Dissertations / Theses on the topic 'Polyoxazoline'

Polyoxazolines are class of polymers which are suitable for medical applications because they have many interesting properties. These polymers are characterized by antibacterial properties so they can stop bacterial colonization of medical devices and significantly reduce the risk of infection. Furthermore, polyoxazolines are interesting for good biocompatibility. Basic topic of this diploma work is preparation of oxazoline-based thin films by plasma polymerization. Thin films were prepared by plasma polymerization from 2-methyl-2-oxazoline vapors in a nitrogen atmosphere in a dielectric barrier discharge. During the deposition was increased the substrate temperature. Polyoxazoline films were analyzed by several diagnostic methods. Physical and chemical properties of thin films were studied by SEM, AFM, FTIR by measuring contact angles and nanoindentation method. The films were found to be homogeneous, hydrophilic and have a higher nitrogen content. Furthermore, films showed viscoelastic properties. Polyoxazoline films were subjected to antibacterial and biocompatibility tests and the result showed, that films have antibacterial properties and support of viability cells viability.

Hydrophilic POx have very similar behaviour with PEG owing to its peptdomimetic structure, however, POx shows higher chemical stability than PEG and can be further functionalised via substitute R in the side chains or at the end of the chain. In addition, PEtOx has been approved as an indirect food additive by FDA which may indicate the possibility of good immunogenicity of POx-based materials. Synthetic surfaces with reproducibility and biocompatibility for in vitro cell culture offer lots of advantages on adherent cells. A variety of synthetic polymers as well as properties like mechanical and chemical robustness resulting polymer brushes prior to other surface modification methods. Synthetic hydrogels can be further modified and allow a variety of mechanical and biochemical properties that determine the cell phenotype which makes it a good candidate for biomedical applications. Our work has focused on the design of polyoxazolines with controlled end chains for the design of such hydrogels and polymer brushes. In the second chapter, we review the synthesis of defined polyoxazoline and its applications, synthesis of non-fouling surfaces, fabricated hydrogels and characterisations. In the third chapter, we explore the design of poly(2-oxazolines) with controlled end chains and characterise the structure and control of initiation and termination steps. A range of initiators (bromide, iodide as well as tosylates) and termination agents were used to introduce functionalisable or polymerisable end groups on poly(2-oxazolines). Microwave assisted synthesis was used for polyoxazoline synthesis. Polyoxazolines can be simply synthesized in relatively mild conditions using this approach. The structure of the resulting polymers is characterised by NMR, MALDI-ToF and FTIR. In the third chapter, we explore the use of polymerisable polyoxazolines for the design of grafted from polymer brushes. The growth of poly(oxazoline) brushes was studied first and the resulting polymer brushes characterised. We then explored the functionalization of polymer brushes using thiol-ene chemistry and their protein resistance for cell and protein patterning. Hence, we explored the design of polyoxazoline nonfouling coatings. These surfaces allow the control of surface properties such as protein adsorption and bio-functionalization. In the fourth chapter, we designed a series of thiolated poly(oxazolines) to be used for the design of hydrogels crosslinked via thiol-ene chemistry. We fully characterised the thiolated polymers designed and studied the formation of hydrogels using an alkene-functionalised polyoxazoline and a range of thiolated crosslinkers with polyethylene glycol and poly(oxazoline) backbones. Synthetic hydrogels have attracted much attention recently for in vitro cell culture as they allow the control of the properties of soft biomaterials (mechanics, cell adhesion, degradation). Importantly, the gelation conditions used for 3D cell encapsulation are essential as they allow controlling the mechanics and stability of the gel, whilst curing in mild, non-toxic conditions. Properties such as hydrogel chemistry, macroscopic and nanoscale mechanical properties and degradation have indeed been shown to strongly affect cell phenotype and the use of these materials for tissue engineering. To study gelation in situ, photo-rheology was used to characterise the properties and kinetics of the resulting hydrogels. Here, we investigated the formation of hydrogels with different multi-arm PEG thiols. This allowed us to improve the properties of hydrogel even at low weight concentration of materials where gelation is particularly challenging.

