This work is focused on the occurrence of surface-active substances in the environment. It deals with the development and optimization of methods for the determination of selected surfactants in samples from rivers and from influent and effluent of wastewater treatment plants. Representatives of anionic, nonionic and zwitterionic surfactants were selected as target compounds. Based on optimization of analytical methods and their pilot testing abroad on samples of surface water, the selection of analytes for the conditions in the Czech Republic were corrected and operatively expanded. For the final analysis liquid chromatography with mass spectrometry was used. Analysis of cationic surfactants was realized using liquid chromatograph with UV-VIS detector. This optimized method for analysis of anionic surfactants was applied to real samples. Samples of surface running water were from the River Thurso in Scotland and then from watercourses in the catchment area of Moravia river were collected. In addition to the grab sampling also continuous weekly sampling of water from Tvaroženský potok and Litava was realized. Waste water was collected at inflow and outflow of three wastewater treatment plants (WWTP) in South Moravia (Brno – Modřice, Břeclav and Hodonín).

Abstract Biodegradation is an aerobic or anaerobic degradation reaction where bacteria use organic materials as an energy source. In the aerobic biodegradation reaction, bacteria need oxygen as an electron acceptor, whereas an anaerobic reaction takes place in the absence of oxygen. Compounds degrade totally or partially, and produce simple inorganic species, such as CO2, CH4, NH3, NO3−, and H2O, as well as by-products that may be non-biodegradable and/or toxic. In this thesis, the biodegradability of recycled vegetable oils, surface-active agents, and condensing waters from the process of wood drying were studied using the manometric respirometric BOD OxiTop method. The biodegradation of organic compounds was measured under the standard conditions (OECD 301F), and also in other matrices, such as different waters and soils. These are very different environments with respect to the biodegradation reaction in nature. The main differences in waters and soils are their organic and inorganic nutrient contents, bacteria strains, and temperatures. The BOD OxiTop method is based on automatic pressure detection in a closed reactor vessel. Oxygen is consumed and carbon dioxide is formed in the aerobic reaction. The pressure decrease is detected after the carbon dioxide is adsorbed into a NaOH pellet or solution. The pressure change is dependent on oxygen consumption. The degree of biodegradation is calculated from the BOD value of the sample. The studied recycled vegetable oils were found to be 60–83% biodegradable, and the added surface-active agent did not affect their biodegradation. Biodegradation of tall oil soaps was also examined in sand, topsoil, groundwater, and surface water, as well as under OECD 301F standard conditions. Tall oil soaps were proven to be 50–85% biodegradable. Concrete solvent agent (CSA) was also proven to be 78–83% biodegradable under standard conditions. Another detergent, cetyltrimethylammonium bromide (CTAB), was found to be toxic, whereas Triton X-100 biodegraded by only 6% in solution. Biodegradation of the soil matrix was found to be enhanced with added surface-active agents. This can be explained by better wetting of small pores with surface-active agents, as compared to the behavior of pure water. The biodegradation of the matrix occurred even with toxic surface-active agents. Organic pollutants of wastewaters from the process of wood drying were 25–61% biodegradable during a 28-day period, and were proven to be quite pure when considering the carbon content of the samples. Based on these results, the disposal into drainage of condensing waters from wood drying may be regarded as safe, which from an economical viewpoint is a very important conclusion. / Tiivistelmä Biohajoavuus on luonnollinen aerobinen tai anaerobinen hajoamisprosessi, jossa bakteerit käyttävät orgaanista materiaalia energian lähteenä. Aerobisessa reaktiossa bakteerit tarvitsevat happea elektronien vastaanottajaksi, kun taas anaerobinen reaktio tapahtuu hapettomissa olosuhteissa. Yhdisteet hajoavat joko täysin tai osittain sekä tuottavat yksinkertaisia epäorgaanisia yhdisteitä, kuten CO2, CH4, NH3, NO3− tai H2O. Reaktiossa voi myös muodostua sivutuotteita, jotka voivat olla biohajoamattomia ja/tai toksisia. Tässä työssä on tutkittu kierrätettyjen kasviöljyjen, pinta-aktiivisten aineiden sekä jätevesien sisältämien orgaanisen aineksien biohajoavuuksia käyttäen manometristä respirometristä BOD OxiTop-menetelmää. Biohajoavuutta mitattiin standardiolosuhteiden (OECD 301F) lisäksi muissakin olosuhteissa, kuten erilaisissa maissa ja vesissä. Nämä ovat kaikki hyvin erilaisia ympäristöjä luonnossa