Techn. Hochsch., Diss., 2002--Aachen.

Universiẗat, Diss., 2003--Freiburg (Breisgau).

The properties of a series of well-defined new surfactant oligomers (dimers to tetramers)were examined. From a molecular point of view, these oligomeric surfactants consist of simple monomeric cationic surfactant fragments coupled via the hydrophilic ammonium chloride head groups by spacer groups (different in nature and length). Properties of these cationic surfactant oligomers in aqueous solution such as solubility, micellization and surface activity, micellar size and aggregation number were discussed with respect to the two new molecular variables introduced, i.e. degree of oligomerization and spacer group, in order to establish structure – property relationships. Thus, increasing the degree of oligomerization results in a pronounced decrease of the critical micellization concentration (CMC). Both reduced spacer length and increased spacer hydrophobicity lead to a decrease of the CMC, but to a lesser extent. For these particular compounds, the formed micelles are relatively small and their aggregation number decreases with increasing the degree of oligomerization, increasing spacer length and sterical hindrance. In addition, pseudo-phase diagrams were established for the dimeric surfactants in more complex systems, namely inverse microemulsions, demonstrating again the important influence of the spacer group on the surfactant behaviour. Furthermore, the influence of additives on the property profile of the dimeric compounds was examined, in order to see if the solution properties can be improved while using less material. Strong synergistic effects were observed by adding special organic salts (e.g. sodium salicylate, sodium vinyl benzoate, etc.) to the surfactant dimers in stoichiometric amounts. For such mixtures, the critical aggregation concentration is strongly shifted to lower concentration, the effect being more pronounced for dimers than for analogous monomers. A sharp decrease of the surface tension can also be attained. Many of the organic anions produce viscoelastic solutions when added to the relatively short-chain dimers in aqueous solution, as evidenced by rheological measurements. This behaviour reflects the formation of entangled wormlike micelles due to strong interactions of the anions with the cationic surfactants, decreasing the curvature of the micellar aggregates. It is found that the associative behaviour is enhanced by dimerization. For a given counterion, the spacer group may also induce a stronger viscosifying effect depending on its length and hydrophobicity. Oppositely charged surfactants were combined with the cationic dimers, too. First, some mixtures with the conventional anionic surfactant SDS revealed vesicular aggregates in solution. Also, in view of these catanionic mixtures, a novel anionic dimeric surfactant based on EDTA was synthesized and studied. The synthesis route is relatively simple and the compound exhibits particularly appealing properties such as low CMC and σCMC values, good solubilization capacity of hydrophobic probes and high tolerance to hard water. Noteworthy, mixtures with particular cationic dimers gave rise to viscous solutions, reflecting the micelle growth. / Die Eigenschaften einer Reihe gut definierter neuer oligomerer Tenside (von Dimeren bis zu Tetrameren) wurden untersucht. Strukturell bestehen diese oligomeren Tenside aus einfachen monomeren kationischen Tensidfragmenten, die über die hydrophile Kopfgruppe (Tetraalkyl-Ammoniumchlorid) durch „Spacer“-Gruppen unterschiedlicher Natur und Länge miteinander verbunden/gekoppelt sind. Die Eigenschaften dieser kationischen oligomeren Tenside in wässriger Lösung wie Löslichkeit, kritische Mizellbildungskonzentration und Oberflächenaktivität, Mizellgröße und Aggregationszahl werden in Bezug auf die zwei neuen molekularen Variabeln (d.h. dem Oligomerisationsgrad und der Spacer-Gruppe) untersucht, um Struktur-Eigenschafts-Beziehungen abzuleiten. Die Erhöhung des Oligomerizationsgrads verringert stark die kritische Mizellbildungskonzentration (CMC). Eine kurze Spacer-Länge oder ein erhöhte Hydrophobie des Spacers erniedrigt die CMC ebenfalls, aber in einem geringeren Umfang. Die gebildeten Mizellen sind relativ klein und ihre