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Depuis plusieurs décennies, les polyesters aliphatiques (polycaprolactone (PCL), polylactide (PLA), polyglycolide (PGA)) et leurs copolymères ont été retenus pour des applications médicales grâce à leur biodégradabilité et leur biocompatibilité. Parmi leurs applications médicales, on s’intéresse ici à la délivrance des médicaments par des copolymères amphiphiles et à l’ingénierie tissulaire. Les polyesters aliphatiques souffrent cependant d’une hydrophobie importante et de l’absence de groupes fonctionnels. Pour pallier ces problèmes, plusieurs stratégies demodifications chimiques ont été proposées dans la littérature parmi lesquelles on cite : l’hydrolyse, la modification par plasma, la post-polymérisation alcyne azoture et la modification photochimique thiol-yne. Ces modifications servent à introduire des polymères hydrophiles (ex. le polyéthylène glycol) ou des groupes fonctionnels qui peuvent améliorer la biocompatibilité de polyesters. Dans ce manuscrit, on s’intéresse à la modification de la PCL et du PLA par voie photochimique thiol-yne qui présente l’avantage d’être rapide, versatile, applicable en solution comme en surface et de ne pas nécessiter l’utilisation d’un catalyseur métallique qui peut être nocif pour les applications médicales. Dans une première partie, la modification de la PCL a été faite en solution et des copolymères amphiphiles PCL-g-PEG ont été synthétisés. La stratégie de greffage « grafting to » en deux étapes a été choisie en partant de polymères commerciaux. Une optimisation des conditions de modification par voie anionique de PCL, suivi d’une photoaddition thiol-yne, nous a permis d’obtenir des copolymères avec des balances hydrophiles/hydrophobes contrôlées. L’impact de l’hydrophilie des copolymères sur la formation de nanoobjets, leurs concentrations d’aggrégation critique et leurs tailles a été étudié. L’encapsulation de curcumine comme agent anticancéreux et la cytotoxicité des nanovecteurs envers des cellules cancéreuses ont été vérifiées. Dans un second temps, ces copolymères ont été décorés par un peptide de ciblage et un peptide clivable enzymatiquement en vue de leur utilisation dans des traitements anticancéreux. L’effet biologique de ces copolymères encapsulant des principes actifs est vérifié in vitro sur des cellules cibles exprimant plus ou moins d’intégrines ou de métalloprotéases. Dans une seconde partie, des fibres PLA ont été modifiées en surface par des nanoparticules inorganiques afin de générer des hybrides covalents d’intérêts pour des applications en ingénierie tissulaire. De manière analogue aux modifications en solution, ces hybrides ont été obtenus en deux étapes par modification par voie anionique de nanofibres de PLA, suivi par un greffage covalent de nanoparticules d’oxyde de fer en suivant une stratégie photochimique thiol-yne. / For decades, aliphatic polyesters (polycaprolactone (PCL), polylactide (PLA), polyglycolide (PGA)) and their copolymers have been selected for medical applications because of their biodegradability and their biocompatibility. Among their medical applications, we are interested in drug delivery system based on amphiphilic copolymers and tissue engineering. However, aliphatic polyesters suffer from significant hydrophobicity and the absence of functional groups. To overcome these drawbacks, several strategies ofchemical modifications have been reported in literature among which we present: hydrolysis, plasma modification, post polymerization modification by copper catalyzed azide alkyne cycloaddition and thiol-yne post polymerization modification. These modifications have been used to introduce hydrophilic polymers (eg. polyethylene glycol) or functional groups on the polyester chains that can enhance the biodegradability of polyesters. In this manuscript, we are interested in modifying PCL and PLA chains by thiol-yne photochemical route. This method is rapid, versatile, applicable in solution as well as on surface and it does not require the use of a metallic catalyst which can be harmful for medical applications. First, PCL modification was done in solution and amphiphilic copolymers PCL-g-PEG were synthesized. The strategy “grafting to” in two steps has been selected starting from commercial polymers. Conditions optimization of anionic activation, followed by thiol-yne photoaddition, allowed us to obtain copolymers with controlled ratios hydrophilic/hydrophobic. The impact of copolymers hydrophilicity on nanoobjets formulation, critical micelle concentration and sizes was studied. Curcumin encapsulation as an anticancer agent and nanocarriers cytotoxicity towards cancer cells were verified. In addition, these copolymers were then decorated with a targeting peptide and an enzymatically cleavable peptide in the aim of using them in cancer treatment. The biological effect of anticancer loaded copolymer was verified in vitro on target cells expressing more or less integrins or metalloproteases. Second, PLA fibers were modified with inorganic nanoparticles and generate covalent hybrids for purposes in tissue engineering of neuronal cells. Analogously to the solution modification, these hybrids were obtained in two steps by anionic activation of PLA fibers, followed by covalent grafting of iron oxide nanoparticles according to a thiol-yne photochemical strategy.

