Magister Scientiae - MSc / Solar energy generation arises as a result of direct conversion of sunlight into electricity a by solar cell; which is mainly made up of a semiconducting material incorporated into a system. It is emerging as one of the most reliable and cost efficient renewable energy sources. Within the solar field, organic bulk heterojunction photovoltaic cells have proved of being able to have a great impact in the future years; mainly due to the easy processability of the active layer and substrate, their cost effectiveness and above all, a good power conversion efficiency associated to the close 3-dimensional interpenetrating network that is generated from blending donor and acceptor semiconducting materials together in a bulk heterojunction active layer. In this research work, we therefore report on the study of a newly developed organic bulk heterojunction active layer based on a blend of a star-copolymer generation 1 poly(propylenethiophenoimine)-co-poly(ethylenedioxythiophene) (G1PPT-co-PEDOT) as donor material with N,N-diisopropylnaphthalene diimide (NDI) as acceptor material. Both materials were chemically synthesized. The synthesis of G1PPT-co-PEDOT started first by the functionalization of generation 1 poly(propyleneimine) tetramine, G1PPI into G1PPT by condensation reaction in the presence of 2-thiophene carboxaldehyde under Nitrogen gas followed by the copolymerization of G1PPT with ethylene dioxythiophene (EDOT) monomer in the presence of ammonium persulfate, (NH4)2S2O8 as oxidant. On the other hand, NDI was also synthesized via condensation reaction of 1,4,5,8-naphthalene tetracarboxylic dianhydride in the presence of two (2) equivalences of N,N-diisopropylamine at 110 oC overnight in DMF. Both materials were characterized using FT-IR, UV-Vis spectroscopy, Fluorescence spectroscopy, Voltammetry, HRSEM microscopy and XRD. Based on the cyclic voltammetry and UV-Vis results, we were able to calculate the HOMO, LUMO and band gap energy (Eg) values of both the donor and acceptor to be -4.03 eV, -6.287 eV and 2.25 eV for iii the donor G1PPT-co-PEDOT respectively and -4.302 eV, -7.572 eV and 3.27 eV for the acceptor respectively. From these results, the energy diagram for both donor and acceptor was drawn and it comes out that the separation between the HOMO of the donor and the LUMO of the acceptor ΔEg = 1.985 eV, the ideal value for a good donor-acceptor combination. Also the offset energy that is, the energy difference between the LUMO of the donor and the LUMO of the acceptor is 0.302 eV.

L'obtention de copolymères à blocs occupe maintenant une place considérable dans la chimie macromoléculaire depuis l'avènement de nouvelles techniques de polymérisations contrôlées (polymérisation anionique coordinée, polymérisation cationique. polymérisation radicalaire contrôlée, ...) en plus de la polymérisation anionique Ces polymérisations contrôlées sont le seul moyen d'obtenir des polymères bien définis et plus particulièrement des copolymères à blocs en étoile. Pour ces copolymères à blocs, le couplage de deux polymères offre l'avantage de combiner leurs propriétés souvent divergentes (des blocs hydrophiles et des blocs hydrophobes, des blocs ioniques et des blocs non ioniques, des blocs rigides et des blocs mous, des blocs amorphes et des blocs cristallins) dans une seule structure. Un intérêt croissant s'est récemment développé pour les copolymères à blocs comportant des polymères biocompatibles et des polymères fonctionnalisés. L'auto-assemblage de copolymères à blocs dans des solvants sélectifs ainsi que la micellisation des copolymères à blocs et leur efficacité en tant que stabilisants d'émulsions sont particulièrement étudiés dans la littérature. Les PDMS sont des matériaux extrêmement intéressants, car ils possèdent de nombreuses propriétés physico-chimiques comparés aux autres polymères: températures de transition vitreuse faibles (env. -120°C) très grande flexibilité de la chaîne, bonne résistance à l'oxydation, résistance thermique et aux UV hydrophobicité, biocompatibilité, haute perméabilité aux gaz et faible énergie de surface. En dépit de leurs nombreuses propriétés particulières, les homopolymères PDMS sont mécaniquement trop faibles pour être utilisés dans différentes applications pratiques. En raison de leurs grands volumes de leur faible énergie de surface et de leur haute flexibilité de chaîne, les PDMS tendent à être rejetés de la matrice quand ils sont mélangés avec d'autres polymères. Un moyen efficace d'augmenter la compatibilité de ces mélanges est de former des copolymères siloxane-polymère organique. La poly(e-caprolactone) (PCL), un polyester aliphatique linéaire, est un polymère biocompatible et