Aggregationszahl nimmt mit zunehmendem Oligomerisationsgrad ab, genau wie mit zunehmender Spacerlänge oder sterischer Behinderung. Außerdem wurden Pseudo-Phasendiagramme für die Gemini-Tenside in komplexen Systemen, nämlich in inversen Mikroemulsionen untersucht. Auch hier zeigt die Spacer-Gruppe einen großen Einfluß auf das Tensidverhalten. Weiterhin wurde der Einfluss von Zusätzen auf das Eigenschaftsprofil der dimeren Tenside untersucht. Starke Synergien wurden beobachtet, wenn man spezielle organische Anionen (z.B. Natriumsalicylat, Natriumvinylbenzoat, etc.) zu den dimeren Tensiden in stöchiometrischen Mengen hinzugibt. Für solche Mischungen wird die Mizellbildungskonzentration stark zu niedrigen Konzentrationen verschoben, wobei der Effekt für die Dimere ausgeprägter als für die analogen Monomere ist. Eine Verringerung der Oberflächenspannung wird ebenfalls erreicht. Gemini-Tenside mit geeigneten Spacer-Gruppen bilden nach Zugabe ausgewählter organischer Anionen viskoelastische Lösungen, selbst wenn die dimeren Tenside nur über relativ kurz Alkylketten verfügen. Dies wurde mittels rheologischer Messungen gezeigt. Dieses Verhalten resultiert aus der Bildung langer Zylinder-Mizellen aufgrund der starken Wechselwirkung der Anionen mit den kationischen Tensiden, die die Krümmung der mizellaren Strukturen verringern. Es wurde auch festgestellt, dass das assoziative Verhalten durch die Dimerisation erhöht wird. Für ein gegebenes Gegenion kann die Spacer-Gruppe den verdickenden Effekt verstärken, in Abhängichkeit von seiner Länge und Hydrophobie. Als weitere Zusätze wurden entgegengesetzt geladene Tenside wurden mit den kationischen Dimeren kombiniert. Einige Mischungen mit dem käuflichen anionischen Tensid SDS bilden Vesikel in Lösung. Mit Blick auf diese katanionischen Mischungen wurde ein neues anionisches Gemini-Tensid, das auf EDTA basiert ist, synthetisiert und charakterisiert. Der Syntheseweg ist relativ einfach und das Tensid zeigt interessante Eigenschaften wie niedrige CMC- und scmc-Werte, gute Solubilisierungskapazität von hydrophoben Substanzen und hohe Toleranz gegen hartes Wasser. Mischungen dieses anionischen Tensids mit bestimmten kationischen Dimeren bilden visköse Lösungen, was ein starkes Mizell-Wachstum widerspiegelt.

Universiẗat, Diss., 2004--Düsseldorf.

The contamination of foods with hydrocarbon mixtures migrating from food contact materials (FCM) was first observed for jute and sisal bags treated with batching oil in the 1990s. Since the millennium, the focus has shifted to printing inks and recycled cardboard packaging as most recognized sources for hydrocarbon contamination from FCM. Mineral oil containing printing inks can either release hydrocarbons directly from the printing of folding boxes into food or indirectly entering the recycling chain of cardboard material by printed products, such as newspapers. The contamination of dry foods with mineral oil hydrocarbons (MOH) from recycled fiber packaging has been reported to reach up to 100 mg/kg [1]. Using LC-GC-FID technique the MOH were categorized into mineral oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH). The molecular mass, which is assumed to be toxicological relevant, is derived from the GC retention times of accumulated MOSH in human tissues and is limited to n C16 to n-C35 [2]. MOSH is the most significant contaminant of the human body reaching 1-10 g per person, which is of particular concern since a formation of microgranulomas (causing inflammatory reactions) in the liver was observed in rats fed with saturated hydrocarbons [3]. Furthermore, some MOAH are assumed to be genotoxic analogous to polycyclic aromatic hydrocarbons [3]. In the latest draft of a German ‘Mineral Oil Regulation’ the following limits for the migration of MOH from recycled fiber are proposed: for MOSH C16-20 4.0 mg/kg, MOSH C21-35 2.0 mg/kg and for MOAH 0.5 mg per kg food [4]. Functional barriers reducing the migration of undesirable compounds from recycled cardboards (such as MOH and other contaminants) could be a part of the solution for this issue. Supporting that approach in this study, the boxes of recycled cardboard featuring a barrier layer on the internal surface or an integrated adsorbent available early in 2014 were investigated for their efficiency in