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Die vorliegende Arbeit befasst sich mit dem Einfluss der Ladungsarchitektur auf den ZIC-Retentionsmechanismus. Die Synthese der untersuchten Materialien erfolgte über eine kupferbasierte Funktionalisierungsmethode angelehnt an ein ATRP-Schema. Durch Modifikation der Synthesevorschrift hinsichtlich der verwendeten Katalysatorsysteme, Makroinitiatoren und Reaktionsbedingungen konnten sowohl Ionenaustauscher als auch hochkapazitive zwitterionische Austauschermaterialien auf Basis der Trägermaterialien DVB/EVB und Methacrylat dargestellt werden. Die Ladungsanordnung wurde durch die Struktur der eingesetzten Monomere festgelegt. Neben der Optimierung bestehender Vorschriften zur Darstellung sulfobetainbasierter Monomere wurden in diesem Kontext neue sulfobetainbasierte Monomere inverser Ladungsanordnung synthetisiert. Der Einfluss der Ladungsanordnung auf den Anteil an Ionenaustausch am ZIC-Retentionsmechanismus wurde mittels Variation der Eluentionenkonzentration untersucht. Als Analyten wurden UV-aktive Anionen sowie Kationen der Erdalkali- und Alkalielemente verwendet. Weiterhin wurde der Einfluss des Trägermaterials und der Kapazität auf das Austauschverhalten analysiert. Die Anwendung der zwitterionischen Phasen zur Trennung organischer Analyten unter ZIC-HILIC-Bedingungen unter Verwendung einer LC-ESI-MS-Kopplung wurde geprüft. Die Detektion der Anionen erfolgte mittels Bestimmung einerseits der Leitfähigkeit und andererseits der Absorption im UV/VIS-Bereich. Im Zusammenhang der Detektion der anorganischen Kationen wurde eine LC-ICP-MS-Kopplung genutzt. Im Zusammenhang mit der Ladungsanordnung konnte keine Präferenz hinsichtlich Anionen- oder Kationenaustausch festgestellt werden. Größere Abstände der Ladungen und deren chemische Umgebung begünstigen hingegen Ionenaustausch., This work focuses on the influence of charge architecture on the ZIC-retention mechanism. The synthesis of the stationary phases investigated was carried out using a method based on ATRP. Through modification of the synthetic prescription concerning catalytic systems, macroinitiators and reaction conditions ion exchangers as well as zwitterionic exchangers of high capacity were created on basis of DVB/EVB and methacrylat polymers.The arrangement of the charges was preset through the structure of the monomers used. The synthesis of known sulfobetaines has been optimised and new sulfobetains of inverted charge structure were prepaired. The influence of the charge architecture on the amount of ion exchange within the ZIC retentionmechanism was investigated via variation of the eluention concentration. UV-active anions and cations of earthalkaline and alkaline elements were used as substrats. Furthermore the influence oft he base material as well as the capacity has been analyzed through variations of both. The application of the materials synthesized to seperate organic substrates under ZIC-HILIC-conditions using a LC-ESI-MS has been tested. The detection of anions was carried out through determination of conductivity and of UV/VIS absorbance. For anorganic cations LC-ICP-MS was used. Based on the arrangement of charges neither anion nor cation exchange occured preferentially. Increasing charge distances and the chemical surrounding of the charge carrying functionalities seem to further ion exchange.