tapahtuville biohajoavuusreaktioille. Pääasialliset erot ovat sekä orgaanisten että epäorgaanisten ravinteiden määrässä, bakteerikannoissa ja lämpötilassa. BOD OxiTop-menetelmä perustuu automaattiseen paineen muutoksen havainnointiin suljetussa astiassa. Aerobisessa reaktiossa kuluu happea ja muodostuu hiilidioksidia, joka imeytetään NaOH-pelletteihin tai -liuokseen ja tästä muodostuu alipaine. Paineen muutokset muunnetaan hapenkulutuksen arvoiksi, joista lasketaan biohajoavuusaste. Tutkittujen kierrätettyjen kasviöljyjen biohajoavuusasteet vaihtelivat välillä 60–83 %, eikä lisätty pinta-aktiivinen aine vaikuttanut kyseisten ekoöljyjen biohajoavuuteen. Mäntysaippuoiden biohajoavuus tutkittiin standardiolosuhteiden lisäksi hiekassa, mullassa, pohjavedessä sekä pintavedessä. Niiden biohajoavuusasteet vaihtelivat välillä 50–85 %. Betoninpesuaineen biohajoavuusaste standardiolosuhteissa oli 78–83 %. Kahdesta tutkituista pinta-aktiivisista aineista setrimoniumbromidi (CTAB) oli myrkyllinen liuosolosuhteissa eikä täten biohajonnut ja Triton X-100 biohajosi vain 6 %. Pinta-aktiivisen aineen lisääminen maahan aiheutti matriisina käytetyn maan biohajoamisen. Tämä voitiin selittää siten, että pintajännityksen laskemisen jälkeen neste voi paremmin tunkeutua maan pieniin huokosiin ja näin tuoda hajoamatonta orgaanista ainesta ja uusia bakteereita biohajoavuuskäyttöön. Tämä ilmiö havaittiin myös myrkyllisen pinta-aktiivisen aineen lisäyksen jälkeen. Jätevesien sisältämät orgaaniset ainekset hajosivat 25–61 % 28 päivän aikana ja niiden havaittiin olevan hiilen määrän huomioon ottaen hyvin puhtaita. Tässä tutkimuksessa saatujen tulosten perusteella tutkitut puunkuivauksen kondenssivedet voidaan laskea viemäriin, mikä on erittäin tärkeä tulos ekologiselta ja taloudelliselta kannalta katsottuna.

Les tensioactifs dérivés de sucres représentent la principale famille de tensioactifs bio-sourcés et constituent de bons candidats pour substituer les tensioactifs dérivés du pétrole puisqu'ils sont issus de ressources renouvelables et peuvent être autant, voire plus performants dans diverses applications, comme la formulation (détergents, cosmétiques,…), la récupération assistée du pétrole ou des minéraux, etc. Différentes propriétés amphiphiles permettent de caractériser la performance des tensioactifs dans de telles applications, comme la concentration micellaire critique, la tension de surface à la concentration micellaire critique, l'efficience et le point de Krafft. Prédire ces propriétés serait bénéfique pour identifier plus rapidement les tensioactifs possédant les propriétés désirées. Les modèles QSPR sont des outils permettant de prédire de telles propriétés, mais aucun modèle QSPR fiable dédié à ces propriétés n'a été identifié pour les tensioactifs bio-sourcés, et en particulier les tensioactifs dérivés de sucres. Au cours de cette thèse, de tels modèles QSPR ont été développés. Une base de données fiables est nécessaire pour développer tout modèle QSPR. Concernant les tensioactifs dérivés de sucres, aucune base de données existante n'a été identifiée pour les propriétés ciblées. Cela a donné suite à la construction de la première base de données de propriétés amphiphiles de tensioactifs dérivés de sucres, qui est en cours de valorisation. L'analyse de cette base de données a mis en évidence différentes relations empiriques entre la structure de ces molécules et leurs propriétés amphiphiles, et permis d'isoler des jeux de données les plus fiables et au protocole le plus homogène possibles en vue du développement de modèles QSPR. Après établissement d'une stratégie robuste pour calculer les descripteurs moléculaires constituant les modèles QSPR, qui s'appuie notamment sur des analyses conformationnelles des tensioactifs dérivés de sucres et des descripteurs des têtes polaires et chaînes alkyles, différents modèles QSPR ont été développés, validés, et leur domaine d'applicabilité spécifié, pour la concentration micellaire critique, la tension de surface à la concentration micellaire critique, l'efficience et le point de Krafft. Pour les trois premières propriétés, des modèles quantitatifs performants ont pu être obtenus. Si les descripteurs quantiques ont apporté un gain prédictif important pour la tension de surface à la concentration micellaire critique, et un léger gain pour la concentration micellaire critique, aucun gain n'a été observé pour l'efficience. Pour ces trois propriétés, des modèles simples basés sur des descripteurs constitutionnels des parties hydrophile et hydrophobe de la molécule (comme des décomptes d'atomes) ont aussi été obtenus. Pour le point de Krafft, deux arbres de décision qualitatifs, classant la molécule comme soluble ou insoluble dans l'eau à température ambiante, ont été proposés. Les descripteurs quantiques ont ici aussi apporté un gain en prédictivité, même si un modèle relativement fiable basé sur des descripteurs