The mechanism in addition to reducing free radical damage, reducing mitochondrial damage, more importantly, within the endoplasmic reticulum-based regulation of signal transduction: reducing calpain, caspase 12 to inhibit apoptosis. In addition, STS can also be activated AKT, JNK and NFκB pathway down to achieve the purpose of regulation of apoptosis. Conclusion: The results of this study suggested Danshen has a protective effect to Epirubicin induced cardiotoxicity and possible mechanism for instructions. Expect future clinical treatment of cancer patients can be used in adjunctive therapy to reduce side effects of Epirubicin- based chemotherapy.

碩士
中國文化大學
應用化學研究所
88
Experimental results show that the surface tension of shampoo appears to decrease with increasing the concentration of sodium dodecylbenzene sulfonate, and that the viscosity of shampoo increase with increasing the concentration of sodium dodecylbenzene sulfonat, as a result of increased free volume resulting from the intermolecular interaction. The experimental results also indicate that the contact angle of oil drop on the surface of the glass plat is seen to increase with increasing the concentration of sodium dodecylbenzene sulfonat. Although the contact angle of oil drop on the glass surface is smaller than 90∘, it is considered to possess partially efficacy of removing oil stain. In order to increase the capability of removing oil stain, we tried to increase the concentration of sodium chloride and to fix the concentration of other ingredients used in the formulation of shampoo. It was found that the viscosity of shampoo is seen to increase with increasing the concentration of sodium chloride, as a result of the intermolecular interaction. It is seen that the contact angle of oil drop on the glass surface appears not to increase with an increase of the concentration of sodium chloride, indicating that use of sodium chloride in the formulation of shampoo has no efficacy of removing oil stain.

碩士
國立中央大學
生命科學研究所
89
Linear alkylbenzene sulfonates (LAS) are the most widely used anionic surfactants today. These compounds accumulate in the environment and show toxic effects on organisms in polluted water. This strain utilized sodium dodecylbenzene sulfonate (DBS) as sole source of sulfur in a minimal salts medium containing 0.3 % succinate. The bacterium can’t be identified by BioLog method in Gram-negative database. Further identification by 16S rDNA sequence was performed and showed 98 % identity to many Enterobacter species. Phylogenetic tree was constructed from an alignment of 1,193 nucleotides of 16S rDNA sequences showing the highest phylogenic relationship with Enterobacter agglomerans. And the bacterium was designated Enterobacter sp. SH3. The growth of strain was demonstrated as a function in the decreasing of DBS, which was analyzed by liquid chromatography-mass spectroscopy (LC-MS). It’s specific that Enterobacter. sp. SH3 can utilize several alkanesulfonates and aromatic sulfonates as sole sulfur source to grow. The action of the release of sulfite from DBS was measured using Ellman’s reagent followed by the absorbance increased at 430 nm as an enzyme assay. The highest enzyme activity was observed in the addition of 500 mM NADPH and 3 mM FMN in 0.3 ml 10 mM Tris-HCl, pH 9.0. The preliminary biochemical feature of the enzyme acting in Enterobacter sp. SH3 was showed to be similar to an FMNH2-dependent alkanesulfonate monooxygenase from Escherichia coli EC1250. A series of column chromatography was applied to purify the desulfonation enzyme. The active fraction from chromatofocusing chromatography was at pI of 5.18－4.12. The native molecular weight was at the range of 60－150 kDa by Sephacryl S-200 gel filtration chromatography. This highly purified desulfonation enzyme pool (240 mg) was further separated by 2D-gel electrophoresis and identified by MALDI-TOF Mass.

碩士
國立清華大學
化學系
101
Norovirus is a category of small non-enveloped and single-stranded RNA viruses from Caliciviridae family, that virus is a major cause of epidemics of acute nonbacterial gastroenteritis in the world. Approximately 50% of all gastroenteritis outbreaks have been reported to be caused by norovirus in the United States. Although outbreaks of norovirus infection often occur in the world, but there is no specific medicine to treat people with norovirus illness. There is thus an unmet need for potent antiviral compounds. Prof. Bolognesi at the university of Milano found two high-potency norovirus inhibitors: Suramin and 8,8'-[carbonylbis(imino-3,1-phenylenecarbonylimino)]bis- 1,3,5-naphthalene-trisulphonic¬ acid hexasodium salt (NF023), thus we cooperate with his team and focus on NF023, that we hope to improve the activity by synthesizing structural analogs of NF023 as anti-norovirus agents. We successfully synthesized three new conjugate compounds containing urea linker by using triphosgene under the condition of adjusted pH value, and confirmed the struture by 1H-NMR, 13C-NMR and high resolution mass spectrometry. From water solubility experiment and partition coefficient data, we can conclude we increase drug lipophilicity successfully compared with NF023 and Suramin.