biodégradable et il est bien connu pour être miscible avec une grande variété de polymères. Les copolymères à blocs basés sur le PDMS et la PCL combinent les excellentes propriétés du PDMS avec l'effet de compatibilisation de la PCL. Cela en fait d'excellents candidats comme additifs pour la modification de surface, l'encapsulation de médicaments et dans des applications en tant que biomatériaux. La première partie de ce travail de thèse porte sur la synthèse de différents copolymères diblocs (PCL-b-PDMS), triblocs (PCL-b-PDMS-b-PCL) et en étoile (PCL)2-PDMS de masses molaires variables, par polymérisation anionique coordinée de l'e-caprolactone à partir d'un macroamorceur PDMS mono- ou dihydroxylé. Les copolymères à blocs synthétisés ont été caractérisés pour montrer l'influence de leur structure (linéaire ou étoile) sur leurs propriétés thermiques (température de transition vitreuse, température et enthalpie de fusion) et leur morphologie (taux de cristallinité).Le poly(chlorure de vinyle) non plastifié (PVC) est un polymère amorphe, linéaire, thermoplastique, avec un grand intérêt commercial. Quand il est plastifié, le PVC présente des propriétés intéressantes permettant des applications dans le domaine biomédical (tubes de sang pour l'hémodialyse, tubes endotrachéales, cathéters, lentilles de contact, gants, ainsi que l'emballage pour l'entreposage des médicaments). Parmi les plastifiants polymères qui peuvent être utilisés pour le PVC, les polyesters aliphatiques sont d'un grand intérêt, en particulier la poly(e-caprolaclone). Pour conférer une hémocompatibilité il peut être ajouté à ces mélanges des polysiloxanes, en particulier des poly(dimethylsiloxanes). / Synthesis and characterizationof block copolymers and star block copolymers from new heteromultifuntional initiators Synthesis of block copoymers occupies an important place in macromolecular chemistrv since the advent of new techniques for controlled polymerizations (coordinated anionic polymerization, cationic polymerizatio, controlled radical polvmerization,...) in addition to anionic polymerization.

<p>One of the most powerful aspects of conducting polymers is their ability to be nanostructured through innovative, synthetically manipulated, transformations, such as to tailor-make the polymers for specialized applications. In the exponentially increasing wide field of nanotechnology, some special attention is being paid to innovative hybrid dendrimer-core based polymeric smart materials. Star copolymers are a class of branched macromolecules having a central core with multiple linear polymer chains extending from the core. This intrinsic structural feature yields a unique 3D structure with extended conjugated linear polymer chains, resulting in star copolymers, which have higher ionic conductivities than their corresponding non-star conducting polymer counterparts. In this study an in-depth investigation was carried out into the preparation and characterization of specialized electronic &lsquo / smart materials&rsquo / . In particular, the preparation and characterization of novel conducting dendrimeric star copolymers which have a central poly(propylene imine) (PPI) dendrimer core with conducting polypyrrole (PPy) chains extending from the core was carried out. This involved, first, the preparation of a series of dendrimeric polypyrrole poly(propylene imine) star copolymers (PPI-co-PPy), using generations 1 to 4 (G1 to G4) PPI dendrimer precursors. The experimental approach involved the use of both chemical and electrochemical synthesis methods. The basic procedure involved a condensation reaction between the primary amine of a diamino functional PPI dendrimer surface and 2-pyrrole aldehyde, to afford the pyrrole functionalized PPI dendrimer (PPI-2Py). Polymerization of the intrinsically contained monomeric Py units situated within the dendrimer backbone was achieved via two distinctly different routes: the first involved chemical polymerization and the second was based on potentiodynamic oxidative electrochemical polymerization. The star copolymers were then characterized using various sophisticated analytical techniques, in-situ and ex-situ. Proton nuclear magnetic resonance spectroscopy (1HNMR) and Fourier transform infrared spectroscopy (FTIR) were used to determine the structures. Scanning electron microscopy (SEM) was used to determine the morphology. Themogravimetric analysis (TGA) was used to study the thermal stability of the prepared materials. X-ray diffraction analysis (XRD) was used to study the structural make-up of phases, crystallinity and amorphous content. Hall effect measurements were carried out to determine the electrical conductivity of the chemically prepared