constitutionnels des parties hydrophile et hydrophobe de la molécule a aussi été obtenu. Enfin, nous avons montré comment ces modèles QSPR peuvent être utilisés, pour prédire les propriétés de nouvelles molécules avant toute synthèse dans un contexte de screening, ou les propriétés manquantes de molécules existantes, et pour le design in silico de nouvelles molécules par combinaison de fragments. / Sugar-based surfactants are the main family of bio-based surfactants and are good candidates as substitutes for petroleum-based surfactants, since they originate from renewable resources and can show as good as, or even better, performances in various applications, such as detergent and cosmetic formulation, enhanced oil or mineral recovery, etc. Different amphiphilic properties can characterize surfactant performance in such applications, like critical micelle concentration, surface tension at critical micelle concentration, efficiency and Kraft point. Predicting such properties would be beneficial to quickly identify surfactants that exhibit desired properties. QSPR models are tools to predict such properties, but no reliable QSPR model was identified for bio-based surfactants, and in particular sugar-based surfactants. During this thesis, such QSPR models were developed. A reliable database is required to develop any QSPR model. Regarding sugar-based surfactants, no database was identified for the targeted properties. This motivated the elaboration of the first database of amphiphilic properties of sugar-based surfactants. The analysis of this database highlighted various empirical relationships between the chemical structure of these molecules and their amphiphilic properties, and enabled to isolate the most reliable datasets with the most homogeneous possible protocol, to be used for the development of the QSPR models. After the development of a robust strategy to calculate molecular descriptors that constitute QSPR models, notably relying upon conformational analysis of sugar-based surfactants and descriptors calculated only for the polar heads and for the alkyl chains, different QSPR models were developed, validated, and their applicability domain defined, for the critical micelle concentration, the surface tension at critical micelle concentration, the efficiency and the Kraft point. For the three first properties, good quantitative models were obtained. If the quantum chemical descriptors brought a significant additional predictive power for the surface tension at critical micelle concentration, and a slight improvement for the critical micelle concentration, no gain was observed for efficiency. For these three properties, simple models based on constitutional descriptors of polar heads and alkyl chains of the molecule (like atomic counts) were also obtained. For the Krafft point, two qualitative decision trees, classifying the molecule as water soluble or insoluble at room temperature, were proposed. The use of quantum chemical descriptors brought an increase in predictive power for these decision trees, even if a quite reliable model only based on constitutional descriptors of polar heads and alkyl chains was also obtained. At last, we showed how these QSPR models can be used, to predict properties of new surfactants before synthesis in a context of computational screening, or missing properties of existing surfactants, and for the in silico design of new surfactants by combining different polar heads with different alkyl chain

Nous présentons au cours de ce manuscrit diverses expériences de dépôt de tensioactifs solubles dans l'eau à l'interface entre deux fluides. Après quelques développements théoriques, nous étudions l'étalement de tensioactifs solubles déposés à une interface eau/air. Nous présentons au cours de cette partie deux configurations expérimentales dans lesquelles ces molécules exhibent une vitesse caractéristique d'écoulement induit ainsi qu'une distance finie d'étalement dépendant de la CMC du surfactant utilisé, qui se traduit par l'apparition d'une tache centimétrique à la surface de l'eau. Nous mettons alors au point un protocole de mesure simple et rapide de CMC utilisant notre dispositif expérimental. À cet étalement s'ajoutent une déformation verticale de l'interface, la mise en place d'une double recirculation toroïdale, ainsi qu'une instabilité hydrodynamique de surface tout autour de la tache. La deuxième expérience porte sur l'étalement de tensioactifs solubles à une interface eau/huile. Dans cette expérience, les déformations verticales induites par l'étalement peuvent devenir très importantes, si bien que sous certaines conditions cette déformation crée un trou dans la couche d'huile. Nous nous penchons donc sur l'étude de ces déformations verticales, ainsi que sur les caractéristiques de ce cratère. Enfin, la dernière partie traite du dépôt d'une goutte de Triton X-100 à la surface de l'eau. Ce tensioactif