reducing migration of mineral oil hydrocarbons into dry food. A practice-oriented one-year storage test was performed with wheat flakes in seven configurations: a box of virgin fibers, two boxes of unprotected recycled cardboard, three cardboards with barrier layers (a flexo-printed polyacrylate layer, a polyvinyl alcohol coating and a multilayer involving polyester) and a cardboard containing activated carbon. The highest migration of MOH (C16-24) was observed in the boxes of unprotected recycled cardboard (MOSH: 11.4 mg/kg, MOAH: 2.4 mg/kg). Of the three investigated barrier layers only two reduced migration of MOH into food below the limits of the 3rd draft of the German mineral oil ordinance (2014) until the end of shelf life. The cardboard box involving active carbon as adsorbent prevented detectable migration of mineral oil hydrocarbons (<0.1 mg/kg). In the case of virgin fiber, which was virtually free of MOH (<1 mg/kg), migration close to the proposed limits was detected (C16-24, MOSH: 1.5 mg/kg, MOAH: 0.4 mg/kg). Therefore, it has been proven that the transport box (corrugated board) substantially contributed to the transfer of MOH into food. Plastic FCM can also release hydrocarbons, such as polyolefin oligomeric hydrocarbons (POH), into food. These POH are of synthetic nature and are formed during the polymerization process of polyolefins (150 – 3000 mg/kg in granulates of homo/hetero polymers involving ethylene and propylene). This group of synthetic contaminants contain also saturated hydrocarbons (POSH) analogous to mineral oils, but contrary no aromatic hydrocarbons. Further, a significant amount (10 – 50%) of monounsaturated hydrocarbons (POMH) was determined in the oligomeric fraction of polyolefins, which are not detectable in mineral oil products. Therefore, these POMH can be used as a marker for POH migration. A method based on two-dimensional high performance liquid chromatography on-line coupled to gas chromatography (on-line HPLC-HPLC-GC) was developed to enable the separate analysis of saturated, monounsaturated and aromatic hydrocarbons in extracts of packaging materials like polyolefins or paperboard and foods, repectively. It is an extension of the HPLC-GC method for MOSH and MOAH [1] using an additional argentation HPLC column, since normal-phase HPLC on silica gel did not preseparate saturated from monounsaturated hydrocarbons. Further, this method and comprehensive two-dimensional GC (GCxGC) was used to investigate the concentration of different oligomer types in polypropylene (PP) and polyethylene (PE) based sealing layers as well as their corresponding granulates. The analyzed sealing layers contained 180-995 mg/kg POSH and 90-435 mg/kg POMH (C16-35). Only in sealing layers involving low-density PE, oxidized polyolefin oligomers as well as cyclic oligomers (alkylated cyclopentanes and hexanes) have been detected. The transfer of POH (C16-35) from the investigated sealing layers into food can be substantial (>50%) and can reach more than 2 mg per kg food. The level of contamination depends on the oligomer content of the sealing layer, the fat content of the food, the processing temperature and the surface-volume ratio. Hot melt adhesives are widely utilized to glue cardboard boxes used as food packaging material. The analysed raw materials of hot melts mainly consisted of paraffinic waxes, hydrocarbon resins and polyolefins. The hydrocarbon resins, functioning as tackifiers, were the predominant source of hydrocarbons of sufficient volatility to migrate via gaseous phase into dry foods. The 18 hydrocarbon resins analyzed contained 8.2-118 g/kg saturated and up to 59 g/kg aromatic hydrocarbons (C16-24). These synthetic tackfier resins, especially the oligomers ≤C24, have been characterized structurally and migration into food was estimated using a food simulant and by the analysis of real food samples. About 0.5-1.5 % of the potentially migrating substances (C16 24) of a hot melt were found to be transferred into food under storage conditions, which can result in a food contamination of approximately 1 mg/kg food in this case. The order of magnitude depends on the absolute amount of potentially migrating substances from the hot melt, the hot melt surface, contact time, amount and type of foods.