One of the largest problems that stands before us is the quest to find sustainable alternatives to fossil-based materials. Fossil-based products can be found all around us in our society. This quest has forced us to look for new ways to build materials. Synthetic polymer materials have traditionally been produced from fossil-based starting materials however, in modern times studies regarding biobased superseders for the unsustainable starting materials has been conducted. One of these new potential building blocks is ferulic acid (FA) that is an aromatic cinnamic acid. FA has previously been used as an antioxidant but since it in addition is aromatic, have more than two functional groups and contains a double bond between two carbons it holds a large potential for polymeric synthesis. FA has been isolated from agricultural side streams such as sugar beet pulp, flax shives, wheat- and corn bran through enzymatic release and pressurised low-polarity water extraction (PLPW). One of the largest areas of use regarding FA is the biological applications. It has been proven to be effective protection against UV-radiation which open up possible uses in the textile industry, cosmetics and skincare. FA has also shown biomedical properties such as antiallergic, anti-inflammatory, anti-diabetic, anticarcinogenic and antiviral properties among others. Two of the most common polymerization methods are free radical- and step-wise polymerization. FA shows great promise for the possibility to polymerize through both these methods since it has a double bond and more than two functional groups. Polymer materials produced from FA has been done with step-wise polymerization. The polymers showed thermostable and possibly biodegradable properties. Free-radical polymerization requires a monomer with a sterically unhindered double bond and for that reason the FA must be modified in order to polymerize using free radicals. This modified monomer has been produced in a small laboratory scale and can in theory be polymerized through radical polymerization. Ett av de största problemen som vi står inför i modern tid är hur vi ska ersätta material som är producerade från fossila bränslen. Dessa material finns överallt i vårt moderna samhälle och spelar en betydelserik roll i vår infrastruktur. Detta har tvingat oss att undersöka andra miljövänligare källor för att se om dessa kan ersätta de fossila. Polymera material är ett exempel på material som tidigare har haft en fossil bas. På grund av detta har dessa material och hur dem kan producerats undersökt för att se om det finns en alternativ biobaserad källa. Ferulsyra är en aromatisk kanelsyra som är mest känd för att ha antioxidatiova egenskaper. Utöver detta innehåller ferulsyra en dubbelbindning mellan två kol och dessutom fler än två funktionella grupper vilket indikerar att den kan vara en möjlig monomer för polymersyntes. Ferulsyra kan produceras från sidoströmmar från jordbruksindustrin så som till exemper sockerbetsmassa, linhår och vete, både genom enzymatiska reaktioner eller med hjälp av extraktion med ett lösningsmedel. En av de största användningsområdena gällande ferulsyra är inom biologiska applikationer. Den kan bland annat användas som solskydd, både inom hudvårdsindustrin och som ytbeläggning i textilier. Ferulsyra har också uppvisat medicinska egenskaper som visar på att det kan användas mot allergier, inflammationer, diabetes, canser och virussjukdomar. De två vanligaste metoderna för polymersyntes är fri radikalpolymerisation och stegvis polymerisation. Ferulsyra uppvisar stor potential för att kunna användas som monomer i båda metoderna då den innehåller en dubbelbindning mellan två kol och fler än två funktionella grupper. Syntes av ferulsyra genom stegvis polymerisation har genomförts. Resultatet var att de producerade materialen uppvisade termostabila och biologiskt nedbrytbara egenskaper. För att fri radikalpolymerisation ska vara möjligt med ferulsyra som monomer krävs det att dubbelbindningen inte är steriskt hindrad. Detta innebär att ferulsyra först måste modifieras innan polymerisationen är möjlig. Dessa modifieringar har genomförts på labbskala och den producerade monomeren är teoretiskt sätt möjlig att polymerisera genom fri radikalpolymerisation.

Photo-controlled polymerisation uses a photo-excited photocatalyst (PC) to reversibly and deactivate the propagating species. Under regulation by light, photo-controlled polymerisation features temporal control, spatial control, sequence control and high level of selectivity/orthogonality between different systems, leading to a range of applications in advanced macromolecular synthesis such as surface patterning, 3D/4D printing, polymeric micelles, multiblock antimicrobial polymers with precise sequences and architectures. All these unique features of photo-controlled polymerisation are largely dependent on properties and functionalities of PCs. Traditionally, the selection and discovery of appropriate PCs rely heavily on a trail-and-error approach, where extensive experimental screening is needed to identify desired candidates. To reduce costs and circumvent the challenges in laborious experimental work, a rational design strategy emerged where a new PC in application to a photo-controlled polymerisation system can be designed based on understanding of the structure-property-performance relationships. This dissertation aims to enable and streamline a general fully computer-guided rational strategy of designing an efficient and functional PC for a commonly used photocontrolled polymerisation technique, namely photoinduced electron/energy reversible addition-fragmentation chain transfer (PET-RAFT) polymerisation. This thesis starts from using naturally evolved Chl a with various functional substituents and investigating its photocatalytic performance and functionalities in PET-RAFT polymerisation. General orientations for the design of PET-RAFT PCs were inspired from this natural design. On top of this, comprehensive structure-property-performance relationships were established at the quantum chemical level as guiding principles for rational PC design of PET-RAFT polymerisation, by combining experimental and computational studies on a library of halogenated xanthene dyes. Finally, by implementing the most cutting-edged quantum chemical software packages, the fully computer-guided strategy of functional PC design for PET-RAFT polymerisation was enabled based on broadened structure-property-performance relationships. As an example, an efficient pH-switchable organic PC was designed. Application of this rationally designed PC in PET-RAFT polymerisation resulted in the first organocatalysed pH and light dual-gated controlled polymerisation.

A deterministic modelling approach is developed to predict the internal structure of gradient copolymer chains. A key innovation of the modelling approach is the introduction of a positional variable that gives direct access to quantitative gradient characteristics: the ensemble average composition and the gradient deviation. This positional variable is used to develop multi-dimensional population balance equations that can be solved numerically to calculate gradient quality measures. The methodology is illustrated using the gradient copolymerisation of ethylene and 1-octene via coordinative chain transfer mechanism, which is representative of a variety of polymerisation schemes for gradient copolymers. Simulation results are validated with those obtained by stochastic simulations which, until now, were the only means of predicting detailed gradient quality.