碩士
逢甲大學
化學工程學所
97
This study has prepared sodium polystyrene sulfonate – b –polystyrene (NaPSS-b-PS), which exhibits surface activity with NaPSS block as the hydrophilic moiety and PS block as the hydrophobic moiety. Using mixtures of NaPSS-b-PS and sodium dodecyl sulfate (SDS) as the emulsifier, we performed the emulsion polymerization of styrene and investigate the entry of oligomeric radicals into the emulsion particles. The surfactant NaPSS-b-PS was prepared by using the stable free-radical polymerization technique. Using benzoyl peroxide and 2, 2, 6, 6- tetramethyl- piperidinooxy (Tempo) as initiator , we prepared NaPSS macroradical first, then polymerized with styrene to have the PS block. The NaPSS block has Mw of 66700, and the PS block has Mw of 29300, according to the gel permeation chromatographic determination. The value of polymer number per particle (np)increases monotonously with increasing the volume – average particle diameter (Dv). The Dv at turning point of the recipe series of using singlesurfactant of SDS (D series) is smaller than that of the recipe series of using mixed-surfactant of SDS and NaPSS-b-PS (E series). The E series have the lower capture rate (hence, the PS has higher molecular weight), and the higher polymerization rate. Compared the results using NaPSS (Mw=70000) and SDS reported elsewhere, we found our E series have the smaller particle size, lower capture rate , and the faster polymerization.

碩士
文化大學
應用化學研究所
82
This research is mainly to explore: 1)the effect of varying the concentrations of RnSC3Na with different carbon chain lengths in water on their surface tensions, 2)the effect of varying the concentrations of RnSO3Na with different carbon chain lengths in the presence of fixed concentration of methylcelluluse (MC) on their surface tensions, 3)the effect of varying the concentrations of RnSO3Na with different carbon chain lengths in the presence of fixed amount of sodium carboxy methyl celuluse (Called CMC) on their surface tensions, 4)the effect of varying the concentrations of hexaethyl cellulose (termed HEC) in the presence of fixed amount of Nonyl phenylpoly ethylem ether (NPn：n=6,8,10,12,16) on their surface tensions, 5)the effect of varying the respective concentrations of HEC,MC and CMC in the presence of fixed amount of NPn(N=6,8,10,12,16) in water on their surface tensions, 6)the effect of varying the shear rate for NPn'S(n=6,8,10,12,16) with different concentrations in the presence of HEC and MC, respectively, on their shear rate, 7)the effect of varyingthe shear rate for NPn'S(n=6,8.10,12,16) with different concentrations in the presence of HEC (0.6%), MC(0.8%) and CMC(0.4%), respectively, on their viscosities, and 8)the effect of varying the concentrations of HEC, MC and CMC on their viscosities. The experimental results indicate that the surface tension of C2H5SO3Na in the presence of fixed amount of MC and CMC, respectively, decreases rapidly with increasing the concentration of C2H5SO3Na. In addition, since the plot of the surface tension versus the concentration of C2H5SO3Na containing fixed amount of MC does not provide the critical micelle concentration, therefore, MC is seen not to be considered as a surfactant. The surface tension of aqueous RnSO3Na decreases with increasing the concentration and carbor chain length of RnSO3Na and then reaches a pleatu, as the concentration of RnSO3Na further increases. But, under the condition of carbon chain length of RnSO3Na increased from 2 to 10, coupled with the fixed amount of CMC increased from 0.01% to 0.3%, the surface tension of aqueous RnSO3Na decreases insignifcantly, as the concentration of RnSO3Na increases. Experimental results demonstrate that the viscosity of aqueous MC exhibits non-netwon behavior and that, in the presence of NPn's concentration increased from 0% to 2% by wight, the viscosity of aqueous MC increases with increasing the shear rate and then reached a pleatu as the shear rate further increases. This is because the interation between MC molecules themselves and between MC and NPn molecules takes place since this interation leads the molecules adsorbed at the air-water interface to make rearrangement and to become even more ordered, therefore, the viscosity increases. However, increased shear rate will not change the structure of the MC nialecules and, therefore, the viscosity remains as a constant.

碩士
元智大學
化學工程學系
90
In this study we use dynamic light-scattering(DLS), membrane osmotic pressure and dynamic viscoelasticity analyzer to study the dynamic and physical properties from NaPSS in methonal/H2O (4/1 wt ratio) solution at 25℃. The concentration was ranged from 0.1 to 4.0 mg/mL. Dynamic light scattering experiments were carried out at scattering angles in the range of 30°£q£120°. Frequency of dynamic viscoelasticity analyzer was between 1 and 100 1/sec. From the experimental data of viscosity and membrane osmotic pressure, we found that when [NaPSS]＞1.0 mg/mL the solution was close to the theta-condition. DLS data revealed two relaxation modes, i.e. fast mode and slow mode. Fast mode is a diffusion mode and is a hydrophobic aggregation of polymer molecules and the fast mode relaxation time tf, increases upon dilution. When [NaPSS]＜1.0 mg/mL, the slow mode is an intra-particle motion of secondary ionic aggregation and ts was increases upon dilution. When [NaPSS]＞1.0 mg/mL, the slow mode is a viscoelastic mode and ts was independent of NaPSS concentration. From the study of dynamic viscoelasticity data show that n1’≈2 and n1” ≈1 at low frequency region, which are consistent with Zimm and Rouse theory, indicating that the solutions are liquid state.