Nous décrivons dans ce manuscrit la synthèse et l'étude de surfactifs à base de poly(2-méthyl-2-oxazoline) et de corps gras. Pour cela, deux voies de synthèse ont été réalisées. La première qui consiste à amorcer la polymérisation avec un alcool gras tosylé. La deuxième voie de synthèse a été réalisée en amorçant la polymérisation par un alcane iodé. Les surfactifs ainsi obtenus ont une chaîne grasse saturée ayant douze ou dix-huit atomes de carbone et des longueurs de chaînes polymères variables.Ces surfactifs sont examinés afin d'évaluer leur aptitude à la formulation. Ainsi, la valeur de leur concentration micellaire critique a été déterminée par tensiométrie et spectrofluorimétrie. Ensuite, l'évaluation de leurs pouvoirs mouillant et moussant, de leur HLB, de leur température de point de trouble… ont été déterminés afin de les comparer avec leurs homologues POE, les Brij®. Dans l'optique d'une application à la formulation, des tests d'évaluation de leur toxicité ont également été réalisés. Enfin, des préparations cosmétiques ont été formulées, à base de ces surfactifs et des Brij®. Parallèlement, une étude a été menée démontrant l'intérêt du carbonate de glycérol tosylé comme amorceur de la polymérisation de la 2-méthyl-2-oxazoline. Cet amorceur a permis de fonctionnaliser les polyoxazolines en extrémité de chaîne par des fonctions terminales (hydroxy)uréthane
In this manuscript, we describe the synthesis and the study of surfactants based on poly(2-methyl-2-oxazoline) and vegetable oil derivatives. Two ways for the synthesis are realized. The first path consists to initiate the polymerization with a tosylate fatty alcohol. The second synthetic route was realized by initiating the polymerization by an iodoalkane. The obtained surfactants have au saturated fatty chain with twelve or eighteen carbon atoms and various lengths of polymeric chain. This surfactants are reviewed to assess their suitability for the formulation. Thus, the value of their critical micelle concentration was determined by tensiometry and spectrofluorimetry. After, the evaluation of their wetting and foaming powers, their HLB, their cloud point temperature… was determinded in order to compare with their homologous POE, the Brij®. In the context of an application in the formulation, evaluation tests of toxicity were also made. Next, cosmetic preparations were realized, based on this surfactants and Brij®. In parallel, a study was conducted to demonstrate the tosylate gycerol carbonate interest as initiator in the 2-methyl-2-oxazoline polymerization. This initiator enable to fonctionalize the polyoxazoline in the chain end with (hydroxy)uréthane terminal function

Trois architectures de copolymères (dibloc, tribloc et hétérogreffé) amphiphiles photo-stimulables à base de polyoxazoline et de groupements photo-sensibles de type coumarine sont étudiées dans ce travail. Ces copolymères s’auto-assemblent en milieu aqueux sous forme de nanoparticules de morphologies sphériques, ovales mais également de nanofibres hélicoïdales de plusieurs micromètres de longueur. Selon les cas, les morphologies sont induites par de la cristallisation des motifs coumarine entre eux ou bien des interactions polyoxazoline-coumarine. Par ailleurs, la photo-réponse des nanoparticules a été examinée après irradiation UV des groupements coumarine, capables de dimériser de manière réversible selon la longueur d’onde utilisée. Elle diffère selon l’architecture du copolymère qui constitue les nanoparticules et donne lieu à des phénomènes de (pré-)photo-dimérisation ou photo-réticulation du cœur de celles-ci avec des réversibilités sous UV variables et un maximum d'efficacité dans le cas des copolymères triblocs. La stabilité de ces auto-assemblages a également été examinée avant et après exposition UV. Dans tous les cas, l’irradiation des nanoparticules améliore leur stabilité en température et dans le temps avec un effet maximal dans le cas de la pré-photodimérisation (tribloc). Enfin, la réticulation et la cristallisation se sont révélées être des freins au piégeage de molécules hydrophobes, illustrées ici avec le Nile Red, alors que les copolymères diblocs se sont révélés être les systèmes les plus efficaces. En somme, les nanoparticules de copolymères triblocs présentent le meilleur compromis entre stabilité, efficacité UV et piégeage
Three photo-responsive amphiphilic copolymer architectures (diblock, triblock and heterografted) based on polyoxazoline and coumarin photo-sensitive units are studied in this work. These copolymers self-assemble in water into spherical or ovalic nanoparticles and also supramicrometer helicoidal nanofibers. Depending on the macromolecular architectures, these morphologies are induced by crystallization of coumarin units or polyoxazoline-coumarin interactions. Moreover, the nanoparticle photo-response is examinated after the UV-exposure of coumarin units, that are able to reversibly dimerize according to the wavelength used. This photo-response varies with the copolymer structure and leads to (previous) photo-dimerization or photo-crosslinking phenomena. These latters present various photo-reversibility behaviors under UV and a maximal efficiency for triblock copolymers. The nanoparticle stability was additionally studied before and after UV-irradiation. In both cases, the nanoparticle stability is improved towards time and temperature with a maximal impact for the previous photo-dimerization (triblock). Finally, the crosslinking and the crystallization appear as brakes for the hydrophobic molecule entrapment, illustrated here by Nile Red, whereas diblock copolymers seem to be the most efficient systems. To conclude, previously photo-dimerized nanoparticles (triblock) are the best way combining stability, UV-efficiency and entrapment

La peau, principale barrière protectrice avec l’extérieur, est de plus en plus agressée par des sources environnementales (UV, pollution, tabac…). Ces agressions génèrent une surproduction de radicaux libres conduisant à terme au vieillissement prématuré de la peau et parfois à l’apparition de cancers cutanés. Afin de neutraliser ces radicaux présents en excès dans l’épiderme, nous avons élaboré des nanoformulations à base de polyoxazolines pour la délivrance topique d’antioxydants tels que la quercétine. Ces polyoxazolines amphiphiles sont une alternative intéressante au poly(éthylène glycol) dont l’utilisation accrue induit des problèmes de santé chez l’homme. Plusieurs architectures macromoléculaires de polyoxazolines ont été synthétisées et deux nanoformulations innovantes : micelles mixtes et nanocapsules lipidiques ont été mises au point. Ces formulations présentent une grande stabilité, un bon taux de chargement et maintiennent l’activité antioxydante de la quercétine encapsulée. La pénétration cutanée des polyoxazolines seuls et formulés a été étudiée sur plusieurs modèles de peau (GUV, modèle non biologique, oreille de souris, explant de peau humaine). Il a été montré que les nanoformulations sont capables de modifier les propriétés physico-chimiques de surface du modèle de peau non biologique, favorisant leur étalement et que les polymères peuvent pénétrer dans les couches lipidiques de modèles de membranes simples à plus complexes et in vivo sur oreille de souris. En conclusion, les polyoxazolines peuvent substituer le poly(éthylène glycol) dans les formulations et permettre la délivrance topique d’antioxydants dans l’épiderme de souris, ouvrant ainsi la voie vers des applications cutanées pour traiter des pathologies comme le psoriasis ou les mélanomes
The human skin, considered as the main barrier from the outside, is more and more assaulted by environmental sources (UV, pollutants, tobacco…). These aggressions over generate free radicals within the skin then leading to skin aging and potentially skin cancer. Therefore, nanoformulations based on polyoxazolines for topical delivery of antioxidants were investigated in order to quench the excess of free radicals located in the epidermis. As a side objective, this research project intends to demonstrate the potential of amphiphilic polyoxazolines in formulation as an alternative to poly(ethylene glycol), which overuse has led to clinical awareness. Various macromolecular architectures of polyoxazolines were synthesized and two main nanoformulations were elaborated: mixed micelles and lipid nanocapsules. These last showed a high stability overtime, a good drug loading and maintained the antioxidant activity of the encapsulated quercetin. The skin penetration study of polyoxazolines and polyoxazolines based formulations was conducted on various skin models (GUV, nonbiological skin model, mice ears, human skin explants). Nanoformulations were able to modify physicochemical skin surface properties to enhance their spreading and polyoxazolines penetrated from simple to complex lipids membranes and in vivo in mice skin. As a conclusion, polyoxazolines were proved to be an excellent alternative to poly(ethylene glycol) overuse for designing formulations and show promise for delivering topically antioxidants into epidermis creating new possibilities for skin treatment such as psoriasis or melanomas