This work deals with the investigation, by means of scanning tunneling microscopy under ultra-high vacuum, of supramolecular networks resulting from the self-assembly of organic precursors on surfaces such as Cu(111), Au(111), Si(111)-B and HOPG, but also the investigation of on-surface reactions. The first chapter describes the state-of-the-art of supramolecular networks and on-surface reactions on surfaces. The second chapter presents the experimental setup and theoretical concepts, as well as the preparations of the substrates, the probe tip and the method of molecular deposition.The third chapter presents the supramolecular networks formed by the depositions of molecules functionalized by bromine atoms or nitrogen atoms on the Cu(111) and Si(111)-B surfaces. For both cases, the surface plays a key role in the formation of networks: on Cu(111), the two linear networks are stabilized by metal-organic interactions between the Cu adatoms and the organic molecules; on Si(111)-B, the nanoarchitectures are commensurable with the reconstruction √3 × √3 of the surface. As function of the competition between the intramolecular and intermolecular interactions, the networks could be 2D or 1D.The fourth chapter presents the first example of on-surface radical polymerization, which is developed by the tandem synthetic method. For this end, four arylalkylether molecules and two arylalkane molecules are synthetized and deposited on different types of surfaces such as Cu (111), Au (111) and HOPG. The proposed mechanism suggests that this reaction is initialized by the inelastic electron tunneling (IET) process, which provides the free and stable radicals for the further on surface radical polymerization.; Ce travail présente les études, par microscopie à effet tunnel (STM) sous ultravide, d’une part de la formation de réseaux supramoléculaires, résultant de l’auto-assemblage des précurseurs organiques sur les surfaces Cu(111), Au(111), Si(111)-B et HOPG, et d’autre part, de l’étude de réactions chimiques sur les surfaces Cu(111), Au(111) et HOPG. Le premier chapitre décrit l’état de l’art des réseaux supramoléculaires ainsi que les réactions chimiques sur les surfaces. Le deuxième chapitre présente le dispositif expérimental et les théories sous-jacentes, ainsi que les préparations des substrats, de la pointe et la méthode de déposition des molécules.Le troisième chapitre présente les réseaux supramoléculaires formés par les dépositions des molécules fonctionnalisées par des atomes de brome ou d’azote sur les surfaces Cu(111) et Si(111)-B. Dans tous les cas, le rôle de la surface est prédominant lors de la formation des réseaux. Sur Cu(111), deux réseaux linéaires sont stabilisés par des interactions organométalliques entre les adatomes de Cu et les molécules organiques. Sur Si(111)-B, les réseaux formés sont commensurables avec la reconstruction √3 × √3 de la surface. En fonction de la compétition entre les interactions intermoléculaires et molécule-surface, les réseaux peuvent être 2D ou 1D.Le quatrième chapitre présent le premier exemple de polymérisation radicalaire sur une surface. Pour ce faire, quatre molécules de type arylalkyléthers et deux molécules arylalkanes furent synthétisées et déposées sur les surfaces de Cu (111), Au (111) et HOPG. Le mécanisme proposé pour cette réaction débute par une étape d’initialisation grâce à un processus de transfert inélastique d’électron tunnel (IET), générant des radicaux libres qui peuvent ensuite polymérisés par voie radicalaire sur la surface.

One of the long-term goals of polymer chemistry is to develop techniques for synthesis of polymers with exact molecular weight (MW) along with precise control over microstructure. Recently, a new approach based on template polymerisation and block copolymers (BCP) self-assembled into nanoreactors has been reported [McHale et al, Nature Chemistry. 2012, 4 (6), 491 497]. The method utilises a combination of hydrogen bonding templated radical polymerisation (TRP) within micellar nanoreactors to synthesise daughter polymers of high MW with low dispersity. Size exclusion chromatography (SEC) analysis of the TRPs in nanoreactors show the daughter polymer eluting as a secondary peak before the elution of the BCPs that are used to form nanoreactors and act as templates. In this work, the ability of BCPs to self-assemble into nanoreactors suitable for template polymerisation is investigated with respect to block lengths and overall MW of BCPs, as well as type of solvents and temperature. TRP in nanoreactors is subsequently investigated through modification of various physical-chemical parameters (solvent and BCP chain lengths and composition), and kinetic parameters (temperature, time, monomer, monomer concentration and initiator concentration of polymerisation) to provide insight into the polymerisation mechanism. SEC, 1H nuclear magnetic resonance (1H NMR) and dynamic light scattering (DLS) investigations of various TRPs in nanoreactors clearly demonstrated that the secondary SEC peak, originally attributed to pure daughter polymer, is in fact consisting of nanoparticles of daughter polymer and the template BCPs. Despite the claims of the original work being invalidated, the results of this study did imply that polymerisation via a templating mechanism within segregated micellar nanoreactors is occurring and further work is necessary to elucidate the product of the polymerisations.

Metal-mediated reversible deactivation radical polymerization (RDRP) is now a cornerstone of functional polymer synthesis, dominated by copper complexes and the Atom Transfer Radical Polymerization (ATRP) moniker. A limitation of this approach is the contamination of the resultant polymers by the coloured copper complexes, thus requiring further purification, although protocols to reduce the amount of copper catalyst have been developed. Iron is an interesting alternative because of its low cost, low toxicity and reduced intensity of its optical absorption spectrum. Use of this metal in RDRP began in the late 90s and has continuously intensified. This review comprehensively covers all the work reported so far on RDRP mediated by iron complexes, organized according to ligand type, and discusses the specificities of this metal in terms of the multitude of accessible spin states and the interplay of different equilibria: atom transfer vs. direct radical trapping, associative vs. dissociative exchange, chain transfer by direct beta-H atom transfer vs. beta-H elimination from the dormant alkyl species. (C) 2014 Elsevier Ltd. All rights reserved.