star copolymers. The PPI-co-PPy exhibited improved thermal stability compared to PPI-2Py, as confirmed by TGA. SEM results showed that the surface morphology of the functionalized dendrimer and star copolymer differed. The surface morphology of the chemically prepared star copolymers resembled that of a flaky, waxy material, compared to the ordered morphology of the electrochemically grown star copolymers, which resembled that of whelk-like helixes. In the case the electrochemically grown star copolymers, SEM images recorded at higher magnifications showed that the whelk-like helixes of the star copolymers were hollow tubes with openings at their tapered ends, and had an average base diameter of 2.0 &mu / m. X-ray diffraction analysis of the first generation star copolymer G1PPI-co-PPy revealed a broadly amorphous structure associated with PPy, and crystalline peaks for PPI. Cyclic voltammetry (CV), square wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) techniques were used to study and model the electrochemical reactivity of the star copolymer materials. Electrochemical impedance spectroscopy data showed that the G1PPI-co-PPy exhibited slightly higher ionic conductivity than pristine PPy in lithium perchlorate. The second generation star copolymer G2PPI-co-PPy electrochemically deposited on a platinum (Pt) electrode had a lower electrochemical charge transfer resistance compared to electrodeposited polypyrrole (PPy) on a Pt electrode, and bare Pt. The decrease in charge transfer resistance was attributed to an increase in the conjugation length of the polymer as a result of the linking of the highly conjugated PPy to the PPI dendrimer. Bode impedimetric analysis indicated that G2PPI-co-PPI was a semiconductor, with a maximum phase angle shift of 45.3&deg / at 100 MHz. The star copolymer exhibited a 2- electron electrochemistry and a surface coverage of 99%. Results of Hall effect measurements showed that the star copolymer is a semiconducting material, having a conductivity of 0.7 S cm-1, in comparison to the 1.5 S cm-1 of PPy. To the best of my knowledge, these new star copolymers have not been reported in the open literature. Their properties make them potentially applicable for use in biosensors.</p>

<p>One of the most powerful aspects of conducting polymers is their ability to be nanostructured through innovative, synthetically manipulated, transformations, such as to tailor-make the polymers for specialized applications. In the exponentially increasing wide field of nanotechnology, some special attention is being paid to innovative hybrid dendrimer-core based polymeric smart materials. Star copolymers are a class of branched macromolecules having a central core with multiple linear polymer chains extending from the core. This intrinsic structural feature yields a unique 3D structure with extended conjugated linear polymer chains, resulting in star copolymers, which have higher ionic conductivities than their corresponding non-star conducting polymer counterparts. In this study an in-depth investigation was carried out into the preparation and characterization of specialized electronic &lsquo / smart materials&rsquo / . In particular, the preparation and characterization of novel conducting dendrimeric star copolymers which have a central poly(propylene imine) (PPI) dendrimer core with conducting polypyrrole (PPy) chains extending from the core was carried out. This involved, first, the preparation of a series of dendrimeric polypyrrole poly(propylene imine) star copolymers (PPI-co-PPy), using generations 1 to 4 (G1 to G4) PPI dendrimer precursors. The experimental approach involved the use of both chemical and electrochemical synthesis methods. The basic procedure involved a condensation reaction between the primary amine of a diamino functional PPI dendrimer surface and 2-pyrrole aldehyde, to afford the pyrrole functionalized PPI dendrimer (PPI-2Py). Polymerization of the intrinsically contained monomeric Py units situated within the dendrimer backbone was achieved via two distinctly different routes: the first involved chemical polymerization and the second was based on potentiodynamic oxidative electrochemical polymerization. The star copolymers were then characterized using various sophisticated analytical techniques, in-situ and ex-situ. Proton nuclear magnetic resonance spectroscopy (1HNMR) and Fourier transform infrared spectroscopy (FTIR) were used to determine the structures. Scanning electron microscopy (SEM) was used to determine the morphology. Themogravimetric analysis (TGA) was used to study the thermal stability of the prepared materials. X-ray diffraction analysis (XRD) was used to study the structural make-up of