Ce travail de thèse examine trois voies de valorisation de l'huile de pépins de raisin au travers de l'élaboration de matériaux polymères auto-associatifs, réticulés ou hybrides. L'huile végétale ou un modèle lipidique (l'oléate de méthyle) sont d'abord fonctionnalisés grâce à leurs insaturations menant à des huiles hydroxylées, aminées, ou phosphorées.Dans une première étude, l'huile et l'oléate de méthyle ont été hydroxylés par réaction thiol-ène. Les alcools gras sont ensuite transformés en macroamorceurs capables d'amorcer la polymérisation cationique par ouverture de cycle de la 2-méthyl-2-oxazoline. Les lipopolymères (LipoPOx) amphiphiles ainsi synthétisés sont capables de s'auto-associer et de former des nanoparticules monodisperses observées par DLS. Dans une deuxième étude, l'huile et certains de ses dérivés amide ont été modifiés sous UV par addition radicalaire du chlorure de cystéamine, conduisant à une diamine linéaire et à une polyamine ramifiée. Ces dernières ont été utilisées comme durcisseurs d'huile époxydée permettant la réticulation de résines époxy à fort taux de carbone biogénique. L'étude thermomécanique par analyse rhéologique montre que ces matériaux thermodurcissables ont des Tg comprises entre -38 et -9°C.Dans une troisième étude, les lipides ont été fonctionnalisés par addition radicalaire de diméthylphosphite par voie photochimique ou thermique. La transformation ultérieure des esters phosphonés en fonctions silylées a rendu ces composés réactifs vis-à-vis du titane et de ses oxydes. L'ancrage de lipides sur des particules de TiO2 ou des feuilles de Titane influe sur leurs propriétés de surface
This Ph-D work deals with the valorization of grapeseed oil for the preparation of novel and various bio-based polymers. Three pathways are developed starting from lipids and leading to polymeric materials such as self-assembled polymers, thermosets and hybride polymers. First, the vegetable oil and methyloleate were modified using radical addition on their double bonds. Following, hydroxylated, aminated and phosphonated lipids were synthesized.In a first study, the oil was hydroxylated via thiol-ene coupling reaction. The fatty alcohol was then converted into initiator for the cationic ring-opening polymerization of 2-methyl-2-oxazoline. These Lipopolymers so-called LipoPOx exhibit hydrophilic POx block and fatty block. Their amphiphilic nature confer them a self-organization ability in water. A monomodal and narrow distribution of nanoparticles was observed by DLS and AFM.In a second study, the oil and some fatty amides were also functionalized by UV-induced radical addition using cysteamine hydrochloride. A linear diamine and a branched polyamine were synthesized and used as hardeners of epoxidized vegetable oil leading to thermosets with high level of bio-carbone. The investigation on thermo-mechanical properties showed a Tg between -38 and -9°C.In a last study, the lipids were modified by radical addition of dimethylphosphite using thermal or photochemical process. Then, the phosphonate esters were converted into silylated moieties making them reactive toward titanium. The anchoring of lipids onto titanium based materials induced a modification of their surface properties

The diploma thesis deals with the deposition of layers of 2-ethyl-2-oxazoline monomer in a dielectric barrier discharge in a nitrogen atmosphere. The theoretical part describes polyoxazolines, dielectric barrier discharge, plasma polymerization and diagnostic methods that describe the characteristics of the prepared layers. The experimental part deals with the deposition of layers and the determination of physicochemical properties. Finally, the results are compared with layers that were made of 2-methyl-2-oxazoline.

Thesis (Ph.D.)--Chemical Engineering, Georgia Institute of Technology, 2009.
Committee Chair: Peter Ludovice; Committee Member: Amyn Teja; Committee Member: Arthur Ragauskas; Committee Member: William Koros; Committee Member: Yulin Deng.

The two projects covered by this thesis represent advancements in the field of biofabrication. The first project was a proof-of-principle study focused on the development of a new polymer ink for 3D-printing. Scaffold structures were printed with a hydrophilic polymer and characterized to determine optimum printing parameters. Crosslinking strategies to create hydrogels with properties similar to human tissue were also explored. The second project was focused towards developing adipose grafts for soft tissue defects. Microfibre scaffolds were designed and 3D-printed with pores suitably sized for seeding with aggregates of human stem cells, and differentiated into fat tissue under in vitro conditions.