<p dir="ltr">First, we aimed to incorporate stable tetracyanocyclopentadienide (TCCp) aromatic ani­ons into polynorbornene-based electrolytes, emphasizing controlled synthesis and properties through ring-opening metathesis polymerization (ROMP). Here, we first successfully incorporate a stable tetracyanocyclopentadienide (TCCp) aromatic anion into polynorbornene (PNb)-based elec­trolytes (PNb-TCCp) through ring-opening metathesis polymerization (ROMP) with controllable molecular weight and low polydispersity. PNb-TCCp shows a high ionic conductivity of 4.5 × 10^–5 S/cm in thin films. Due to its highly stable aromatic anion groups and favorable interactions with aromatic cations, it could improve thermal stability of doped conjugated polymers. Pairing with doped poly(3,4-ethylenedioxythiophene) (PEDOT) through salt metathesis, the generated poly ion complex PEDOT:PNb-TCCp retains its conductivity up to 180 °C.</p><p dir="ltr">Second, we aim to develop new photocatalysts for O-ATRP. We discovered a novel one-pot synthetic approach elu­cidates the formation of core-extended <i>N,N</i>′-disubstituted diaryl dihydrophenazine diradical dica­tions (DRDCs) via chemical oxidation. These DRDCs were reduced to their neutral state and found to have photocatalytic abilities, expanding the knowledge for O-ATRP photocatalysts.</p><p dir="ltr">Finally, we aim to understand the fundamental structure property relationship of the n-doped n-PBDF. The n-doped poly(benzodifurandione) (<b>n-PBDF</b>) is an n-type conducting polymer with characteristics such as high electrical conductivity, solution processability, and weathering stability. Here, we sys­tematically in­vestigate the structure property relationship on the impact of structural mod­ifications through aromatic substitution on the photophysical, electrical, and structural properties of <b>n-PBDF</b> and its oligomeric derivatives. We demonstrated that an electron donation group (methyl) raised the highest occupied molecular orbital energy level (+0.15 eV), while electron withdrawing halogens (Br and Cl) decreased the lowest unoccupied molecular orbital energy level (−0.12 eV and −0.13 eV, respectively) in the polymers. Additionally, in the both the undoped and doped oligo­meric systems, these substitutions introduce large torsion angles (<i>θ </i>> 17°), causing the material to twist significantly. Moreover, the methyl substituted polymer,<b> n-PBDF-Me</b>, was evaluated for its potential as a transparent organic conductor, due to its high optical transmittance (<i>T</i>₅₅₀> 93%). However, <b>n-PBDF-Me</b> films have significantly lower con­ductiv­ity than <b>n-PBDF</b> (0.40 S/cm vs 1330 S/cm) at similar thickness.</p>

Two diverse projects illustrate the application of various materials characterization techniques to investigate the structure and properties of nanostructured functional materials formed in both bulk as well as in solutions. In the first project, ordered magnetic nanostructures were formed within polymer matrix by novel metallopolymers. The novel metal-functionalized block copolymers (BCPs) enabled the confinement of cobalt metal ions within nanostructured BCP domains, which upon simple heat treatment resulted in room temperature ferromagnetic (RTFM) materials. On the contrary, cobalt functionalized homopolymer having similar chemical structure and higher loading of metal-ion are unstructured and exhibited superparamagnetic (SPM) behavior at room temperature. Based on a series of detailed investigations, using various materials characterization techniques, it was hypothesized that the SPM cobalt particles within BCP microdomains exhibited a collective behavior due to increased dipolar interactions between them under the nanoconfinement of cylindrical domains in BCP, resulting in RTFM behavior. On contrary, the same SPM cobalt particles formed within homopolymer, without any confinement exhibited SPM behavior either due to lack of interactions or random interactions between them. To further support this hypothesis, a series of BCPs were prepared in which the BCP morphology was varied between the cylindrical, lamellar, and inverted cylindrical phases and their magnetic properties were compared. All these BCPs, which are nanostructured, exhibited RTFM behavior, further supporting the proposed hypothesis. Different dimensionality or degree of nanoconfinement in BCP morphologies affected the magnetization reversal processes in these BCPs, yielding different macroscopic magnetic properties. Most strongly constrained cylindrical morphology has shown best magnetic properties (highest coercivity) among other BCP morphologies. Inverted cylindrical morphology, in which a 3-D matrix is confined between the non-magnetic cylinders, had second highest and