Diese Arbeit befasst sich mit der Kinetik der Fehlfaltung und Aggregation von Proteinen. Anhand dreier Beispiele, der Phosphoglyceratkinase (PGK) aus Hefe, einer Variante von Barstar und des Prion-Proteins des Syrischen Hamsters (SHaPrP(90-232)) wurde insbesondere die Kinetik der Bildung von Amyloidfibrillen und deren kinetischer Vorläuferstrukturen mittels dynamischer und statischer Lichtstreuung, Circulardichroismus, Infrarotspektroskopie, Elektronenmikroskopie und teilweise analytischer Chromatographie untersucht. Die Kinetiken wurden mit Konzepten der Aggregationstheorie von Kolloiden und der chemischen Kinetik beschrieben. Die Modellierung der Kinetiken weist ausgehend von der monomeren PGK bei pH 2 und 190 mM NaCl auf eine zweistufige Reaktionskaskade, bestehend aus irreversiblen, bimolekularen Elementarschritten hin. Während der ersten Stufe wird ein engverteiltes Ensemble von Oligomeren mit einer mittleren Masse von 10 Monomeren und wesentlichen Anteilen an beta-Faltblattstrukturen gebildet. Die Protofibrillen entstehen durch die Vereinigung der strukturell polaren Oligomere, die durch die erste Reaktionsstufe bereitgestellt werden und als kritische Oligomere bezeichnet werden. Die gefundene Kopplung des Wachstums der intermediären Zustände und die Zunahme der beta-Faltblattstruktur kann innerhalb eines verallgemeinerten Diffusions-Kollisions-Modells interpretiert werden, bei dem die beta-Stränge durch intermolekulare Wechselwirkungen stabilisiert werden. Die Fehlfaltung und Aggregation des SHaPrP(90-232) bei pH 4.2 und 1 M GuHCl und geeigneten Zusätzen an Salz zeigt einen augenscheinlichen Zweizustandsübergang mit hoher Reaktionsordnung ( >2.5) zwischen dem monomeren, alpha-helikalen Ausgangszustand und einem beta-faltblattreichen, ringförmigen Oktamer. Die Progresskurven der Umwandlung der Sekundärstruktur lassen sich mit dem Zeitverlauf einer bimolekularen Reaktion anpassen. Das Oktamer bildet bei hohen eingesetzten Proteinkonzentrationen Multimere. Auf sehr langen Zeitskalen setzt die Bildung von Protofibrillen ein. Das kritische Oktamer stellt die Vorstufe der nachgeschalteten Wachstumsphänomene dar. Unter geeigneten Umgebungsbedingungen kann der nicht-nativ, partiell gefaltete Zustand von Barstar bei niedrigem pH (A-Zustand) in einem zweistufigen Prozess erst in Protofibrillen und anschlie"send in reife Amyloidfibrillen konvertiert werden. Zur Aktivierung der Konversion des oligomeren A-Zustandes (mittlere Masse von 16 Monomeren) sind moderate Ionenstärken ([NaCl]>0) und erhöhte Temperaturen (T>50°C) notwendig. Die Bildung der Protofibrillen ist unabhängig von der eingesetzten Proteinkonzentration. Bei Raumtemperatur und entsprechender Ionenstärke bilden sich amorphe Aggregate. Dagegen führt die Erhöhung der Temperatur in Abwesenheit von Salz zur Dissoziation des oligomeren A-Zustandes. Alle drei Proteine müssen zur Ausbildung protofibrillärer Strukturen und gegebenenfalls reifer Fibrillen oligomere Zustände mit partiell gefalteter Konformation einnehmen. Diese kritischen Oligomere sind langlebige Intermediate, die den Dreh- und Angelpunkt für die Bildung nachgeordneter Strukturen darstellen. Die Bildung von Amyloidfibrillen ist somit ein mehrstufiger hierarchischer Strukturbildungsprozess. Die in der Literatur bekannten Modelle der nukleierten Polymerisierung und der nukleierten Konformationskonversion werden dem höchstens in gewissen Teilaspekten gerecht. Die Annahme einer universellen Kinetik der Amyloidbildung kann im Lichte der Ergebnisse dieser Arbeit nicht aufrechterhalten werden. Dagegen scheinen die Zustände des kritischen Oligomers und der Protofibrille als Hierarchiestufen der Amyloidbildung generische Bestandteile des Prozesses zu sein. Die Kinetik der Bildung der verschiedenen Hierarchiestufen weist keine nennenswerten Gemeinsamkeiten zwischen den drei untersuchten Proteinen auf. / This thesis deals with the kinetics of misfolding and aggregation of proteins. The kinetics of amyloid formation and precursors of three proteins, phosphoglcerate kinase (PGK), a barstar variante and the Syrian hamster Prion protein (SHaPrP(90-232)) were investigated by the use of dynamic and static light scattering, infrared spectroscopy, circular dichroism, electron microscopy and in part by analytical chromatography. The kinetics were described with concepts from the theory of colloidal aggregation and chemical kinetics. The modelling of the kinetics starting from the monomeric PGK at pH 2 and 190 mM NaCl points to a two stage reaction cascade built up by irreversible, bimolecuar elementary reaction steps. During the first stage a narrow distributed ensemble of oligomeric states with an average mass of ten monomers and essentially ordered amounts of beta-sheet structure is built up. Protofibrils are formed by coalescence of the structural polar oligomers provided by the first stage which are termed critical oligomers. The found coupling between growth