Les propriétés hydrophobes des polymères extracellulaires (PEC) exercent l’influence profonde sur les propriétés de la surface cellulaire. Cependant, de nombreux facteurs tels que les méthodes d'extractions, le type de substrat influencent les caractéristiques des PEC et les informations concernant des caractéristiques hydrophobes sont rarement documentées. L'objectif principal de cette étude est de développer une méthode appropriée pour étudier l'hydrophobicité des PEC, puis d'étudier les caractéristiques hydrophobes des PEC.Le fractionnement hydrphobe par la résine Supelite™ DAX-8 a d'abord été appliqué sur les PEC extraits de boues granulaires anaérobies, deux conditions de pH d'élution (pH 2 et 5) ont été testées. L'impact de sept méthodes d'extraction sur les caractéristiques hydrophobes des PEC a été évalué. Les résultats ont montré que les méthodes d'extraction et le pH de la solution extraitante ont influencé la composition des PEC et leur hydrophobicité. En outre, les extraitants des PEC, par exempe le formaldéhyde, l'éthanol, le dodécylsulfate de sodium (SDS) et Tween 20, ont non seulement introduit une teneur supplémentaire en carbone pendant la mesure du carbone organique total (COT), mais ils ont également interagit avec la résine DAX-8. En comparant la répartition du poids moléculaire apparent (aMW) des échantillons des PEC non traités et ajustés au pH détectés par chromatographie d'exclusion stérique (en anglais SEC), l’information plus complète d’aMW a été préservée à pH 5. Ainsi, le fractionnement hydrophobe par la résine DAX-8 à pH 5 et les méthodes physiques d'extraction PEC ont été préférés dans cette étude.Une analyse qualitative détaillée des caractéristiques hydrophobes des EPS a été étudiée par la technique de la matrice de fluorescence d’excitation-emission (EEM). Les résultats ont montré que les substances de type humique (HS-like) représentaient la majorité des composés organiques des PEC extraits de la boue granulaire anaérobie, et constituaient également le principal support moléculaire de l'hydrophobicité des extraits. Ces composés hydrophobes de type HS étaient essenciellement des molécules petites tailles de 8 kDa à <1 kDa. L’hydrophobité contributée par les protéines (PN) et les polysaccharides (PS) présentait un moindre rapport.Afin d’explorer les propriétés hydrophobes de PN et de PS, ainsi évaluer l'impact de l'addition de Ni(II) sur l'hydrophobicité des extraits des champignons, fongi Phanerochaete chrysosporium a été choisi. Les résultats ont montré que la teneur de PN et de PS dans les PEC extrait de ce type de fongi variait en fonction de la concentration de Ni(II). Avec une augmentation de la concentration de Ni de 0 mg/L à 25 mg/L, la teneur en PN a diminué alors que celle de PS a été augmentée. L'hydrophobicité des PEC du fongi, déterminée par le traitement de la résine DAX-8, a diminué lors que la concentration de Ni augmentait. Par ailleurs, l'intensité du pic de SEC correspondant aux molécules PN-like (Ex/Em = 225/345 nm) de 1,9 × 103 à 10 kDa a été augmentée par l'addition Ni; en même temps, la distribution d’aMW des composés organiques totaux (UV/210) dans les PEC restait presque stable. Ces résultats ont indiqué que les composés de type PN-like peuvent avoir déterminé l'hydrophobicité des PEC fongique dans des conditions de stress.Dans l’extrait plus hétérogène des PEC de boues granulaires anaérobies, des composés HS-like représentaient le composant organique majeur, ainsi le principal support moléculaire de l'hydrophobicité des PEC. En étudiant les caractéristiques hydrophobes des PEC extrait du champignon Phanerochaete chrysosporium, le PN et le PS des PEC jouaient un rôle actif dans la protection du champignon sous le Ni. La concentration élevée de Ni a diminué l'hydrophobicité des PEC fongique, mais elle a augmenté l'hydrophobicité de la surface cellulaire du champignon. Il semble que la présence de Ni favorise l'apparition d'un champignon plus hydrophobe / The hydrophobic properties of extracellular polymeric substances (EPS) exert a profound influence on the cell surface properties. However, many factors such as EPS extractions methods, substrate type influence EPS characteristics, and limited information regarding to the hydrophobic features of EPS can be found. The main aim of this study is to develop a proper method to study EPS hydrophobicity, and then investigate the hydrophobic features of EPS.The hydrophobic fractionation by Supelite™ DAX-8 resin was first applied on the