In der vorliegenden Arbeit soll das weit gefächerte Thema der chemischen Nanotechnologie um neue Resultate bereichert werden. Im Einzelnen handelt es sich um neue Synthesemethoden für magnetische Nanorods (Nanoteilchen mit länglicher Form) und Nanoshells (oxidische Nanokristalle mit einer Hülle aus Edelmetall), ein Verfahren zur Modifizierung diverser Oberflächen mit heterogenen Polymerbürsten durch kontrollierte binäre radikalische Polymerisation, neuartige Copolymere zur Stabilisierung und Funktionalisierung von Nanopartikeln und Herstellung von amphiphilen Nanopartikeln durch Oberflächenbehandlung mit Niotensiden. Es sollen ferner die möglichen Anwendungen diskutiert werden. Die Abb. 1 illustriert die Zusammenhänge der bearbeiteten Thematik.

Les multicouches de polyelectrolytes, systèmes auto-assemblés par adsorption successive de polycations et de polyanions, constituent un matériau d’intérêt pour la fonctionnalisation de surface. Ce type de revêtement possède toutefois quelques limitations majeures : leur construction est lente et fastidieuse ; leur tenue mécanique et chimique est faible. Récemment, une méthode basée sur l’auto-construction de films par l’utilisation d’un morphogène, i.e. un gradient de catalyseur généré depuis une surface, a été développé permettant ainsi une rapide construction de revêtements robustes. Cette technique reste toutefois limitée à des systèmes particuliers basés sur la chimie click ou sur des interactions hôtes-invités. Nos travaux ont permis de diversifier cette approche de construction tout-en-un par l’utilisation de morphogènes. Dans un premier temps, des brosses de polymères ont été construites en une étape depuis une surface par la réaction de polymérisation ATRP. Cette réaction a été catalysée par la formation d’ions Cu(I) (le morphogène) par électrochimie depuis la surface de travail. L’approche morphogénique a également été utilisée afin de construire des films de polyélectrolytes et de polyampholytes en une étape par la génération électrochimique d’un gradient de protons (le morphogène) depuis la surface de travail. Ces films ont été fonctionnalisés pour présenter une activité enzymatique. / Polyelectrolyte multilayers, i.e. self-assembled systems based on successive polycation and polyanion adsorptions, constitute interesting materials for surface functionalization. These coatings possess several limitations: they are weak towards chemical and mechanical constraint and their buildup is long and tedious. Recently, a new method based on the self-construction of films by the means of a morphogen (a catalyst gradient generated from a surface) has attracted attention since it allows the quick self-assembly of robust films. Nevertheless, this technique was quite limited to peculiar systems based on click chemistry or on host-guest interactions.This present work generalize the one-pot morphogenic approach to other systems. In the first place, polymer brushes were built up from a surface by ATRP polymerization. The Cu(I) catalyst (the morphogen) was electrochemically generated at the interface.The morphogenic approach was later used to buildup polyelectrolytes and polyampholyte films in a one-pot manner by electrochemically generating protons (the morphogens) at the interface. These films exhibited an enzymatic activity.

Les micelles apparaissent comme prometteuses dans le domaine de la vectorisation de médicaments. Afin d’améliorer leur biocompatibilité nous nous intéressons ici à des synthèses originales de copolymères amphiphiles comportant un bloc hydrophobe lipidique biosourcé. Un polymère intelligent constitue le bloc hydrophile. L’huile de lin subit une modification chimique afin d’introduire un site amorceur de polymérisation. Le bloc hydrophile est alors ajouté par polymérisation contrôlée. Deux copolymères sont obtenus, le lipide-b-poly(acide acrylique), pH-sensible et le lipide-b-poly(2-isopropyl-oxazoline), thermo-sensible. Une caractérisation physico-chimique complète révèle des concentrations micellaires critiques basses et des micelles de 10 nm. Un système mixte est préparé par mélange des deux copolymères. L’étude de ce système prouve une sensibilité aux deux stimuli. Afin d’améliorer la stabilité des micelles, nous proposons la photo-réticulation des insaturations de la chaîne lipidique. / Small micellar systems seem to be really promising candidates for drug delivery applications. In order to improve the bio-assimilation of our system, the original synthesis of amphiphilic copolymers from linseed oil is carried out. First, linseed oil is chemically modified in order to introduce a polymerization initiating site. Then, the lipoinitiator is engaged in the controlled polymerization of the hydrophilic block. Two amphiphilic copolymers are obtained through this strategy: a pH-sensitive lipid-b-poly(acrylic acid), and a thermo-sensitive lipid-b-poly(2-isopropyl-oxazoline). Both present a low critical micellar concentration and form small micelles (~10 nm). By mixing both copolymers, mixed micelles responding to both stimuli were obtained. In order to improve the system’s stability, the photo-cross-linking of the lipidic double bonds in the micelle’s core is finally realized.