lamellar morphology with least confinement among BCPs, exhibited lowest coercivity. The proposed hypothesis was further tested by systematically varying the dipolar interactions between the SPM cobalt nanoparticles by reducing the density of cobalt within the cylindrical domains and varying the dimensions of the cylindrical domains (i.e. diameter). A series of novel ferrocene-cobalt containing block copolymers were developed and cobalt density within the cylindrical domains of BCP was varied by changing the chemical composition of the metal functionalized block. Further, the diameter of the cylindrical domains was varied by varying the molecular weight of the cobalt-containing BCPs. These studies allowed us to understand the fundamental correlations between the self-assembled nanostructures and their macroscopic magnetic properties. In the second part of the thesis, a novel amphiphilic block copolymer (ABC), composed of a hydrophilic zwitterionic block and a hydrophobic PS block, was synthesized by ROMP. The formation of zwitterionic vesicles in an ionic liquid, as well as in PBS buffer, was confirmed by TEM and DLS characterization. The dispersion of vesicles within ionic liquid enabled the usage of conventional, room temperature TEM to visualize them in their solution state. This technique of materials characterization could be extended for the visualization of other hydrophilic soft matter.

A poluição de corpos d´água por metais pesados é um problema mundial, mas particularmente importante em países que apresentam atividades intensas de mineração, como o Brasil. Os contaminantes, de maneira especial aqueles conhecidos como metais pesados, podem apresentar toxicidade altíssima, como é o caso do cádmio, chumbo e outros. Por esse motivo, os efluentes industriais, quando não devidamente tratados, ainda são uma grande fonte de contaminação do ecossistema que vivemos. Diante dessa atual situação, esforços para o aprimoramento de técnicas de remoção de cátions de metais pesados da água são necessárias e podem ter impacto positivo na Saúde Pública e em outras áreas. Portanto, como solução viável e alternativa para o que já se é feito, o presente projeto propõe a produção e estudo do uso de materiais poliméricos com propriedades distintas para captação de metais pesados de soluções aquosas. Para a síntese dos polímeros foram usadas técnicas de polimerização via radical livre, e posterior hidrólise para geração de copolímeros, com o intuito de aperfeiçoar a capacidade de remoção. Os polímeros tiveram como base a metacrilamida que tem a presença do grupo funcional amida e, após hidrólise, a geração de unidade de ácido metacrílico com presença do grupo funcional de ácido carboxílico, ambos os grupos quando combinados possuem uma elevada capacidade de adsorção de cátions. Paralelamente foi aperfeiçoado um sistema de remoção de cátions de solução aquosa usando polímeros confinados em membranas de diálise. A influência da massa molar média, do grau de hidrólise e da presença do grupo funcional de ácido carboxílico foi estudada. Por fim, foi realizado um estudo da capacidade máxima de remoção de Cu(II), em que os parâmetros temperatura, pH da solução, velocidade e tempo de agitação foram fixados. A capacidade máxima de remoção dos íons de Cu(II) variou entre 1,55-1,71 mmol/g para os copolímeros sintetizados e hidrolisados em laboratório, para o copolímero comercial obteve-se um valor de 2,17 mmol/g, e para o copolímero sintetizado diretamente por PRL a partir dos monômeros metacrilamida e ácido metacrílico a capacidade de máxima de captação foi de 3,87 mmol/g , a partir dos resultados foi possível observar uma relação positiva entre a massa molar média das cadeias e a capacidade de ligação aos cátions metálicos. Foi comprovado também que a presença do ácido metacrílico na cadeia polimérica é fundamental para o aumento da capacidade de ligação do cobre. A partir desses estudos foi possível concluir que os polímeros sintetizados e imobilizados em sacos de diálise são eficientes na remoção de íons de Cu(II), Cd(II) e Pb(II) de soluções aquosas, sendo que o estudo da capacidade de remoção dos outros dois cátions Cd (II) e Pb (II) são perspectivas futuras para estudo. No trabalho, destaca-se, além da eficiência, a praticidade do uso do método desenvolvido. / The water pollution by heavy metals is a worldwide problem, but particularly important in countries with intensive mining activities, such as Brazil. Contaminants, especially those known as heavy metals, such as cadmium, lead and others, may have very high toxicity. For this reason, industrial effluents, when not properly treated, are still a big source of contamination of the ecosystem we live in. In order to deal with this current situation, it is necessary