In the latest years, many studies especially on characterization and synthesis of polyoxazolines have been made. During these studies, new polyoxazolines such as poly(2-isopropyl-2-oxazoline) (PIPOX), poly(2-(3-butenyl)-2-oxazoline) (PBOX) and modified PBOX were synthesized. However, there has been no investigation on their thermal characteristics such as thermal stability and thermal degradation products. In this study, thermal degradation characteristics, thermal degradation products and thermal stability of PIPOX, PBOX and modified PBOX polymers PBOX-Perf, PBOX-Thiop, PBOX-Sug, PBOX-SP and PBOX-TP were investigated. In this study mercaptans 1H,1H,2H,2H-perfluoro-octanethiol, 3-mercapto-1,2 propanediol, thio-&beta
-D-glucose derivative and their mixture were used in PBOX modifications. The effect of modification of PBOX with different mercaptans on thermal characteristics was also analyzed. For the PIPOX, formations of protonated monomer and oligomers from dimer to heptamer were observed. However, when the isopropyl group changes with 3-butenyl group, protonated oligomers up to trimer were observed because the crosslinking formed during the polymerization of unsaturated butenyl inhibited the production of oligomers. In addition to this, thermal degradation at lower temperatures was observed. The change in thermal stability and thermal degradation products were observed as a result of modification of PBOX with different mercaptans. Unlike PBOX-Sug thermal degradation started at very low temperatures for PBOX-Thiop and PBOX-Perf. This degradation observed at lower temperatures disappeared for PBOX-SP and PBOX-TP. For PBOX-Perf, PBOX-Sug and PBOX- Thiop, decomposition of side chains at low temperatures and decomposition of the main chain at high temperatures were observed. Although the same thermal degradation behavior for PBOX-TP and PBOX-Thiop was expected, since PBOX-TP was obtained as a result of modification of PBOX with high amounts of mercaptan used in PBOX-Thiop and small amounts of mercaptan used in the PBOX-Perf, the results show that neither PBOX-Thiop nor PBOX-Perf thermal degradation behavior are dominant. This is also valid for PBOX-SP. PBOX-SP has higher thermal stability when compared to PBOX-Sug.

In this work, a toolbox was provided to create three-component polymer conjugates with a defined architecture, designed to bear different biocomponents that can interact with larger biological systems in biomacromolecular recognition experiments. The target architecture is the attachment of two biomolecule ‘arms’ to the alpha telechelic end point of a polymer and fixating the conjugate to the gold surface of SAW and SPR sensor chips with the polymer’s other omega chain end. This specific design of a conjugate will be implemented by using a strategy to yield novel double alpha as well as omega telechelic functionalized POx and the success of all cascade reaction steps leading to the final conjugation product will be proven through affinity measurements between covalently bound mannose and ConA. All reactions were performed on a low molecular model level first and then transferred to telechelic and also side chain functionalized polymer systems
In der vorliegenden Arbeit wurden hydrophile Polymere und Biomakromoleküle chemoselektiv und vicinal miteinander an einer Bindungsstelle verknüpft. Die Kombination der Native Chemical Ligation (NCL) mit der Thiol–En-Reaktion stellte hierfür eine geeignete Methode dar. Ein Machbarkeitsbeweis wurde anhand einer niedermolekularen Modellreaktion erbracht und nachfolgend unter der Verwendung von Polyoxazolinen auf makromolekulare Polymersysteme übertragen. Die erfolgreiche Darstellung der Konjugate wurde durch biomakromolekulare Bindungsaffinitäts-Messungen zu dem Lektin ConA bestätigt

Chemoselective poly(oxazolines) (POx) and poly[(oligo ethylene glycol) acrylates] were synthesized. An initiator was produced for the preparation of poly(oxazoline)s capable of participating in click chemistry reactions which allows the functionalization of the polymer at the α terminus which was confirmed by 1H NMR spectroscopy. The initiator was used for the polymerization of hydrophilic 2 methyl 2 oxazoline (MeOx), whereby chemoselective, alkyne functionalized polymers could be prepared for Cu-catalyzed azide–alkyne cycloaddition. The desired molecular weight could be achieved through the living, ring opening cationic polymerization and was confirmed by 1H NMR, SEC and MALDI ToF measurements. Polymers were terminated