phases, crystallinity and amorphous content. Hall effect measurements were carried out to determine the electrical conductivity of the chemically prepared star copolymers. The PPI-co-PPy exhibited improved thermal stability compared to PPI-2Py, as confirmed by TGA. SEM results showed that the surface morphology of the functionalized dendrimer and star copolymer differed. The surface morphology of the chemically prepared star copolymers resembled that of a flaky, waxy material, compared to the ordered morphology of the electrochemically grown star copolymers, which resembled that of whelk-like helixes. In the case the electrochemically grown star copolymers, SEM images recorded at higher magnifications showed that the whelk-like helixes of the star copolymers were hollow tubes with openings at their tapered ends, and had an average base diameter of 2.0 &mu / m. X-ray diffraction analysis of the first generation star copolymer G1PPI-co-PPy revealed a broadly amorphous structure associated with PPy, and crystalline peaks for PPI. Cyclic voltammetry (CV), square wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) techniques were used to study and model the electrochemical reactivity of the star copolymer materials. Electrochemical impedance spectroscopy data showed that the G1PPI-co-PPy exhibited slightly higher ionic conductivity than pristine PPy in lithium perchlorate. The second generation star copolymer G2PPI-co-PPy electrochemically deposited on a platinum (Pt) electrode had a lower electrochemical charge transfer resistance compared to electrodeposited polypyrrole (PPy) on a Pt electrode, and bare Pt. The decrease in charge transfer resistance was attributed to an increase in the conjugation length of the polymer as a result of the linking of the highly conjugated PPy to the PPI dendrimer. Bode impedimetric analysis indicated that G2PPI-co-PPI was a semiconductor, with a maximum phase angle shift of 45.3&deg / at 100 MHz. The star copolymer exhibited a 2- electron electrochemistry and a surface coverage of 99%. Results of Hall effect measurements showed that the star copolymer is a semiconducting material, having a conductivity of 0.7 S cm-1, in comparison to the 1.5 S cm-1 of PPy. To the best of my knowledge, these new star copolymers have not been reported in the open literature. Their properties make them potentially applicable for use in biosensors.</p>

Theory has been used to complement experiment in the development of both drugs and delivery systems. Theoretical methods are capable of identifying the molecular basis of drug formulation inadequacies and systematic theoretical studies may suggest fruitful avenues for material modification. This thesis highlights the utility of computer-based theoretical calculations for guiding the design of drug formulations and enhancing material-drug compatibility and stability. Specifically, the present work explores the applications of semi-empirical methods and atomistic molecular dynamics (MD) simulations to enhance the performance of nano-emulsions and polymer micelle formulations for the delivery of hydrophobic drugs. This work includes three separate studies preceded by an introductory summary of available theoretical techniques. The first study evaluates the accuracy and reliability of semi-empirical methods and MD simulations as means to select suitable excipients to formulate the anti-cancer drug docetaxel in an emulsion. Here, simulations accurately predict the rank order of drug solubility in various excipients, suggesting that simulation is useful for library enrichment. In the second study, a drug conjugation approach is used to further improve the stability and solubility of docetaxel in a triglyceride-based nano-emulsion. Here, optimal conjugates are identified with computer-based theoretical calculations and conjugates with formulation-compatible moieties are synthesized. As predicted, the conjugates exhibit enhanced solubility and loading efficiency in a nano-emulsion. The goal of the third study is to rationally design a stable unimolecular star copolymer that, as a unimer, does not disassemble upon the dilution that accompanies intravenous injection. Here, MD simulation is used to systematically investigate the solution properties of differently composed star copolymers. Overall, star copolymers with a hydrophobic PCL core ≤ 2 kDa and hydrophilic PEG blocks approaching 14.6 kDa per arm are predicted to form unimolecular micelles that remain unimeric at high concentrations. The studies presented in this thesis demonstrate that theoretical approaches are useful for fast pre-screening of drug formulation materials and for the development of delivery systems and drug derivatives.