to improve metallic cation removal techniques from water what may have a positive impact on Public Health and other areas. Therefore, as a feasible and alternative solution to current metal removal techniques, the present project proposes the production and study of polymeric materials based on partially hidrolised polymethacrylamide with different characteristic for the capture of heavy metals in aqueous solutions. Free radical polymerization techniques were used to synthesize the polymers followed by hydrolysis for the copolymers generation, in order to improve the removal capacity. The amide functional group and, after hydrolysis, the carboxylic group when combined have a high cation adsorption capacity. At the same time, a cation removal system that uses polymers entrapped in a dialysis membrane was improved. The influence of the average molar mass, degree of hydrolysis and the presence of the carboxylic acid functional group was studied. Finally, a study of the maximum Cu (II) removal capacity was carried out, in which the parameters of temperature, solution pH, speed and agitation time were fixed. The maximum removal capacity of Cu (II) ions ranged from 1.55-1.71 mmol/g for the copolymers synthesized and hydrolyzed in the laboratory, the commercial copolymer yielded a value of 2.17 mmol/g, and for the copolymer directly synthesized by PRL from the methacrylamide and methacrylic acid monomers the maximum capacity was 3.87 mmol/g. From the results it was possible to observe a positive relation between the average molar mass of the chains and the ability to connect to the metal cations. It has also been proven that the presence of methacrylic acid in the polymer chain is fundamental for increasing the copper bonding capacity. From these studies it was possible to conclude that both polymers synthesized and immobilized in dialysis bags are efficient in the removal of Cu (II), Cd (II) and Pb (II) ions from aqueous solutions, and the study of the ability to remove the other two cations Cd (II) and Pb (II) are perspectives to future studies. In the work, it is highlighted, besides the efficiency, the convenience of the developed method.

This thesis begins with a brief analysis of the synthetic methodologies utilized in polymer science. A conclusion is drawn inferring that upper limits in molecular design are inevitable, arising as a direct consequence of the predominance of covalent strategies in the field. To address these concerns, the universal polymer backbone (UPB) concept has been hypothesized. A UPB has been defined as any copolymer, side-chain functionalized with multiple recognition elements that are individually capable of forming strong, directional, and reversible non-covalent bonds. Non-covalent functionalization of these scaffolds can lead to the formation of a multitude of new polymer structures, each stemming from a single parent or universal polymer backbone. To prepare such a UPB, isomerically pure exo-norbornene esters containing either a PdII SCS pincer complex or a diaminopyridine residue were synthesized, polymerized, and copolymerized via ROMP. All polymerizations were living under mild reaction conditions. Kinetic studies showed that the kp values are highly dependent upon the isomeric purity but completely independent of the terminal recognition units. Non-covalent functionalization of these copolymers was accomplished via 1) directed self-assembly, 2) multi-step self- assembly, and 3) one-step orthogonal self-assembly. This system shows complete specificity of each recognition motif for its complementary unit with no observable changes in the association constant upon functionalization. To explore potential applications of this UPB concept, random terpolymers possessing high concentrations of pendant alkyl chains and small amounts of recognition units were synthesized. Non-covalent crosslinking using a directed functionalization strategy resulted in dramatic increases in solution viscosities for metal crosslinked polymers with only minor changes in viscosity for hydrogen bonding motifs. The crosslinked materials were further functionalized via self-assembly by employing the second recognition motif, which gave rise to functionalized materials with tailored crosslinks. This non-covalent crosslinking/functionalization strategy could allow for rapid and tunable materials synthesis by overcoming many difficulties inherent to the preparation of covalently crosslinked polymers. Finally, the current status of the UPB concept is reviewed and methodological extensions of the concept are suggested. Evaluation of how UPBs may be used to optimize materials and their potential use in fabricating unique electro-optical materials, sensors, and drug delivery vesicles are explored.