Photoinduced atom transfer radical polymerization (ATRP) was achieved using a simple household fluorescent lamp as the light source. In solution, methyl methacrylate could be polymerized to welldefined polymers; the photoinduced ATRP system did only convert monomers during irradiation and was inactive in the dark. In situ monitoring by UV-vis spectroscopy revealed the photoredox cycle between Cuᶦᶦ and Cuᶦ species. The linear development of the polymer number average molar mass with monomer conversion, the low dispersity as well as chain extension experiments showed the controlled nature of the polymerization. Photoinduced ATRP was also used to prepare homo- and block copolymer brushes and patterned brushes on surfaces by photoinduced surface-initiated ATRP (PSI-ATRP).

In der vorliegenden Arbeit soll das weit gefächerte Thema der chemischen Nanotechnologie um neue Resultate bereichert werden. Im Einzelnen handelt es sich um neue Synthesemethoden für magnetische Nanorods (Nanoteilchen mit länglicher Form) und Nanoshells (oxidische Nanokristalle mit einer Hülle aus Edelmetall), ein Verfahren zur Modifizierung diverser Oberflächen mit heterogenen Polymerbürsten durch kontrollierte binäre radikalische Polymerisation, neuartige Copolymere zur Stabilisierung und Funktionalisierung von Nanopartikeln und Herstellung von amphiphilen Nanopartikeln durch Oberflächenbehandlung mit Niotensiden. Es sollen ferner die möglichen Anwendungen diskutiert werden. Die Abb. 1 illustriert die Zusammenhänge der bearbeiteten Thematik.

In this study, the zwitterionic monomer [2-(methacryloyloxy)ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide (SBMA) was polymerized in a controlled manner by reversible addition-fragmentation chain transfer (RAFT) polymerization. The SBMA was also polymerized by atom transfer radical polymerization (ATRP) but in a less controlled manner why ATRP was discarded for further use in the study. The RAFT polymerized p(SBMA) was end-group modified through aminolysis forming a thiol end-group. The zwitterionic polymers have considerable anti-fouling properties and could be of use in contact lenses to prolong the wear-time. Model contact lens hydrogel substrates were synthesized, through free radical polymerization, consisting of 1/3 of silicone monomer, 2/3 of dimethyl acrylamide (DMA) and small percentages of glycidyl methacrylate (GMA) and ethylene glycol dimethacrylate (EGDMA) cross-linker. These had poor mechanical strength and could only be used to explore the effect of surface chemical modification. The p(SBMA)-thiol was ‘graftedto’, by applying thiol-epoxide ring-opening, at a free radical polymerized co-polymer consisting of DMA and GMA indicating that this could work for the model hydrogel surfaces. / I denna studie polymeriserades den zwitterjoniska monomeren [2- (metakryloyloxi) etyl] dimetyl (3-sulfopropyl) ammoniumhydroxid (SBMA) på ett kontrollerat sätt genom ”reversible additionfragmentation chain transfer” (RAFT) polymerisation. SBMA polymeriserades också genom “atom transfer radical polymerization" (ATRP) men på ett mindre kontrollerat sätt varför ATRP då förkastades för vidare användning i arbetet. p(SBMA) blev ändgruppsmodifierad genom aminolys som då bildade en tiol ändgrupp. Zwitterjoniska polymerer kan vara bra för att förhindra tillväxt av biofilmer/beläggningar och kan därför bidra till att användningstiden för kontaktlinser kan förlängas. Modellytor baserade på hydrogel framställdes genom friradikalpolymerisation, med syfte att efterlikna en kontaktlins. Modellmaterialet består av 1/3 av silikoninnehållande monomer, 2/3 av dimetylakrylamid (DMA) och små mängder glycidylmetakrylat (GMA) samt etylenglykoldimetakrylat (EGDMA) som tvärbindare. Dessa modellytor hade dålig mekanisk hållfasthet och kunde endast användas för att utvärdera effekterna av ytmodifiering. Genom att använda tiol-epoxi ring-öppning utav p(SBMA)-tiol på en sam-polymer bestående av (DMA) och (GMA) indikerade detta att "ympning-till" skulle kunna fungera för hydrogels modellytorna.