possède la propriété de gélifier lorsqu'il est hydraté, ce qui lui permet de flotter. On observe alors un phénomène d'auto-propulsion de la goutte. Nous nous intéressons plus particulièrement à la structure microscopique de cette phase gel, ainsi qu'aux trajectoires erratiques empruntées par la goutte. / We report experiments about the deposition of water soluble surfactants at the interface between two fluids. After some theoretical developments, we study the spreading of water soluble amphiphiles at the water/air interface. In this part, we present two experimental setups where these molecules show a typical induced flow velocity, and a finite spreading distance, depending on the CMC of surfactant we use, which results in the apparition of a coronna on the surface of the liquid. We then set up a fast and simple CMC measurement protocole using our experimental setup. This spreading induces also a vertical deformation of the interface, a double toroidal recirculation in the bulk, and a beatiful hydrodynamic surface instability all around the coronna. The second experiment is about the spreading of amphiphiles at the interface between oil and water. In this experiment, the vertical deformations induced by the spreading can become so important that under certain circumstances, we manage to create a hole in the oil layer. We focus on the study of these vertical deformations and on the caracteristics of this hole. Finally, the last experiment is about the deposition of a Triton X-100 drop at the water/air interface. This molecule has the ability to gelify when it gets hydrated, allowing him to float. Then we can observe the self propulsion of the droplet. We focus on the microscopic structure of this gel phase, and also on the erratic trajectories followed by the drop.

Grâce à la qualité des cordons de soudure produits, le soudage TIG est l’un des procédés de soudage à l’arc les plus répandus dans l’industrie nucléaire. Au cours des travaux de cette thèse, nous proposons un modèle physique pour la simulation numérique du bain de fusion en soudage TIG d’aciers inoxydables austénitiques avec des teneurs en éléments tensioactifs différentes. L’objectif du modèle développé est de prédire la morphologie et les dimensions du cordon de soudure ainsi que les contraintes thermiques résultantes dans les pièces soudées en fonction des paramètres opératoires du procédé mais aussi en fonction des teneurs en éléments tensioactifs des métaux assemblés. Pour ce faire, les équations de la thermohydraulique sont couplées à celles de l’électromagnétisme et sont résolues en se basant sur le module « électrique » de Code_Saturne. Ce modèle a été vérifié dans un premier temps sur des configurations de soudage de matériaux homogènes avant d’être confronté à la simulation du soudage de matériaux de teneurs en éléments tensioactifs différentes. Des simulations des essais expérimentaux correspondants ont été réalisées et comparées aux mesures. La démarche adoptée a consisté à étudier les effets thermo-capillaires de manière découplée des effets électromagnétiques à partir d’essais de soudage laser en mode conduction. Les résultats de la confrontation des résultats numériques aux mesures expérimentaux démontrent que le modèle reproduit globalement bien la physique du procédé. Les limitations de notre modèle et les phénomènes qu’elle a permis de mettre en évidence ont été discutés et ont permis de proposer des pistes d’amélioration pour la modélisation. / The high quality of the weld bead makes GTA welding one of the most used welding processes in the nuclear industry. During this work, a physical model is proposed to simulate the weld pool during the GTA welding of stainless steels with different concentrations of surface active elements. This model aims to predict the weld bead shape, its geometrical characteristics and the thermal field induced by the process according to the operating parameters but also as a function of the surface active elements concentrations of welded metals.Based on the “electric” module of Code_Saturne®, the set of solved equations includes both fluid dynamics equations and electromagnetic ones. Before applying the model to the simulation of welding of stainless steels with different concentrations of surface active elements, this model has been studied through configurations of homogenous materials welding. Experiments are carried out and are compared to the corresponding simulations. In the approach used in this study, the thermo-capillary effects are studied separately from electromagnetic ones using conduction mode laser beam welding. The agreement obtained from comparative analysis between experimental results and numerical ones shows good reproduction of the process physics by the model developed. The modeling limitations and the phenomena identified by this study are discussed and orientations for future development are defined.