Namen diplomske naloge je bil pripraviti porozne polimerne membrane iz pentaeritritol tetrakis(3-merkaptopropionata) in trimetilolpropan triakrilata ter trimetilolpropan triakrilata in divinil adipata. Membrane smo pripravili tako, da smo fotopolimerizirali kontinuirno fazo emulzije z visokim deležem interne faze (HIP emulzije), kjer kontinuirno fazo predstavlja monomerna mešanica, interno fazo pa vodna raztopina kalcijevega heksahidrata. HIP emulzijo smo pri uporabi pentaeritritol tetrakis(3-merkaptopropionata) stabilizirali s surfaktantom Pluronic, pri uporabi trimetilolpropan triakrilata pa s surfaktantom Span 65. Stabilno HIP emulzijo z določeno kemijsko sestavo smo nato s pomočjo posebnih »nožev« različnih debelin nanesli na stekleno ploščo in v UV-komori izvedli polimerizacijo. Nastale so porozne poliHIPE membrane z debelinami 300–1000 μm. Z infrardečo spektroskopijo smo preverili kemijsko sestavo membran, z vrstičnim elektronskim mikroskopom pa morfologijo sintetiziranih membran. The purpose of the graduation thesis was to prepare porous polymeric membranes from pentaerythritol tetrakis(3-mercaptopropionate) and trimethylolpropane triacrylate trimethylolpropane triacrylate and divinyl adipate. We prepared membranes by photopolymerisation of the continuous phase of a high internal phase emulsion (HIP emulsion), where the continuous phase is represented by the monomer mixture and the internal phase by the aqueous solution of calcium hexahydrate. In the case of pentaerythritol tetrakis(3-mercaptopropionate), HIP emulsion was stabilised with the surfactant Pluronic, and in the case of trimethylolpropane triacrylate with the surfactant Span 65. Afterwards, we applied stable HIP emulsion with a specific chemical composition on a glass plate using special “knives” of different thicknesses and performed polymerisation in UV chamber. PolyHIPE porous membranes with thicknesses of 300-1000 micrometers were formed. By using infrared spectroscopy, we checked the chemical structure of membranes, and by using scanning electron microscope, we checked the morphology of the synthesized membranes.

Cellulose nanocrystals (CNC) and starch nanocrystals (SNC) were grafted by ozone-initiated free-radical polymerisation of styrene in a heterogeneous medium. Surface functionalisation was confirmed by infrared spectroscopy, contact angle measurements, and thermogravimetric and elemental analysis. X-ray diffraction and scanning electron microscopy showed that there was no significant change in the morphology or crystallinity of the nanoparticles following ozonolysis. The grafting efficiency, quantified by (13)C NMR, was greater for SNC, with a styrene/anhydroglucose ratio of 1.56 compared to 0.25 for CNC. The thermal stability improved by 100°C. The contact angles were 97° and 78° following the SNC and CNC grafting, respectively, demonstrating the efficiency of the grafting in changing the surface properties even at low levels of surface substitution. The grafting increased the compatibility with the polylactide, and produced nanocomposites with improved water vapour barrier properties. Ozone-mediated grafting is thus a promising approach for surface functionalisation of polysaccharide nanocrystals.