with piperidine if no further functionalization was needed, or with an ester derivate for enabling amine attachment in a subsequent step. In addition, polymers were functionalized by termination with NaN3 in order to provide the counterpart to the azide–alkyne reaction. IR spectroscopy was suitable for the azide detection. The coupling of polymers showed the reactivity and could be confirmed by SEC, 1H NMR and IR spectroscopy. The composition of cysteine functionalized POx was completed by thiol–ene chemistry. Since the commercially available iso 2 propyl 2 oxazoline is not available for the cationic polymerization, 2 butenyl and 2 decenyl 2 oxazoline (ButenOx and DecenOx) were first prepared. The synthesis of both copolymers, based on MeOx could be confirmed by 1H NMR as well as with SEC, whereby narrow distributions with dispersities of 1.06 could be achieved. The cysteine functionalization of the copolymers was enabled by the creation of a thiazolidine component which could be synthesized by acetal and formyl protection of cysteine and subsequent functionalization with a thiol. The component enabled the reaction with a polymer by thiol–ene reaction which was started by the addition of dimethoxyphenyl-acetophenone and was catalyzed by irradiation with UV light. Both copolymers, with a shorter (polymers with BuenOx) and longer (polymers with DecenOx) hydrophobic sidechain could be functionalized. 1H NMR spectroscopic analysis showed a quantitative reaction with the thiazolidine derivate. After deprotection by acidic workup the desired, cysteine functionalized polymer could be isolated. Quantification of cysteine functions was ensured by a modified TNBSA assay, whereby the thiols were first oxidized in order to confirm an independent measurement of amine functions. Both, the TNBSA assay as well as the NMR measurement showed the desired number of cysteine residues. The cytotoxicity of functionalized polymers with different compositions was tested by a luminescent cell viability assay (LCVA). Both, the amount of cysteine functions (5–10%) in the copolymers as well as the length of the hydrophobic side chain were varied. All polymers did not show cytotoxicity up to concentrations of 10 mg∙mL-1. The cell activity and cell numbers only decreased below 50% and 20% respectively, when copolymers with 5% cysteine and longer sidechains were measured, which was attributed to a contamination of the sample itself. The cooperation partner performed Native Chemical Ligation (NCL) with model peptides and purified the products by HPLC. A sterically non demanding peptide was synthesized, consisting of an aromatic amino acid and four glycine units. The aromatic unit was used for the quantification of the polymer–peptide conjugate in the 1H NMR spectroscopy. A polymer having five cysteine side chains has been fully implemented by NCL to a conjugate of one polymer with five peptides. A sterically more demanding peptide was additionally used and MALDI ToF measurements confirmed the successful conjugation. Furthermore the cysteine functionalized polymer was used for nanogel synthesis. The thiol of the cysteine function was oxidized in an inverse mini-emulsion by H2O2, resulting in nanogels (~500 nm) which could be confirmed by SEM, AFM, DLS and NTA measurements. Besides POx, oligo (ethylene glycol)acrylates (OEGA) were polymerized; by copolymerization with the reactive pentafluorophenyl acrylate (PFPA) reactive and amphiphilic polymers were obtained. The synthesis of PFPA could be confirmed spectroscopically by 1H , 19F NMR, and by FT IR. Copolymers were synthesized by RAFT polymerization with narrow dispersities. Functionalization with an amine functionalized thiazolidine led to a hydrophilic cysteine functionalized polymer after acidic deprotection. Apart from this polymer, a thioester functionalization was successfully performed by reaction of the active polymer with a cyclic amine functionalized thioester which does not release a toxic by product (such as the resulting thiol) during NCL and thus features a very high potential to replace former thioester