EPS extracted from anaerobic granular sludge, two elution pH conditions i.e. pH 2 and 5 were tested. The impact of seven EPS extraction methods on the hydrophobic features of EPS was assessed. The results showed that the extraction methods and bulk solution pH dramatically influenced the EPS composition and their hydrophobicity. Besides, the EPS extracting reagents namely formaldehyde, ethanol, sodium dodecyl sulfate (SDS) and Tween 20 not only introduced extra carbon content during total organic carbon (TOC) measurement, but also interacted with the DAX-8 resin. By comparing the apparent molecular weight (aMW) distribution of the untreated and pH-adjusted EPS samples detected by size exclusion chromatography, more complete EPS aMW information was preserved at pH 5. Thus, the hydrophobic fractionation by DAX-8 resin at pH 5 and physical EPS extraction methods were preferred in this study.After identifying the proper conditions for DAX-8 resin fractionation, detailed qualitative analysis of the EPS hydrophobic features was further investigated. The results showed that the humic-like substances (HS-like) were the major organic constituent of the EPS extracted from the anaerobic granular sludge, and they were also the main molecular support of the EPS hydrophobicity. Those hydrophobic HS-like compounds were mainly small molecules ranging from 8 kDa to <1 kDa. Proteins (PN) and polysaccharides (PS) contributed to the EPS hydrophobicity to a lesser extent.The role of PN and PS in the EPS hydrophobicity was difficult to be shown. It is known that the major organic constituents of the EPS extracted from bacteria, algae and fungi are PN and PS. Therefore, to explore the hydrophobic features of PN and PS, as well as to investigate the impact of Ni(II) addition, on the EPS hydrophobicity, the fungus Phanerochaete chrysosporium was chosen. The results showed that the contents of PN and PS in the extracted fungal EPS varied with the Ni(II) concentration. With an increase in the Ni concentration from 0 mg/L to 25 mg/L, the PN content was decreased whereas the PS content was increased. The fungal EPS hydrophobicity, determined by the DAX-8 resin treatment, was decreased as the Ni concentration increased.Besides, the peak intensity on the size exclusion chromatography (SEC) corresponding to the PN-like molecules (Ex/Em = 225/345 nm) ranging from 1.9×103 to 10 kDa were intensified by the Ni addition, while the aMW distribution of the total organics (UV/210) in the EPS remained almost stable. These results indicated that those PN-like compounds may determine the hydrophobicity of fungal EPS under stress conditions.For the more heterogeneous EPS extracted from anaerobic granular sludge, HS-like compounds were identified as the major organic component, as well as the main molecular support of the EPS hydrophobicity. By studying the hydrophobic features of the EPS extracted from the fungus Phanerochaete chrysosporium, it showed that the PN and PS in the EPS played an active role in protecting the fungus under Ni stress. The increased Ni concentration decreased the hydrophobicity of fungal EPS, but it increased the cell surface hydrophobicity of the fungus. It seems that the presence of Ni promoted the fungus becoming more hydrophobic

Characterization of cellulose by its molecular weight distribution is afforded after polymeranalogeous dissolution. Additionally, a molecular dispersion of the polymer is a prerequisite. Common processes are dissolution of cellulose in dimethylacetamide-lithiumchloride, nitration and carbanilation. Degradation of the polysaccharide chains can occur in each of the mentioned processes. It is shown that degradation in pyridine occurs via beta-elimination at carbonyl groups along the cellulose chains. Carbanilierung in DMSO is much more pronounced. It comprises oxidation along the Pfitzner-Moffatt-mechanism and subsequent beta-elimination at the thus formed carbonyl-groups. This was elucidated with model systems and by investigation of the carbanilation in different media. Carbonyl groups of cellulose are masked through reaction with phenylisocyanate. This was shown with model. Therefore, the determination of carbonyl groups in cellulose-tricarbanilates is not possible. The separation of low-molecular weight byproducts was optimised. The influence of pretreatment and preactivation of cellulose-samples on the completeness of the conversion was studied. A standard protocol for the carbanilation of cellulose is provided. / Cellulose