V diplomskem delu je prikazana študija vplivov na nabrekanje, poroznost, površino, velikost in porazdelitev velikosti poli(2-hidroksietil metakrilat-ko-N,N'-metilenbisakrilamid) zrn. Polimerna zrna iz monomera 2-hidroksietil metakrilata (HEMA) in zamreževala N,N'-metilenbisakrilamida (MBAA) smo pripravili z inverzno suspenzijsko polimerizacijo, z inciatorjem amonijevim peroksodisulfatom (APS) in stabilizatorjem etil celulozo. Z namenom, da bi ugotovili vpliv zamreževala in porogenih topil na lastnosti sintetiziranih zrn, smo spreminjali količino zamreževala in vrsto dodanega porogena. Prav tako smo izvedli poskus sinteze zrn brez prisotnosti vode v monomerni fazi. Sintetizirana zrna smo preiskali z optičnim mikroskopom pri 40-kratni povečavi, določili sestavo z infrardečo spektroskopijo in izmerili povprečno specifično površino zrn z N2 adsorpcijsko porozimetrijo z BET metodo. Nabrekanje polimernih zrn z različnim deležem zamreževala smo preverili v vodi, etanolu, diklorometanu, toluenu in dioksanu. Ugotovili smo, da se z zniževanjem deleža zamreževala zvišuje stopnja nabrekanja v topilih. Med testiranimi topili pa so zrna najbolj nabrekala v vodi, sledita etanol in dioksan. Opazili smo, da se v diklorometanu zrna raztopijo. Poskus sinteze zrn v odsotnosti vode v monomerni mešanici se je izkazal za neuspešnega. Dobljena zrna so nepravilnih oblik. Vpliv deleža zamreževala na velikost zrn smo ugotavljali pri 25, 10, in 2 mas% zamreženih zrnih. Spoznali smo, da velikost zrn ni neposredno povezana s stopnjo zamreženosti, saj smo dobili najmanjša zrna pri največji zamreženosti. Delci so bili polidisperzni, saj so bile porazdelitve velikosti široke (vse do 500 µm). Ugotavljali smo vpliv porogenov izopropanola, toluena, tetrahidrofurana in n-heptana na velikost in poroznost zrn, pri najvišji stopnji zamreženosti. V tem primeru smo dosegli manjše velikosti zrn (70-300 µm). Najmanjša zrna smo dobili z izopropanolom, največja pa z n-heptanom. Obstoječa zrna so bila bela in večinoma pravilnih sferičnih oblik. Izmerjena površina in količina por vseh polimernih zrn sta bili izredno majhni. Ugotovili smo, da smo dobili zrna z zelo majhnimi porami ali celo neporozna zrna. Poroznost različno zamreženih zrn se je sicer povečevala z višanjem količine zamreževala. Z nobenim od porogenov nismo dosegli odprte porozne strukture. Rezultati so nakazovali na možnost zaprte poroznosti HEMA/MBAA zrn. The thesis presents the study of influences on swelling, porosity, surface area, size and size distribution of poly(2-hydroxyethyl methacrylate-co-N,N'-methylenebisacrylamide) beads. Polymer beads from monomer 2-hydroxyethyl methacrylate (HEMA) and crosslinker N,N'-methylenebisacrylamide (MBAA) have been prepared by inverse suspension polymerisation, with ammonium peroxodisulfate (APS) as the initiator and ethyl cellulose as the stabilizer. In order to study the influence of crosslinker and porogenic solvents on properties of polymer beads, the quantity of crosslinker and type of porogen have been varied. We also attempted to synthesize the beads without the presence of water in the monomer phase. Synthesized beads have been characterized with an optical microscope at 40-fold magnification, with infrared spectroscopy and with N2 adsorption porosimetry, where the specific surface area of beads has been determined using BET method. We checked the swelling capacities of differently crosslinked beads in water, ethanol, dichloromethane, toluene and dioxane. It has been noticed that swelling capacity increases with reducing the amount of crosslinker. Among the tested solvents the beads were the most swollen in water, followed by ethanol and dioxane. We found out that our beads dissolve in dichloromethane. We failed at the attempt to synthesize our beads without water in the monomer phase. The obtained product was irregularly shaped. We determined the influence of crosslinker on the bead size in beads with 25, 10 and 2 w% of crosslinker. We have noticed that the bead size does not entirely depend on the degree of crosslinking, because we obtained the smallest beads at the highest crosslinking degree. Particles were polydisperse, as the size distributions were broad (up to 500 µm). We have also been studying the influence of porogens isopropanol, toluene, tetrahydrofuran and heptane on bead size and porosity at the highest crosslinking degree. In this case, smaller bead sizes were obtained (70-300 µm). We gained the smallest beads with isopropanol and the largest with n-heptane. Prepared beads were white and mostly in proper spherical shapes. Measured surface area and volume of pores in polymer beads were very small in all cases. We came to the conclusion that our beads have very small pores or are even nonporous. Otherwise, porosity of variously crosslinked beads was increasing with the amount of crosslinker. We did not achieve an open porous nature with neither of porogenic solvents. Results indicated a possibility of closed porosity of HEMA/MBAA beads.