Orientador: Eneida de Paula / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Biologia / Made available in DSpace on 2018-08-07T20:44:09Z (GMT). No. of bitstreams: 1 Prete_PauloSergioCastilho_D.pdf: 3376950 bytes, checksum: fd06e65f64531668e35cf4a9cb817913 (MD5) Previous issue date: 2006 / Resumo: Surfatantes ou detergentes são compostos anfifílicos que, na presença de água, têm a característica de formar agregados micelares. Surfatantes induzem a desestruturação de outros agregados como bicamadas sendo, por isso, usados para ruptura celular ou solubilização de lipídios e proteínas de membrana. A capacidade lítica dos surfatantes resulta de sua estrutura química, que determina o modo de interação dos mesmos com as membranas. Em concentrações mais altas (acima da concentração micelar crítica), os surfatantes desestabilizam as bicamadas lipídicas, levando à formação de micelas-mistas. Ensaios hemolíticos são bons modelos para estudo do efeito lítico de surfatantes em biomembranas. Aplicando em eritrócitos humanos o tratamento quantitativo proposto por Lichtenberg (1985) para estudo da solubilização de bicamadas lipídicas mensurou-se, neste trabalho, as concentrações para início (Csat) e 100% de hemólise (Csol), induzidas por 25 surfatantes clássicos, pertencentes a cinco diferentes famílias. A variação dos valores de Csat, Csol determinada com diferentes hematócritos permitiu o cálculo da constante de ligação surfatante/membrana e da razão surfatante/lipídio de membrana (Re) para início e 100% de hemólise. O parâmetro Re foi usado para classificar os detergentes como fortes, médios ou fracos agentes solubilizantes, com boa correlação com dados da literatura o que nos permitiu propor seu uso para descrever o efeito lítico de surfatantes, como uma alternativa simples e aplicável as membranas biológicas. As transições durante o processo hemolítico foram acompanhadas pela técnica de Ressonância Paramagnética Eletrônica, com uso marcador de spin 5 doxil-estearato (incorporado a 1 mol% nas membranas de eritrócito) e lise induzida pelo surfatante não iônico Triton X100. Concomitante ao aparecimento de hemoglobina e fosfato livres no sobrenadante - indicadores da ruptura da membrana, medidas do parâmetro de ordem daquele marcador de spin permitiram estudar as transições que acontecem durante (membrana:membrana mista) e após (membrana mista:micela mista) a hemólise / Abstract: Surfactants or detergents are amphiphilic compounds that form micellar aggregates in the presence of excess water. Surfactants are able to induce disruption of lamellar aggregates, justifying their use for cell lysis or in the extraction of membrane constituents such as lipids and proteins. The lytic capacity of a given surfactant is determined by its chemical structure, that rules its interaction with the membranes. At high concentration (above the critic micelle concentration), surfactants destabilize lipid bilayer leading to mixed micelle formation. Hemolytic assays are a good model to study the lytic effect of surfactants on biomembranes. In this study we have applied to human erythrocytes the quantitative treatment proposed by Lichtenberg (1985) to describe the solubilization of model lipid membranes. The concentration for onset (Csat) and complete (Csol) hemolysis induced by 25 classic surfactants from five different families were measured. Changes in Csat and Csol values at different hematocrits allowed the determination of the surfactant/membrane lipid molar ratio (Re) for beginning and 100% lysis. The Re arameter was used to classify the surfactants as strong, medium or weak membrane solubilizers. The classification was in good correlation with data in the literature, allowing us to recommend the use of Re parameter to describe the lyric effect of surfactants on biomembranes. The transitions in the hemolytic process were accompanied by Electron Paramagnetic Resonance, using the 5-doxyl-stearate spin-probe (1 mol%, incorporated in the erythrocyte membrane) and the non-ionic surfactant Triton X100. Simultaneously to the appearance of hemoglobin and phosphate released in the supernatant, measurements of the order parameter of the spin probe were used to characterize the transitions that take place during (membrane :mixed membrane) and after (mixed: membrane: mixed micelle) hemolysis / Doutorado / Bioquimica / Doutor em Biologia Funcional e Molecular