and acquisition of beta-sheet structure is interpreted in terms of a generalized diffusion-collision model, where stabilization takes place by intermolecular interactions. The misfolding and aggregation of SHaPrP(90-232) shows an apparent two-state transition between the initial monomeric, alpha-helical state and an beta-sheet rich, annular octamer with high reaction order (>2.5) at pH 4.2 and 1 M GuHCl with appropriate amounts of salt added. Progress curves monitoring the secondary structure transition can be fitted by the time-course of bimolecular reactions. The octamer forms multimers at high protein concentrations. Formation of protofibrils sets up on very long time-scales. The critical octamer is a precursor for all subsequent growth processes. The non-native, partially folded state of barstar at low pH (A-state) can be converted in a two-stage process first to protofibrils and then to mature amyloid fibrils under appropriate environmental conditions. Conversion of the oligomeric A-state (average mass of 16 monomers) can be activated by elevated temperatures (T>50°C) in the presence of moderate amounts of salt ([NaCl]>0). Formation of protofibrils is independent of protein concentration. Amorphous aggregates are formed at room temperature with sufficient amounts of salt added. In contrast elevated temperatures in absence of salt lead to dissociation of the oligomeric A-state. All three proteins have to populate an oligomeric, partially folded state to form protofibrils and eventually mature fibrils. These critical oligomers are long-lived intermediates which are the pivotal point from which all other structures arise. Formation of amyloid fibrils is a hierarchical assembly process where structures are built up by several stages. Models known from the literature, in particular nucleation polymerization and nucleated conformational conversion, only master partial aspects of amyloid formation. The wide-spread assumption of a universal kinetics of amyloid formation turns out to be unjustified. In contrast, the states of critical oligomer and protofibril seem to be generic parts of the hierarchical assembly process. Comparison of the kinetics of each hierarchical level amoung the three investigated proteins shows no considerable similarities.

Übergewicht, Diabetes oder Fettstoffwechselstörungen sind mit erniedrigten Adiponectinspiegeln assoziiert. Eine Modulation des Adiponectins kann durch genetische und metabolische Gegebenheiten erfolgen. Das Ziel dieser Arbeit war die Analyse von Faktoren, welche die Adiponectinspiegel beeinflussen können, sowie eine Charakterisierung der Oligomerverteilung unter verschiedenen metabolischen Bedingungen. In der MeSyBePo-Kohorte waren die zirkulierenden Adiponectinspiegel mit den Promotorpolymorphismen ADIPOQ -11377 C/G und ADIPOQ -11391 G/A im Adiponectingen assoziiert. Im Hinblick auf die metabolischen Faktoren korrelierte Adiponectin eng mit Parametern des Glukose- und Fettstoffwechsels sowie dem Übergewicht. Innerhalb von hyperinsulinämischen euglykämischen Clamps führte eine akute Hyperinsulinämie zu einer Abnahme der Adiponectinspiegel. Adiponectin zirkuliert im Serum als hochmolekulare (HMW), mittelmolekulare (MMW) und niedrigmolekulare (LMW) Spezies. Mit zunehmendem Körpergewicht konnte eine Verlagerung von HMW-Spezies hin zu den LMW-Spezies beobachtet werden. Durch eine moderate Gewichtsabnahme erhöhten sich die Anteile an HMW- und MMW-Adiponectin wieder. Während sich in Abhängigkeit vom Glukosemetabolismus keine Unterschiede in den Gesamtspiegeln ergaben, wurden bei Personen mit normaler Glukosetoleranz signifikant höhere Anteile an MMW-Adiponectin detektiert als bei Personen mit einem gestörten Glukosestoffwechsel. Insgesamt scheinen die HMW- und MMW-Spezies gegensätzlich zur LMW-Spezies reguliert zu werden. Die Arbeit unterstreicht die wichtige Rolle des Adiponectins im Glukose- und Fettstoffwechsel sowie bei einer Adipositas in vivo. Dabei waren Änderungen der Adiponectinspiegel bei Vorliegen von Insulinresistenz und Adipositas stets mit einer Umverteilung der Oligomerfraktionen verbunden. Vor allem die HMW- und MMW-Spezies des Adiponectins scheinen von entscheidender Bedeutung zu sein. / Experimental data suggest that a dysregulation of adiponectin might be involved in the development of the metabolic syndrome. Adiponectin circulates as a variety of multimeric forms and its concentration was found to be decreased in obesity, type 2 diabetes mellitus, and dyslipidemia. Polymorphisms within the adiponectin gene, as well as the metabolic status, may modulate the adiponectin level. The aim of this work was to evaluate factors that may modulate total adiponectin levels as well as the distribution of its multimeric complexes under specific metabolic conditions. In the caucasian MeSyBePo population, serum adiponectin concentrations were associated with two promoter polymorphisms, ADIPOQ -11377 C/G and ADIPOQ -11391 G/A, respectively. Mean serum adiponectin levels were related to obesity, glucose metabolism, and lipid metabolism. Additionally, hyperinsulinemic euglycemic clamps acutely lowered serum adiponectin concentration. Adiponectin circulates in serum as low-, medium-, and high-molecular-weight complexes (LMW, MMW, and HMW, respectively). Adiponectin oligomer composition was related to BMI, with decreased HMW and MMW fractions in case of high BMI levels. According to this, HMW and MMW adiponectin increased after moderate weight reduction. While total adiponectin levels were comparable between patients with type 2 diabetes and control subjects, a reduction of MMW oligomers was observed in patients with impaired glucose metabolism. Finally, these studies all suggested a differential regulation of HMW and MMW species compared to the LMW fraction. The data presented underline the important role of adiponectin within the glucose- and lipid metabolism as well as in obesity. We showed that modulation of total adiponectin levels in case of insulin resistance or obesity are always accompanied with changes of adiponectin oligomer composition. Thereby the HMW and MMW species seem to play a crucial role in affecting metabolic changes.

Oligomers and polymers based on functionalized Rf-amides were successfully synthesized for the fabrication of hydrophobic surfaces with either linear or network structure. Firstly, new functionalized Rf-amides (RfCONH-, Rf is a perfluoroalkyl segment) were developed in most cases by a one step reaction and a simple work-up procedure. The reaction behaviors of synthesized Rf-amides in polyreactions were well understood. New fluorinated oligoester polyols, blocked IPDI's, and end-hydroxyl terminated oligo(urea urethane)s have been synthesized, the detail structures and properties are well understood. These materials could be suitable components of powder coatings. On the other hand, the end-hydroxyl terminated oligo(urea urethane)s could be used as reactive additives in high solid content and water-borne coatings. Hydrophobic smooth surfaces based on linear polymers, poly(urea urethane)s and alternating MI copolymers, containing fluorinated side groups were successfully constructed. The attachment of fluorinated side groups into polymers can dramatically alter the surfaces of corresponding polymers from more hydrophilic to hydrophobic due to the enrichment of fluorinated side groups on the top of the surface. The backbone configuration, the polarity of backbones, and the thermal treatment on surfaces can influence the surface properties of corresponding materials. Finally, hydrophobic surfaces of cross-linked polyurethanes as model top coatings were constructed under melt condition at high temperature (180 and 190 oC) using the combination of fluorinated oligouretdiones and non-fluorinated oligoester polyols. It was found that the hydrophobicity of resulting cured films is a matter of the competition between the formation of cross-linking network and the segregation of fluoromoieties on the top of the surface.

No description available.

Oligomers and polymers based on functionalized Rf-amides were successfully synthesized for the fabrication of hydrophobic surfaces with either linear or network structure. Firstly, new functionalized Rf-amides (RfCONH-, Rf is a perfluoroalkyl segment) were developed in most cases by a one step reaction and a simple work-up procedure. The reaction behaviors of synthesized Rf-amides in polyreactions were well understood. New fluorinated oligoester polyols, blocked IPDI's, and end-hydroxyl terminated oligo(urea urethane)s have been synthesized, the detail structures and properties are well understood. These materials could be suitable components of powder coatings. On the other hand, the end-hydroxyl terminated oligo(urea urethane)s could be used as reactive additives in high solid content and water-borne coatings. Hydrophobic smooth surfaces based on linear polymers, poly(urea urethane)s and alternating MI copolymers, containing fluorinated side groups were successfully constructed. The attachment of fluorinated side groups into polymers can dramatically alter the surfaces of corresponding polymers from more hydrophilic to hydrophobic due to the enrichment of fluorinated side groups on the top of the surface. The backbone configuration, the polarity of backbones, and the thermal treatment on surfaces can influence the surface properties of corresponding materials. Finally, hydrophobic surfaces of cross-linked polyurethanes as model top coatings were constructed under melt condition at high temperature (180 and 190 oC) using the combination of fluorinated oligouretdiones and non-fluorinated oligoester polyols. It was found that the hydrophobicity of resulting cured films is a matter of the competition between the formation of cross-linking network and the segregation of fluoromoieties on the top of the surface.