Theory has been used to complement experiment in the development of both drugs and delivery systems. Theoretical methods are capable of identifying the molecular basis of drug formulation inadequacies and systematic theoretical studies may suggest fruitful avenues for material modification. This thesis highlights the utility of computer-based theoretical calculations for guiding the design of drug formulations and enhancing material-drug compatibility and stability. Specifically, the present work explores the applications of semi-empirical methods and atomistic molecular dynamics (MD) simulations to enhance the performance of nano-emulsions and polymer micelle formulations for the delivery of hydrophobic drugs. This work includes three separate studies preceded by an introductory summary of available theoretical techniques. The first study evaluates the accuracy and reliability of semi-empirical methods and MD simulations as means to select suitable excipients to formulate the anti-cancer drug docetaxel in an emulsion. Here, simulations accurately predict the rank order of drug solubility in various excipients, suggesting that simulation is useful for library enrichment. In the second study, a drug conjugation approach is used to further improve the stability and solubility of docetaxel in a triglyceride-based nano-emulsion. Here, optimal conjugates are identified with computer-based theoretical calculations and conjugates with formulation-compatible moieties are synthesized. As predicted, the conjugates exhibit enhanced solubility and loading efficiency in a nano-emulsion. The goal of the third study is to rationally design a stable unimolecular star copolymer that, as a unimer, does not disassemble upon the dilution that accompanies intravenous injection. Here, MD simulation is used to systematically investigate the solution properties of differently composed star copolymers. Overall, star copolymers with a hydrophobic PCL core ≤ 2 kDa and hydrophilic PEG blocks approaching 14.6 kDa per arm are predicted to form unimolecular micelles that remain unimeric at high concentrations. The studies presented in this thesis demonstrate that theoretical approaches are useful for fast pre-screening of drug formulation materials and for the development of delivery systems and drug derivatives.