The thesis deals with the study of surface-active properties, zeta potential, particle size and adhesion of surfactants (Arkopal N110, Igepal CO-520, Igepal CO-890, Dehyton PL, sodium dodecyl sulfate and dodecyltrimethylammonium bromide) selected for full notch creep test method. To determine the surface phenomena occuring in a solution due to their presence at 25, 50 and 80 °C, the Du Noüy ring method of surface tension measurement was used. The importance of factors such as concentration, ionic character and the molecular structure of the surfactants, temperature and dispersion media (pH, purity) were analysed. Dynamic light scattering measurements were performed in order to evaluate the particle size and the electrophoresis method was used to determine the zeta potential. The results were compared to the contact angle measurements, i. e. adhesion tendency between surfactant solutions and the surface of selected types of high density polyethylene. The optical analysis was used to evaluate the contact angle. The negative impact of water purity was negated. The temperature dependecy was specific for each of the examined surfactant species, however the relationship between temperature and the length of hydrophilic chain was discovered. Alkaline pH was less convenient for amphoteric surfactant than acid or neutral environment, but this might have been caused by components contained in the buffer. The character of surfactant solutions was mostly monodisperse. The only exceptions were 1mM Igepal CO-520 and 3mM Dehyton PL. Further investigation led to conclusion that the molecules tend to form agglomerates. Adhesion was in accordance with surfactant effectiveness of surface reduction and adsorption. However, this theory did not match the data obtained from testing acid and neutral Dehyton PL solutions' adhering to polyethylene species containing carbon black.

<p>Da bi se dobio sistem surfaktanata željenih osobina moguće je hemijski modifikovati već postojeće molekule povr&scaron;inski aktivnih supstanci, a druga mogućnost je konstrukcija binarnih sme&scaron;a surfaktanata. U farmaceutskoj i prehrambenoj industriji uveliko se primenjuju binarne sme&scaron;e povr&scaron;inski aktivnih molekula. Ukoliko je binarna me&scaron;ovita micela termodinamički stabilnija od hipotetičke idealne binarne me&scaron;ovite micele, onda je kritična micelarna koncentracija binarne sme&scaron;e surfaktanata niža čak i od hidrofobnije gradivne jedinice me&scaron;ovite micele, &scaron;to znači da je za isti efekat povr&scaron;inske aktivnosti potrebna manja količina binarne sme&scaron;e nego čistog surfaktanta. Različite gradivne jedinice binarne micele u micelarnoj pseudofazi mogu formirati specifične regije koje mogu vezivati lekove određenih strukturnih karakteristika. Pogodno je da jedna gradivna jedinica bude krute konformacije, npr. soli žučnih kiselina, dok je druga gradivna jedinica konformaciono pokretljiva (ugljovodonični nizovi iznad C10). Na taj način se povećava zapremina hidrofobne micelarne faze u odnosu na zapreminu hidrofobne micelarne faze monokomponentne micelle konformaciono krutog surfaktanta, &scaron;to povećava solubilizacioni kapacitet me&scaron;ovite micele u odnosu na monokomponentnu micelu krutog surfaktanta. Povećanjem dužine ugljovodoničnog niza konformaciono pokretnog surfaktanta povećava se stepen unutra&scaron;nje pokretljivosti u hidrofobnom domenu me&scaron;ovite micele, &scaron;to takođe povećava verovatnoću prihvatanja molekula gosta. Micelarni sistemi, kako monokomponentnih micela tako i binarnih me&scaron;ovitih micela dodatno se mogu termodinamički stabilizovati povećanjem jonske jačine rastvora. Za hidrataciju katjona tro&scaron;e se molekuli vode iz sistema, &scaron;to povećava efekat desolvatizacije hidrofobne povr&scaron;ine surfaktanata, pa se zbog toga pospe&scaron;uje samoasocijacija.</p> / <p>To obtain the surfactant system with the desired properties it is possible to chemically modify existing molecules of surface active agents. The other possibility is the construction of binary mixtures of surfactants. Binary mixtures of surface active molecules are widely used In the pharmaceutical and food industry. If the binary mixture micelle is more thermodynamically stable than the hypothetical ideal binary mixed micelle, then the critical micellar concentration (CMC) of the binary mixture of surfactants is even lower than the CMC of the more hydrophobic building block of the binary mixture. That means that for the same effect of surface activity less the amount of the binary mixture than the pure surfactants is required. The different building blocks