The manuscript of Mrs Marie-Claude Dubois-Clochard reports on the main results obtained in synthesis and structuration of functional polymers at the nanoscale. If the synthesis of functional polymers is the basic of the presented studies, the chronological order of her research activities from 1995 to 2013 shows an evolution from classical polymerisations in solution towards radio-induced polymerisations in confined space controlled by RAFT mechanism. The innovation is about the development of new objects made of polymers and organic/inorganic composites designed at the nanoscale to bring original physical and physico-chemical properties. Three applied fields stand out: Energy-Environment (Engines, Fuel cells, Sensors for water quality), Health (Nanovector for tumour therapies and imaging, Ion and molecules tranlocation through a single nanopore in a polymer membrane) and Nanotechnologies (Magnetoresistance of a single magnetic nanowire). Noteworthy results are: - the setting up of bi-langmuirian adsorption isotherm equations at solid/hydrocarbon interface for macromolecules at low concentrations, and, at high concentration, particular behaviour of reorganisation of these identical macromlecules, not in alternative layers but in reverse hemi-micelles formation. - the synthesis of a novel pH-dégradable polymer allowing an hydrolytic degradation from pH 7.4 (Sang) to pH 5.5 (Intracellular lysosome) to deliver drugs into tumor cells (Santé). - the radiation-induced grafting-through process in solid polymers showed by a cooperative effect of solvent/growing polymer chains into fluoropolymers. - the synthesis of bi-functional nanoporous polymer track-etched membranes having a functionality in the pores and another on the surface. This membrane, after changing in electrode by simple metallisation, has been the subject of valorisation projects to a start-up creation and/or a technological transfer for the development of a sensor able to detect heavy metals ions traces in treated water (Environment). In the same framework, the direct functionalisation of tracks created by Swift Heavy Ions irradiation at GANIL in polymer films has been used to develop new proton exchange membranes for fuel cell (Energy). - Non-described observation of a cooperative effect on ion mobility in a confined space made of a single cylindrical nanopore in a thin polymer membrane. Boost or slow down effect on ions mobility in this single nanopore of charged walls depends only on the chemical nature of the ions and their concentration. - Observation of jumps in the resistance of a biconical magnetic nanowire under a magnetic field (constriction size of 10 nm) beyond the magnetoresistance effect. These jumps depend both on the geometry of the system and the intensity of the injected current. Relaxation effects before and after a jump show an energy-activated system. - Nanopore size tuning of a polymer membrane by radio-induced polymerisation controlled by RAFT mechanism., Le manuscrit HDR de Mme Marie-Claude Dubois-Clochard relate les principaux résultats acquis en synthèse et structuration à l'échelle nanométrique de polymères fonctionnels. Si la synthèse de polymères fonctionnels est à la base des études abordées, l'ordre chronologique des activités de Recherche de 1995 à 2013 montre une évolution des polymérisations classiques en solution vers des polymérisations radio-induites contrôlées par mécanisme RAFT en milieu confiné. L'innovation porte sur le développement de nouveaux objets polymères et composites organique/inorganique façonnés à l'échelle nanométrique aux propriétés physiques et physico-chimiques originales. Trois domaines d'application se détachent : l'Energie-Environnement (Moteurs, Piles à combustible, Capteurs pour la qualité de l'Eau), la Santé (Nanovecteurs pour Thérapie cancéreuse et imagerie, translocation d'ions ou de molécules à travers un nanopore unique dans une membrane polymère) et les Nanotechnologies (Magnétorésistance d'un nanofil magnétique unique de forme cylindrique ou biconique). Les résultats marquants ont été : - l'établissement d'isothermes d'adsorption de type bi-langmuir à l'interface solide/liquide organique pour des macromolécules tensioactives à faible concentration, et, à forte concentration, un comportement particulier de réorganisation de ces mêmes macromolécules, non pas en couches alternées, mais sous forme d'hémicelles inverses. - la synthèse d'un polymère pH-dégradable innovant permettant une dégradation hydrolytique en passant de pH 7.4 (Sang) à pH 5.5 (Lysosome intracellulaire) en vue de délivrer des toxines dans les cellules tumorales (Santé). - la démonstration de l'effet coopératif solvant/polymère en croissance pour la pénétration du greffage induit par irradiation dans des films fluoropolymères. - la synthèse de membranes polymères nanoporeuses à traces attaquées bi-fonctionnelles ayant une fonctionnalité dans les pores et une autre en surface. Cette membrane, après transformation en électrode par simple métallisation aura fait l'objet de projets de valorisation en vue d'une création de start-up et/ou de transfert de technologie pour le développement d'un détecteur de traces métaux lourds dans l'eau traitée (Environnement). Dans la même thématique, la fonctionnalisation directe des traces dans les films de polymères irradiés aux ions lourds rapides du GANIL a permis de développer de nouvelles membranes conductrices de protons pour les piles à combustible (Energie) - l'observation non-décrite d'effets coopératifs sur la mobilité des ions dans un milieu confiné créé par un nanopore cylindrique unique dans une membrane fine de fluoropolymère. L'effet accélérateur ou décélérateur de la mobilité des ions confinés dans le pore aux parois chargées semble dépendre uniquement de la nature chimique des ions et de leur concentration. - L'observation de sauts de résistance bien au-delà de la magnétorésistance d'un nanofil magnétique biconique (constriction de l'ordre de la dizaine de nanomètre) sous champ magnétique ayant une dépendance à la fois en angle et en intensité de courant injecté. Effets de relaxations avant et après saut montrant un système énergétiquement activé. - Le contrôle de taille des nanopores d'une membrane polymère par polymérisation radio-induite contrôlée par mécanisme RAFT.

This work has investigated two routes of synthesising polymers containing L-histidine using maleimide chemistry; grafting of histidine onto an ethylene-alt-maleic anhydride copolymer and AIBN (azobisisobutyronitrile) initiated radical polymerisation of the monomer maleoyl-L-histidine. The grafting technique and monomer synthesis are utilising the maleimide formation between the primary amine of histidine and maleic anhydride. The reactions are conveniently carried out in one step with good yields. The copolymers containing L-histidine were prepared by reacting L-histidine or L-histidine methyl ester with poly(ethylene-alt maleic anhydride) in DMSO at 50 °C for 8-16 h with 80% yields independent of the degree of substitution. The monomer maleoyl-L-histidine was synthesised by reacting histidine and maleic anhydride in acetic acid and the monomer was subsequently polymerised by AIBN radical initiation in DMSO at 80 °C for 48 h to yield poly(N-histidyl maleimide). The resulting polymer had a different optical rotation ([α] D 20 = −11) than the monomer ([α] D 20 = +25), which is ascribed to the threo-diisotactic and/or threo-disyndiotactic stereoregularity of the polymer. Refereed/Peer-reviewed