The research reported in this thesis was carried out in Brisbane, Australia and Calgary, Canada. The aim of the research conducted in Brisbane was to prepare a series of copper(I) and ruthenium(II) based complexes incorporating a hemilabile phosphine ligand and to determine whether or not these compounds possessed catalytic activity. The history, uses, properties and recent work incorporating hemilabile phosphine ligands is discussed in detail as well as the application of hemilabile ligands to atom transfer radical polymerization (ATRP) and the usefulness of the 'windscreen wiper' action of these ligands in polymerization. The literature synthesis and characterization of four hemilabile phosphine ligands is reported with modifications. The (2-chlorophenyl)diphenylphosphine ligand was prepared via a Grignard reaction giving a 11% yield. The (2-bromophenyl) diphenylphosphine ligand was prepared by reaction of 2-bromoiodobenzene with Ph2PSiMe3 in the presence of a palladium catalyst (MeCN)2PdCl2 which yielded 50% product. The 1-chloro-2-diphenylphosphinoethane ligand was prepared following the generation of a lithium diphenylphosphide which was added to 1,2-dichloroethane to give a 43% yield of product. The (2-benzoic-acid)diphenylphosphine ligand was prepared by hydrolysis of (2-methyl-ester-phenyl)diphenylphosphine. Following acidification of the methyl ester phosphine with HCl, the desired product was isolated in 88% yield. The synthesis and characterization of a series of copper(I) based complexes incorporating the prepared phosphine ligands involved reaction in CH3CN of the appropriate ligand with copper halides as starting material. Solution state 31P NMR and mass spectrometry were used to study many of these complexes in the solution state, whilst microanalysis, 31P CP MAS NMR and single crystal X-ray diffraction studies were used to study their solid state properties. The complexes of the type bis(2-halophenyl)diphenylphosphine copper halide were found to be three coordinate with non-chelating ligands and to be isostructural with the previously studied bis(2-methylphenyl)diphenylphosphine copper halide complexes. The synthesis and characterization of ruthenium(II) based complexes incorporating hemilabile phosphine ligands involved reaction of the appropriate ligands in MeOH with RuCl3.3H2O or RuCl2(DMSO)4 as the ruthenium source. Modes of characterization included solution state 31P NMR, mass spectrometry, microanalysis and single crystal X-ray diffraction studies. All ruthenium(II) based complexes were found to incorporate the hemilabile ligands in a chelating mode resulting in 6 coordinate structures. The preliminary polymerization testing of MMA in the presence of the copper(I) and ruthenium(II) based complexes has been reported. All complexes successfully polymerized the monomer and the resulting polyMMA showed polydispersity values ranging from moderate (3.1) to very high (6.7). Chapter 7 discusses research conducted over a 6 month period at the University of Calgary, Canada under an International Resident Fellowship award. This work involved the synthesis and characterization of scandium(III) and yttrium(III) based complexes incorporating a chelating amido-imine ligand, as potential olefin polymerization catalysts.

Poly(acrylic acid) (PAA) was grafted onto both termini of Pluronic F87 (PEO₆₇-PPO₃₉-PEO₆₇) via atom transfer radical polymerization to produce a novel muco-adhesive block copolymer PAA₈₀-b-F₈₇-b-PAA₈₀. It was observed that PAA₈₀-F₈₇-PAA₈₀ forms stable complexes with weakly basic anti-cancer drug, Doxorubicin. Thermodynamic changes due to the drug binding to the copolymer were assessed at different pH by isothermal titration calorimetry (ITC). The formation of the polymer/drug complexes was studied by turbidimetric titration and dynamic light scattering. Doxorubicin and PAA-b-F87-b-PAA block copolymer are found to interact strongly in aqueous solution via non-covalent interactions over a wide pH range. At pH>4.35, drug binding is due to electrostatic interactions. Hydrogen-bond also plays a role in the stabilization of the PAA₈₀-F₈₇-PAA₈₀/DOX complex. At pH 7.4 (α=0.8), the size and stability of polymer/drug complex depend strongly on the doxorubicin concentration. When CDOX <0.13mM, the PAA₈₀-F₈₇-PAA₈₀ copolymer forms stable inter-chain complexes with DOX (110 ~ 150 nm). When CDOX >0.13mM, as suggested by the light scattering result, the reorganization of the polymer/drug complex is believed to occur. With further addition of DOX (CDOX >0.34mM), sharp increase in the turbidity indicates the formation of large aggregates, followed by phase separation. The onset of a sharp enthalpy increase corresponds to the formation of a stoichiometric complex. / Singapore-MIT Alliance (SMA)