Als hydrophile Polymere wurden chemoselektive Poly(oxazoline) (POx) und Poly(oligoethylenglykol)acrylate synthetisiert. Für die Darstellung von „klickfähigen“ Poly(oxazolinen) wurde ein Initiator synthetisiert, welcher eine Funktionalisierung des Polymers am α Terminus ermöglicht. Die erfolgreiche Darstellung wurde mittels 1H NMR Spektroskopie bewiesen. Der Initiator wurde für die Polymerisation von hydrophilem 2 Methyl 2 oxazoline (MeOx) eingesetzt, wodurch chemoselektive, Alkin funktionalisierte Polymere dargestellt werden konnten. Die gewünschten Molmassen konnten durch die lebende, Polymerisation erreicht werden und durch 1H NMR, GPC und MALDI Messungen bewiesen werden. Die Terminierung der Polymere erfolgte durch Abbruch mit Piperidin oder durch Abbruch mit einem Ester Derivat, um die Anbindung mit Aminen zu ermöglichen. Außerdem wurden Polymere durch die Terminierung mit NaN3 funktionalisiert, um das Pendant zur Azid–Alkin¬-Cycloaddition liefern zu können. Die IR-Spektroskopie eignete sich hierbei für die Azid-Detektion. Die Kopplung beider Polymere, zum Nachweis der Reaktivität, konnte durch die GPC, 1H NMR und IR Spektroskopie bestätigt werden. Die Darstellung von Cystein funktionalisierten POx konnte durch Thiol–en Chemie realisiert werden. Dazu wurde ein Copolymer mit Allylseitenketten synthetisiert. Da das kommerziell erhältliche iso-Propyloxazoline nicht für die kationische Polymerisation zur Verfügung steht, wurden Butenyl und Decenyloxazolin (ButenOx und DecenOx) synthetisiert. Die Darstellung des Copolymers, basierend auf MeOx, konnte mit 1H NMR und der GPC bestätigt werden. Enge Verteilungen bis zu einer Disperistät von 1.06 wurden erreicht. Die Cysteinfunktionalisierung der Copolymere wurde durch die Synthese eines Thiazolidinbausteins ermöglicht. Dieser konnte durch Acetal- und Formylschützung von Cystein und anschließender Funktionalisierung mit einem Thiol dargestellt werden. Der Baustein ermöglichte die Umsetzung des Polymers mit dem geschützten Cysteinderivat. Diese wurde durch Zugabe von Dimethoxyphenyl-acetophenon gestartet und durch Bestrahlung mit UV-Licht katalysiert. Sowohl Copolymere mit einer kürzeren (Einsatz von ButenOx) und langen (Einsatz von DecenOx) hydrophoben Seitenkette konnten mittels Thiol–en Chemie funktionalisiert werden. 1H NMR spektroskopische Analysen zeigten eine quantitative Umsetzung mit dem Thiazolidinderivat. Nach Entschützung konnte das gewünschte, Cystein funktionalisierte Polymer isoliert werden. Die Quantifizierung der Cysteinfunktionen wurde durch einen modifizierten TNBSA assay gewährleistet, wobei die Thiole des Cysteins zunächst oxidiert wurden, damit diese keinen Einfluss auf die Messung haben konnten. Sowohl der TNBSA assay als auch die NMR-spektroskopische Messmethode zeigte die gewünschten Anzahlen von Cysteinresten. Die funktionalisierten Polymere wurden mit unterschiedlichen Zusammensetzungen auf Zelltoxizität geprüft. Der Anteil an Cysteinfunktionen (5 10%) und die Länge der hydrophoben Seitenkette wurden variiert. Alle Polymere waren bis zu einer Konzentration von 10 mg∙mL-1 nicht toxisch. Die Zellaktivität und Zellzahl sank nur beim Copolymer mit 5% Cystein und langer Seitenkette unter einen Wert von 50% bzw. 20%, was auf eine Verunreinigung der Probe zurückgeführt wurde. Der Kooperationspartner führte die Native Chemische Ligation (NCL) mit verschiedenen Modellpeptiden durch und reinigte die Produkte mittels HPLC. Es wurden sterisch unanspruchsvolle Peptide synthetisiert, die aus einer aromatischen Aminosäure und vier Glycineinheiten bestanden. Der Aromat konnte in der 1H NMR Spektroskopie für die Quantifizierung der Polymer–Peptid Konjugate genutzt werden. Ein Polymer mit fünf Cysteinseitenketten wurde vollständig mittels NCL zu einem Konjugat aus einem Polymer mit fünf Peptiden umgesetzt. Ein sterisch anspruchsvolleres Peptid wurde im Nachhinein verwendet, wobei MALDI-ToF Messungen die Konjugation bestätigten. Das cysteinfunktionaliserte Polymer wurde außerdem für die Nanogelsynthese verwendet. Hierbei wurde das Thiol der Cysteinfunktion mittels H2O2 in einer inversen Miniemulsion oxidiert, woraus Nanogele resultierten, die mittels REM, AFM, DLS und NTA bestätigt werden konnten. Neben POx wurden Copolymere aus (Oligoehtylenglykol)acrylate und Pentafluorophenylacrylat synthetisiert und reaktive amphiphile Polymere erhalten. Die Darstellung von Pentafluorophenylacrylat konnte durch 1H und 19F NMR als auch durch FT IR spektroskopisch bestätigt werden. Copolymere wurden mittels RAFT Polymerisation mit engen Dispersitäten und den gewünschten Molmassen synthetisiert. Die Funktionalisierung mit einem aminfunktionalisierten Thiazolidin führte nach saurer Entschützung zu einem hydrophilen cysteinfunktionalisierten Polymer. Neben dieser Komponente konnte eine Thioesterfunktionalisierung durch Reaktion mit einem cyclischen aminfunktionalisierten Thiolacton erfolgreich durchgeführt werden