wird u.a. durch ihre Molmassenverteilung charakterisiert, deren Ermittlung ein polymeranaloges Verfahren zur molekulardispersen Auflösung des Polymers erfordert. Hierfür sind die Direktlösung, die Nitrierung und die Carbanilierung in Gebrauch. Bei allen Prozessen kann es zum Abbau der Polysaccharidketten kommen, wobei diesen Prozessen wenig Beachtung geschenkt wurde. In der Arbeit wird gezeigt, daß der Abbau bei der Carbanilierung in Pyridin durch Beta-Eliminierung an vorhandenen Carbonylgruppen erfolgt. Die Carbanilierung in DMSO fällt stets stärker aus als bei Einsatz von Pyridin und umfasst die Prozesse Oxidation nach dem Pfitzner-Moffatt-Mechanismus und anschließende Beta-Eliminierung an den neu gebildeten Carbonylgruppen. Dies wird durch Untersuchungen an Modellsystemen und am Polymer herausgearbeitet. Carbonylgruppen an Cellulose werden durch die Umsetzung mit Phenylisocyanat maskiert, was an Modellverbindungen gezeigt wurde (Bildung von Endioldicarbanilaten und carbanilierten Halbacetalen). Ihre Bestimmung in Cellulosecarbanilaten ist daher nicht möglich. Die Abtrennung von niedermolekularen Nebenprodukten der Umsetzung wurde optimiert. Der Einfluss der Vorbehandlung und Voraktivierung von Celluloseproben auf die Vollständigkeit der Umsetzung wurde eingehend untersucht. Es wird ein Standardverfahren zur Carbanilierung von Cellulose angegeben.

Controlled radical polymerization (CRP) can be viewed as the middle ground between living anionic polymerization (LAP) and conventional free radical polymerization (FRP). It combines the precise control over polymer structure offered by LAP, under a tolerant reaction condition similar to FRP. One of the most studied CRP is atom transfer radical polymerization (ATRP), with over 10,000 papers published since its introduction in 1995. Despite the numerous studies, knowledge on its fundamental mechanism is still lacking, as evident from the lack of expression for full MWD and polydispersity that account for termination reaction. Since termination is unavoidable in ATRP, the existing expressions give inaccurate predictions as dead chains accumulate. In this study, we derived expressions for full MWD at low conversion and for polydispersity. These expressions allow us to quantify and gain better understanding on the contribution of termination. In addition, the resulting polydispersity expression shows better agreement than the existing equation when correlated with experiment data. In addition to the aforementioned questions, there are also controversies regarding the kinetics of surface-initiated ATRP, with researchers divided into two schools of theories. We evaluated the validity of these theories by comparing their predictions to experimental trends. Both theories were found to be inadequate in explaining all the experimental observations, thus triggering an investigation of the graft density. Graft density is an important determining property for polymer brushes, yet little is known about what affects its final value. Through simulations, we investigated the effect of experiment factors on the grafting density. A decrease in the amount of deactivator is found to decrease the grafting density, which could be explained by an increase in the number of monomers added per activation cycle. This knowledge allows us to explain the conflicting experiment observations regarding the growth trends of polymer layers reported in the literatures. / Thesis / Doctor of Philosophy (PhD) / Polymer materials are used almost everywhere in our daily life from clothing to water bottle. This wide range of applications owes to the nearly infinite possible properties that polymer can possess. Different polymerization processes to synthesize polymers have their own weaknesses and strengths. Herein we investigated the fundamental mechanism of one of the currently most attractive polymerization systems, atom transfer radical polymerization (ATRP). This process allows the synthesis of polymers with precisely tailored chain microstructures, making it possible to create polymer with sophisticated properties. Using modeling approaches, we derived explicit expressions for determining chain properties, allowing detailed investigation of how various factors affect these properties. Through these investigations, we obtained better understanding on the mechanism of ATRP in solution and on surface. This knowledge is crucial in providing insight and guiding experimental designs for better control over the material properties.