碩士
國立臺灣科技大學
高分子工程系
92
Polyvinyl alcohol gels crosslinked with sodium styrenesulfonate（SSS） with SSS grafting ratio from 1.3×10-3 to 3.5×10-3 were prepared and drugs（Benzoic acid , Vitamin K3 and Caffeine）permeation and diffusion through gels were determined. The mesh size of gels were determined with hydrogel water contents（swelling）and elasticity data. The diffusion coefficients increase with swelling, and the solubility increases with drug size. Diffusion coefficient and solubility were presented in terms of the ratio of drug diameter to that of mesh size. The diffusion is a controlling step driving the permeation. The tortuosity of drug diffusion data in gels was calculated, which is significantly greater than the predicted value from the transport model in rigid porous media. This deviation is due to the complex structure of gels. Solute diffusion data are fitted with free volume model. We found that the slope of solute diffusion data versus the reciprocal of free volume is smaller than free volume estimation from the relation of ln（D/D0） and （1/H-1）. In the hydrogels, the steady-state adsorption factors of the solutes with higher solubility is smaller than the solute with lower solubility. The initial adsorption factors increase with SSS grafting ratio, because SSS have ionic groups interacting with the solutes. The adsorption increase with the mesh size，and the surface adsorption has greater effect for the solute with lower solubility.

碩士
大葉大學
生物產業科技學系碩士在職專班
99
Breast cancer is the leading cause of cancer death in women all over the world. Anthracycline remained the 1st line of adjuvant chemotherapy. Epirubicin (one of anthracycline) and Taxotere were the most frequently used agents for treating breast cancer, and but it easily leads cardiomyopathy. However, the cardiotocixity of anthracycline remained unsolved. Danshen, (Salvia miltiorrhizae) is a traditional Chinese herbal medicine with cardiovascular protective effect and often used by cancer patients during chemotherapy. Tanshinone IIA (Tan IIA), a lipid-soluble compound, is extracted from Danshen and Tanshinone IIA Sulfonate (STS) a water-soluble derivative of tanshinone IIA, were the two most well known and abundant component of Danshen. However, the pharmacologic effects of Danshen up on the anti-cancer effect of anthracycline in breast cancer patients were unknown. In order to evaluate the effect of STS and Tan IIA on Epirubicin induces apoptosis of BT-20 breast cancer cell.The cytotoxicity was assayed by WST-1. Hoechst staining, and flow cytometry measurement were used to assess apopotic body and apoptosis. Fluorescence intensity by flow cytometry measurement was used to assess Epirubicin uptake. Western blotting was used to evaluate the expression phosphorylation AKT, AKT and PARP-1(Poly(ADP-ribose) polymerase-1) protein. The result showed that Tan IIA inhibited BT-20 breast cancer cell growth and induced apoptosis in a time and dose-dependent manner. Tan IIA had a synergistic effect with epirubicin by inducing apoptosis through increase epirubicin uptake and decreasing the phosphorylation of AKT. STS had no effect on the cell viability of BT-20 cells. However, when used with epirubicin, STS decreased the epirubicin-induced cytotoxicity and apoptosis in BT-20 breast cancer cells. The antagonistic effect of STS on epirubicin-induced cytotoxicity in BT-20 breast cancer cells occurred concomitantly with the reduced epirubicin uptake and the increased phosphorylation of AKT. STS decreased the uptake of epirubicin in BT-20 breast cancer cells and blocked epirubicin-induced apoptosis. Therefore, STS could protect breast cancer cells against epirubicin-triggered cytotoxicity and taxotere-triggered apoptosis. Taken together, taking Danshen in patient undergoing chemotherapy with anthracyclin to be noted that the proportion of each component, especially the percentage of STS. Avoid to interference chemotherapy pharmacological effects.

Dissociation of gas hydrates has been the primary concern of the oil and gas industry for flow assurance, mainly in an offshore environment. There is also a growing interest in the rapid formation of gas hydrates for gas storage, transport of natural gas and carbon sequestration. In this thesis, we experimentally measure the kinetics of formation and dissociation of methane hydrates and the effect of various anionic and cationic surfactants such as sodium dodecyl sulfate (SDS), cetyl trimethylammonium bromide (CTAB) and alpha olefin sulfonate (AOS) on the association/dissociation rate constants. The importance and necessity of micelle formation in these surfactants has been studied. The effect of foam generation on the rate of formation of these hydrates has also been measured. SDS was found to significantly decrease the induction time for hydrate formation. There was an added decrease in the induction time when a foamed mixture of water and SDS was used. On the other hand CTAB and AOS had an inhibiting effect. The contribution of micelles towards promoting hydrate formation was demonstrated with a series of experiments using SDS. The micelles formed by these surfactants appear to serve as nucleation sites for the association of hydrates. New experimental data is presented to show that some surfactants and the use of foam can significantly increase the rate of hydrate formation. Other surfactants are shown to act as inhibitors. A new experimental setup is presented that allows us to distinguish between surfactants that act as promoters and inhibitors for hydrate formation.
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