With the ambition to decrease the utilization of fossil fuels, a development of those raw materials that today only are seen as waste products is necessary. One of those waste products is turpentine. Turpentine is the largest natural source of terpenes in the world today. The main components are the terpenes α-pinene, β-pinene and 3-carene. In this project, different polymerisation techniques have been evaluated to polymerise limonene with the aim to make a material out of the green raw material, turpentine. Limonene is a terpene that can be found in turpentine. It has a planar structure and should work as a model for other terpenes. Previous work on polymerising terpenes has focused on succeeding with performing polymerisations of terpenes utilizing the techniques of cationic polymerisation and radical polymerisation. However, this has been done without the aim to make a material out of the polymers. In this project, on the other hand, the main focus has been to obtain a polymer that can be used as a basis for a material. Techniques that have been applied are: radical polymerisation, cationic polymerisation and thiol-ene polymerisation. In this study, attempts to homopolymerise limonene and also copolymerise it with other synthetic monomers, such as styrene, have been performed with both radical polymerisation and cationic polymerisation. The procedure for the radical polymerisation has been conducted following the work by Sharma and Srivastava. [1] Even though several articles have been published about radical copolymerisations of limonene with other synthetic monomers, the radical polymerisations have not succeeded in this project. Further, the technique of thiol-ene chemistry has shown that limonene can be used in polymerisations; limonene reacts spontaneously with 2-mercaptoethyl ether forming a viscous polymer. The obtained polymers have been characterized with proton nuclear magnetic resonance(1H-NMR), size exclusion chromatography (SEC), matrix-assisted laser desorption ionization-time of flight mass spectroscopy (MALDI-TOF MS), differential scanning calorimetry (DSC), fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy.

The aim of my work is to provide basic understanding of polymerization behavior of cyclic ketene acetals with different vinyl monomers and their properties evaluation. First, functional degradable poly(ester-co-NIPAAm) is synthesized by free radical copolymerization. The copolymerization behavior is intensively analyzed. The resulting polymers are found to be hydrolytic degradable and thermal sensitive leading to a solution-suspension transition in water. Second, the strong reactivity of cyclic ketene acetals with Brönsted acids is intensively investigated, which provides important data for synthesis, cationic polymerization of cyclic ketene acetals and their copolymerization behavior with vinyl acids. Third, ion containing degradable polymers, including ionomers and polyelectrolytes, are synthesized by free radical polymerization and subsequent quaternization of amine in the chain. The resulting polymers obtain a variety of new properties, which can be easily tuned by changing the copolymer compositions and quaternization behaviors. Microstructures are intensively investigated by NMR, SAXA, TEM and DMA to establish the relationship between morphology and property., Die ringöffnende radikalische Polymerisation von Cycloketenacetal führte zu einem Polyester, einer Klasse von abbaubaren Polymeren. Im Rahmen dieser Arbeit wurde die Bioabbaubarkeit mit unterschiedlichen Vinylpolymeren kombiniert, indem Cycloketenacetal mit einem Vinylmonomer radikalisch copolymerisiert wurde. Die neuen Materialien behielten zum Teil die Eigenschaften von beiden Polymeren bei oder zeigten neue Eigenschaften, abhaengig von der Copolymerzusammensetzung. Zu Beginn wurden 5,6-Benzo-2-methylene-1,3-dioxepan (BMDO) und N-isopropylaminoacrylat (NIPAAm) radikalisch copolymerisiert. Die Thermosensitivitaet und die Abbaubarkeit des neuen Copolymers – Poly(BMDO-co-NIPAAm) wurde untersucht. Um wasserlösliche abbaubare Vinylpolymere herzustellen, wurde Cylcoketenacetal mit Methacrylsaeure (MAA) radikalisch copolymerisiert. Die Copolymerisation von BMDO und MAA folgte nicht dem erwarteten konventionelen Weg. Durch saeurekatalysierte Addition von MAA an die Doppelbindung des BMDO wurde ein neue Vinylmonomer (3-methyl-1, 5-dihydrobenzo[e] [1, 3]dioxepin-3-yl methacrylat, (A), gebildet. Nicht nur MAA, sondern auch andere Brönsted Saeuren mit pKa < 18 können die Doppelbindung des BMDO protonieren. Bei dem Ziel abbaubare ionische Vinylpolymere zu synthetisieren, wurden abbaubare kationische Vinylpolymere durch eine zweistufige Reaktion hergestellt. Zuerst wurde eine radikalische Copolymerisation von 5,6-benzol-2-methylene-1,3-dioxepan (BMDO) und N,N-dimethylaminöthyl methacrylat (DMAEMA) durchgeführt. Im zweiten Schritt wurde das Copolymer – Poly(BMDO-co-DMAEMA) mit Alkylbromid (BrCnH2n+1) quaternisiert. Durch Kontrolle der Copolymerzusammensetzung und des Quaternierungsverhaltens wurden neue kationischen Polymere mit unterschiedlicher Wasserlösilchkeit, antibakteriellem Verhalten und Abbaubarkeit hergestellt. In vorhergehenden Arbeiten wurde das bioabbaubare Copolymer – P(MDO-co-MMA) mit 40mol% MDO durch radikalische Polymerisation von MDO und MMA synthetisiert. Um die mechanischen Eigenschaften dieses bioabbaubaren Copolymers zu verbessern, wurde ein Ionomer, dessen Matrix Poly(MDO-co-MMA) ist, hergestellt. Zuerst wurden MDO, MMA und DMAEMA radikalisch terpolymerisiert. Die erfolgreiche Terpolymerisation wurde durch NMR- und GPC-Messungen bewiesen. Als Quaternierungsmaterial wurden Bromethan (BrC2H5) und Bromdodecan (BrC12H25) ausgewaehlt.