Philosophiae Doctor - PhD / One of the most powerful aspects of conducting polymers is their ability to be nanostructured through innovative, synthetically manipulated, transformations, such as to tailor-make the polymers for specialized applications. In the exponentially increasing wide field of nanotechnology, some special attention is being paid to innovative hybrid dendrimer-core based polymeric smart materials. Star copolymers are a class of branched macromolecules having a central core with multiple linear polymer chains extending from the core. This intrinsic structural feature yields a unique 3D structure with extended conjugated linear polymer chains, resulting in star copolymers, which have higher ionic conductivities than their corresponding non-star conducting polymer counterparts. In this study an in-depth investigation was carried out into the preparation and characterization of specialized electronic smart materials. In particular, the preparation and characterization of novel conducting dendrimeric star copolymers which have a central poly(propylene imine) (PPI) dendrimer core with conducting polypyrrole (PPy) chains extending from the core was carried out. This involved, first, the preparation of a series of dendrimeric polypyrrole poly(propylene imine) star copolymers (PPI-co-PPy), using generations 1 to 4 (G1 to G4) PPI dendrimer precursors. The experimental approach involved the use of both chemical and electrochemical synthesis methods. The basic procedure involved a condensation reaction between the primary amine of a diamino functional PPI dendrimer surface and 2-pyrrole aldehyde, to afford the pyrrole functionalized PPI dendrimer (PPI-2Py). Polymerization of the intrinsically contained monomeric Py units situated within the dendrimer backbone was achieved via two distinctly different routes: the first involved chemical polymerization and the second was based on potentiodynamic oxidative electrochemical polymerization. The star copolymers were then characterized using various sophisticated analytical techniques, in-situ and ex-situ. Proton nuclear magnetic resonance spectroscopy (1HNMR) and Fourier transform infrared spectroscopy (FTIR) were used to determine the structures. Scanning electron microscopy (SEM) was used to determine the morphology. Themogravimetric analysis (TGA) was used to study the thermal stability of the prepared materials. X-ray diffraction analysis (XRD) was used to study the structural make-up of phases, crystallinity and amorphous content. Hall effect measurements were carried out to determine the electrical conductivity of the chemically prepared star copolymers. The PPI-co-PPy exhibited improved thermal stability compared to PPI-2Py, as confirmed by TGA. SEM results showed that the surface morphology of the functionalized dendrimer and star copolymer differed. The surface morphology of the chemically prepared star copolymers resembled that of a flaky, waxy material, compared to the ordered morphology of the electrochemically grown star copolymers, which resembled that of whelk-like helixes. In the case the electrochemically grown star copolymers, SEM images recorded at higher magnifications showed that the whelk-like helixes of the star copolymers were hollow tubes with openings at their tapered ends, and had an average base diameter of 2.0 mu;m. X-ray diffraction analysis of the first generation star copolymer G1PPI-co-PPy revealed a broadly amorphous structure associated with PPy, and crystalline peaks for PPI. Cyclic voltammetry (CV), square wave voltammetry (SWV) and electrochemical impedance spectroscopy (EIS) techniques were used to study and model the electrochemical reactivity of the star copolymer materials. Electrochemical impedance spectroscopy data showed that the G1PPI-co-PPy exhibited slightly higher ionic conductivity than pristine PPy in lithium perchlorate. The second generation star copolymer G2PPI-co-PPy electrochemically deposited on a platinum (Pt) electrode had a lower electrochemical charge transfer resistance compared to electrodeposited polypyrrole (PPy) on a Pt electrode, and bare Pt. The decrease in charge transfer resistance was attributed to an increase in the conjugation length of the polymer as a result of the linking of the highly conjugated PPy to the PPI dendrimer. Bode impedimetric analysis indicated that G2PPI-co-PPI was a semiconductor, with a maximum phase angle shift of 45.3&deg; at 100 MHz. The star copolymer exhibited a 2- electron electrochemistry and a surface coverage of 99%. Results of Hall effect measurements showed that the star copolymer is a semiconducting material, having a conductivity of 0.7 S cm-1, in comparison to the 1.5 S cm-1 of PPy. To the best of my knowledge, these new star copolymers have not been reported in the open literature. Their properties make them potentially applicable for use in biosensors. / South Africa