of binary micelles in micelar pseudophase can form specific regions that can bind drugs of certain structural characteristics. It is suitable that one building block is of a rigid conformation, i.e. bile acid salts, while the second building block is of a flexible conformation (above C10 hydrocarbon arrays). In this way the volume of the hydrophobic micellar phase is increased in relation to the volume of the hydrophobic micellar phase of the monocomponent micelles of conformationally rigid surfactant, which increases the capacity of solubilisation of the mixed micelles, compared to the mono-component surfactant micelle of the rigid conformation. By increasing the length of the hydrocarbon array of the the conformational flexible surfactant, the degree of internal mobility in the hydrophobic domain of mixed micelles is also increased, which also increases the likelihood of acceptance of guest molecules. Micellar systems, of both monocomponent micelles and mixed micelles can be additionally thermodynamically stabilized by increasing the ionic strength of the solution. The hydration of cations uses the molecules of water from the system, which increases the effect of desolvatisation of the hydrophobic surface of the surfactants, and therefore promotes self-association.</p>

No description available.

Ce travail s'inscrit dans le cadre de l'amélioration de la connaissance sur la mesure de la surface des aérosols ultrafins. En effet, l'essor des nanotechnologies peut être à l'origine de situations d'exposition professionnelle aux particules nanostructurées dispersées dans l'air, ce qui soulève une problématique nouvelle de prévention. Si à ce jour aucun des trois indicateurs (masse, surface, nombre) ne fait l'objet d'un consensus, il semble que le paramètre de surface des particules permet une bonne corrélation avec les effets biologiques observés lorsqu'elles sont inhalées. Un travail théorique original a donc été mené afin de positionner le paramètre de surface vis-à-vis d'autres grandeurs caractéristiques des aérosols. En vue de caractériser des méthodes de mesure de la surface des aérosols nanostructurés, le banc d'essais CAIMAN (CAractérisation des Instruments de Mesure des Aérosols Nanostructurés) a été dimensionné et réalisé. Celui-ci permet la production d'aérosols nanostructurés de propriétés variables et maîtrisées (taille, concentration, nature chimique, morphologie, état de charge), offrant une très bonne stabilité dans le temps. Les aérosols générés en laboratoire ont été utilisés en vue d'évaluer expérimentalement la réponse des instruments de mesure étudiés (NSAM & AeroTrak 9000 TSI, LQ1-DC Matter Engineering). Les fonctions de réponse expérimentales établies sur des aérosols monodispersés présentent un bon accord avec les courbes théoriques, dans une large gamme d'étude de 15 à 520 nm. Par ailleurs, des hypothèses ont été avancées en vue d'expliquer les écarts raisonnables observés lors des mesures effectuées sur des aérosols polydispersés / This work aims at improving knowledge on ultrafine aerosols surface-area measurement. Indeed, the development of nanotechnologies may lead to occupational exposure to airborne nanostructured particles, which involves a new prevention issue. There is currently no consensus concerning what parameter (mass, surface-area, number) should be measured. However, surface-area could be a relevant metric, since it leads to a satisfying correlation with biological effects when nanostructured particles are inhaled. Hence, an original theoretical work was performed to position the parameter of surface-area in relation to other aerosol characteristics. To investigate measurement techniques of nanostructured aerosols surface-area, the experimental facility CAIMAN (ChAracterization of Instruments for the Measurement of Aerosols of Nanoparticles) was designed and built. Within CAIMAN, it is possible to produce nanostructured aerosols with varying and controlled properties (size, concentration, chemical nature, morphology, state-of-charge), stable and reproducible in time. The generated aerosols were used to experimentally characterize the response of the instruments in study (NSAM & AeroTrak 9000 TSI, LQ1-DC Matter Engineering). The response functions measured with monodisperse aerosols show a good agreement with the corresponding theoretical curves in a large size range, from 15 to 520 nm. Furthermore, hypotheses have been formulated to explain the reasonable biases observed when measuring polydisperse aerosols