This thesis is concerned with the development of new methodologies that could affect the radical synthesis of small molecules and the controlled construction of polymers. A new synthetic approach allowing the synthesis of 1,2-dione derivatives, taking advantage of the radical chemistry of xanthates was established. These diones were then used in the preparation of new pyrazine structures, a family of compounds of potential biological interest. In the course of this work, a new reaction for the preparation of imidazoles and benzimidazoles was discovered. An other study involved the development of polymers on soluble support. These polymers are easily prepared by living radical polymerisation using the xanthate group technique (Madix). Their application overcomes the difficulties encountered with insoluble polymers used in solid supported synthesis which suffers from limitations due to the heterogeneous nature of the chemical transformation. One of the most important characteristic of such polymers is that they facilitate monitoring of the reaction process as there is no need to detach the substrate from the polymer. The last part of this thesis consisted in the identification, synthesis and screening of the properties of new modulating agents for controlled radical polymerisation. The homolytic dissociation of some dihydro-pyrazolone compounds was found capable of initiating a radical polymerisation and partially of controlling the polymer growth. The scope and the limitations of this system were examined in detail., Cette thèse se divise en trois parties. La première concerne le développement d'une nouvelle voie d'accès à des hétérocycles azotés. Cette synthèse est basée sur deux étapes: l'addition radicalaire d'un xanthate, portant une fonction 1,2-dione, sur diverses oléfines suivie de sa condensation sur une diamine. Cette étude a permis de préparer des composés présentant un intérêt biologique certain tels que des pyrazines. De plus, une nouvelle méthodologie permettant l'accès à des structures imidazoles a été mise en évidence. La seconde partie a été consacrée à la préparation d'un support soluble à l'aide du procédé Madix. La dernière étude porte sur le développement de nouveaux agents modérateurs de la polymérisation radicalaire. Cette étude nous a amenés tout d'abord à synthétiser une large gamme de composés originaux de type dihydro-pyrazolone. Par la suite, la mise en place d'une étude modèle nous a permis de mesurer l'aptitude à se dissocier de ces composés puis de sélectionner les meilleurs candidats. Enfin, une étude poussée en polymérisation des agents sélectionnés a permis de mieux comprendre leur mécanisme d'action. Nous sommes en présence d'un système de type initer original. Ce système de polymérisation n'est cependant pas vivant du fait de l'irréversibilité de l'addition du contre radical dihydro-pyrazolone sur la chaîne polymère.

Control over biomolecule interactions at interfaces is becoming an increasingly important goal for a range of scientificfields and is being intensively studied in areas of biotechno logical, biomedical and materials science. Improvement in thecontrol over materials and biomolecules is particularly important to applications such as arrays, biosensors, tissueengineering, drug delivery and ‘lab on a chip’ devices. Furthe r development of these devices is expected to be achievedwith thin coatings of stimuli responsive materials that can have their chemical properties ‘switched’ or tuned to stimulatea certain biological response such as adsorption/desorption of proteins. Switchable coatings show great potential for therealisation of spatial and temporal immobilisation of cells and biomolecules such as DNA and proteins.This study focuses on protein adsorption onto coatings of the thermosensitive polymer poly(N-isopropylacrylamide)(pNIPAM) which can exhibit low and high protein adsorption properties based on its temperature dependentconformation. At temperatures above its lower critical solution temperature (LCST) pNIPAM polymer chains arecollapsed and protein adsorbing whilst below the LCST they are hydrated and protein repellent.Coatings of pNIPAM on silicon wafers were prepared by free radical polymerisation in the presence of surface boundpolymerisable groups. Surface analysis and protein adsorptio n was carried out using X-ra y photoelectron spectroscopy,time of flight secondary ion mass spectrometry and contact angle measurements.This study is expected to aid the development of stimuli-responsive coatings for biochips and biodevices.Keywords: Surface modification, protein adsorption, radical polym erisation, stimuli-responsive polymers, biochips

As an extension of our previous studies concerning the free radical copolymerisation of 25,26,27-tripropoxy-28-(4-vinyl-benzyloxy)-p-tert-butylcalix[4]arene (3) with styrylic monomers, we report herein on the synthesis and characterisation of new terpolymers derived from 3, styrene and divinylbenzene, having nominal crosslinking degrees ranging from 4% to 40% wt. The terpolymers exhibited good thermal stabilities (DSC) and were prepared in good yields. Depending on the reaction conditions (dilution degree and aqueous phase to porogen ratio), materials with identical nominal crosslinking but otherwise differentiated morphologies and swelling abilities were obtained. In a related study, the radical polymerisation of styrene was carried out in the presence of a novel calix[4]arene derivative 4, bearing two distal benzyl–vinyl groups in the lower rim. It is shown that, albeit the presence of two phenolic groups within the calixarene moiety which could have functioned as inhibitors of the free radical polymerisation, the macrocycle was able to take part in the copolymerisation reaction, yielding new soluble and crosslinked polymers. In both cases, no pendant vinyl groups were found in the polymeric materials. The probable mechanisms underlying their formation are discussed.