Le sujet de cette thèse concerne l'élaboration de macromonomères, de copolymères greffés et de polymères étoiles de type 'mikto-arm'. De telles architectures macromoléculaires ont été synthétisées par la combinaison de techniques de polymérisation contrôlées/vivantes telles que la polymérisation par ouverture de cycle (par métathèse) (RO(M)P) etde chimie 'click' orthogonales : cycloaddition 1,3-dipolaireazoturealcyne catalysée au cuivre (CuAAC) et thiol-ène.Dans un premier temps, des macromonomères originaux à fonctionnalité polymérisable (oxa)norbornène portant deux chaînes macromoléculaires poly(e-caprolactone) (PCL) et/ou poly(oxyde d'éthylène) (POE) ont été synthétisés par combinaison ROP/CuAAC. Les macromonomères à fonctionnalité (oxa)norbornène avec deux chaînes PCL de masse molaire moyenne en nombre (Mn) compris entre 1400 et 5000 g/mol ont été obtenus par ROP organocatalysée. La synthèse des macromonomères POE44-b-PCLn à fonctionnalité norbornène avec un bloc PCL de longueur variable (1100 g/mol <Mn< 4100 g/mol) a été réalisée par combinaison CuAAC/ROP à partir d'un POE 2000 g/mol commercial. Ces macromonomères présentent des propriétés d'auto-assemblage dans l'eau avec une concentration micellaire critique et un rayon hydrodynamique dont les valeurs augmentent avec la longueur du bloc hydrophobe PCL. Dans un second temps, la réactivité de la fonctionnalité (oxa)norbornène des macromonomères a été étudiée par spectroscopie RMN 1H, chromatographie SEC et spectrométrie MALDI-ToF. Des copolymères greffés à squelettepoly(oxa)norbornène à haute densité de greffons PCL et POE ont été obtenus par ROMP en présence d'amorceurs de Grubbs selon la stratégie "grafting through". La thiol-ène a également été utilisée avec succès pour accéder à des copolymères étoiles de type 'mikto-arm' à base de PCL, POE poly(N-isopropylacrylamide). / The objective of the present thesis was the preparation of complex macromolecules by the combination of controlled/livingpolymerization methods such as ring-opening (metathesis) polymerization (RO(M)P) and highly efficient orthogonal chemistries: copper-catalyzed azide-alkyne coupling (CuAAC) and thiol-ene reactions.In the first part of this work, a series of well-defined structural (co)polymers containing a cycloolefin (norbornene (NB) oroxanorbornene (ONB)) functionality bearing two polymer chains including poly(ε-caprolactone) (PCL) and/or poly(ethylene oxide) (PEO) have been successfully prepared using the combination of ring-opening polymerization (ROP) and CuAAC ‘click’ chemistry. Well-defined (oxa)norbornenyl-functionalized bis-PCL polymers with PCL chain ranging from 1400 to 5000 g/mol were obtained by organocatalyst-mediated ROP. Norbornenyl-functionalized PEO-b-PCL block copolymers with PCL block in the range 1100 to 4100 g/mol were synthesized from commercially available PEO 2000 g/mol by CuAAC followed by ROP of CL. The presence of a hydrophilic PEO chain and a hydrophobic PCL chain in norbornenylfunctionalizedPEO-b-PCL copolymers gives rise to self-assembling properties in water solution. Critical micellar concentrations (CMC)are in the range of 0.08 – 0.006 g/L for copolymers with PCL chain length ranging from 10 to 36 CL units, respectively. Thecorresponding micelles show hydrodynamic diameters in range of 10 – 23 nm with low polydispersities.In the second part of this work, well-defined copolymers were used to prepare bottle-brush and (mikto-arm) star copolymersthrough reactions involving the cycloolefin functionality. On the one hand, high density grafting bottle-brush copolymerspoly(oxa)norbornene-g-bisPCL, polynorbornene-g-PEO/PCL (PNB-g-(PEO/PCL)) and PNB-b-(PNB-g-(PEO/PCL)) were achieved by ROMP according to the ‘grafting through’ strategy using Grubbs’ catalysts. On the other hand, PCL, PEO, PNIPAM-based 3-arms star, 4-arms star copolymers were obtained via radical thiol-ene reactions as demonstrated by 1H NMR, SEC and MALDI-ToF MS analysis.The high reactivity of these copolymers toward ROMP and thiol-ene reactions makes them interesting candidates in order toprepare new well-defined copolymers with controlled structures and properties through highly efficient synthetic strategies.