Atom transfer radical polymerization (ATRP) which utilizes transition metal based catalysts is a versatile methodology for the synthesis of a wide spectrum of polymers with controlled architectures. However, high concentrations of soluble catalyst required in an ATRP process makes the final polymer colored and toxic. Thus, the catalyst removal/reduction/recycling remains a challenge in the field of ATRP. Supported catalysts on insoluble solids such as silica gel, polystyrene beads, etc. have been used in ATRP to facilitate the catalyst recovery and recycling. However, the ability of the supported catalysts to mediate a polymerization is substantially reduced due to their reduced mobility and leaching problems. In this thesis, we report a series of novel and recyclable physisorbed CuBr2/N, N, N’, N’’-pentamethyldiethylene-triamine supported catalytic systems operating in conjunction with hydration. Supported aqueous-phase catalysis (SAPC) for ATRP was evaluated for different inorganic (Na-clay, silica and zeolite) and organic (polysaccharides) supports. The hydrated physisorbed supported catalysts were used for the polymerization of benzyl methacrylate and methyl methacrylate using an activator generated electron transfer ATRP process. The catalyst was effectively retained on the surface of supports through hydration as was verified by UV-Vis measurements. The supported catalyst was easily removed from the polymerization by simple filtration process affording a colorless polymer solution. The polymerizations produced high conversion and colorless polymers with moderately narrow polydispersity indices (PDI). The catalyst maintained high activity during the recycling experiments. We also investigated the kinetic and mechanistic behavior of these solid supported polymerization systems. Based on split kinetics experiments and UV-Vis studies it was believed that the activation and deactivation processes took place at the diffused hydrated interface between the solid support and organic phase. The branched (stars and graft) polymers were also synthesized using Na-clay supported catalyst. The produced polymers had narrow PDI and good initiator efficiencies. The functionality of the star polymers was confirmed using 1H NMR and dilute solution properties. The synthesis of graft-copolymer was confirmed by 1H NMR and atomic force microscopy. This thesis demonstrates the successful use of SAPC for ATRP to produce contamination free linear and branched polymers with moderately narrow PDI and high recycling efficiency.

In this study, surface modification of both organic and inorganic substrates (in terms of cellulose and silica nanoparticles, respectively) has been explored using surface-initiated atom transfer radical polymerisation (ATRP). The desire to modify bio-based materials to fit into new application areas and the need for bio-based materials with improved material properties is steadily increasing due to environmental concern. Superhydrophobic and self-cleaning cellulose surfaces were fabricated by combining ATRP with post-functionalisation. Glycidyl methacrylate was grafted from filter paper, and the epoxide groups were used as reactive handles to create a branched “graft-on-graft” architecture. Post-functionalisation of this architecture with perfluorinated chains or alkyl chains resulted in the formation of superhydrophobic surfaces. Grafting of N-isopropylacrylamide (NIPAAm) from filter paper yielded cellulose surfaces capable of switching the wettability, from hydrophilic to hydrophobic, in response to changes in temperature. The wettability of cellulose surfaces grafted with poly(4-vinylpyridine) (P4VP) could be adjusted from hydrophilic to hydrophobic by changing pH. Furthermore, cellulose surfaces responding to changes in both pH and temperature were obtained via grafting of block copolymers of PNIPAAm and P4VP. The use of inorganic nano-particles in composites has attracted considerable academic and industrial interest due to their excellent mechanical and thermal properties. Styrene was grafted from the surface of silica nanoparticles using ATRP. The resulting organic-inorganic hybrid materials did not aggregate to the same extent as the un-modified silica particles. The polystyrene-modified silica particles were used for the fabrication of honeycomb membranes. It was evident that the pore sizes and the number of porous layers could be tuned by varying the conditions used for film casting. To broaden the range of polymers available for film casting into honeycomb membranes, a block copolymer of polystyrene and poly(methyl methacrylate) was grafted from silica nanoparticles. Polymer-blends of polystyrene-modified particles and poly(9,9´-dihexylfluorene) (PDHF) were also used as an alternative to incorporate functionality into honeycomb membranes. / QC 20100901