A poluição de corpos d´água por metais pesados é um problema mundial, mas particularmente importante em países que apresentam atividades intensas de mineração, como o Brasil. Os contaminantes, de maneira especial aqueles conhecidos como metais pesados, podem apresentar toxicidade altíssima, como é o caso do cádmio, chumbo e outros. Por esse motivo, os efluentes industriais, quando não devidamente tratados, ainda são uma grande fonte de contaminação do ecossistema que vivemos. Diante dessa atual situação, esforços para o aprimoramento de técnicas de remoção de cátions de metais pesados da água são necessárias e podem ter impacto positivo na Saúde Pública e em outras áreas. Portanto, como solução viável e alternativa para o que já se é feito, o presente projeto propõe a produção e estudo do uso de materiais poliméricos com propriedades distintas para captação de metais pesados de soluções aquosas. Para a síntese dos polímeros foram usadas técnicas de polimerização via radical livre, e posterior hidrólise para geração de copolímeros, com o intuito de aperfeiçoar a capacidade de remoção. Os polímeros tiveram como base a metacrilamida que tem a presença do grupo funcional amida e, após hidrólise, a geração de unidade de ácido metacrílico com presença do grupo funcional de ácido carboxílico, ambos os grupos quando combinados possuem uma elevada capacidade de adsorção de cátions. Paralelamente foi aperfeiçoado um sistema de remoção de cátions de solução aquosa usando polímeros confinados em membranas de diálise. A influência da massa molar média, do grau de hidrólise e da presença do grupo funcional de ácido carboxílico foi estudada. Por fim, foi realizado um estudo da capacidade máxima de remoção de Cu(II), em que os parâmetros temperatura, pH da solução, velocidade e tempo de agitação foram fixados. A capacidade máxima de remoção dos íons de Cu(II) variou entre 1,55-1,71 mmol/g para os copolímeros sintetizados e hidrolisados em laboratório, para o copolímero comercial obteve-se um valor de 2,17 mmol/g, e para o copolímero sintetizado diretamente por PRL a partir dos monômeros metacrilamida e ácido metacrílico a capacidade de máxima de captação foi de 3,87 mmol/g , a partir dos resultados foi possível observar uma relação positiva entre a massa molar média das cadeias e a capacidade de ligação aos cátions metálicos. Foi comprovado também que a presença do ácido metacrílico na cadeia polimérica é fundamental para o aumento da capacidade de ligação do cobre. A partir desses estudos foi possível concluir que os polímeros sintetizados e imobilizados em sacos de diálise são eficientes na remoção de íons de Cu(II), Cd(II) e Pb(II) de soluções aquosas, sendo que o estudo da capacidade de remoção dos outros dois cátions Cd (II) e Pb (II) são perspectivas futuras para estudo. No trabalho, destaca-se, além da eficiência, a praticidade do uso do método desenvolvido. / The water pollution by heavy metals is a worldwide problem, but particularly important in countries with intensive mining activities, such as Brazil. Contaminants, especially those known as heavy metals, such as cadmium, lead and others, may have very high toxicity. For this reason, industrial effluents, when not properly treated, are still a big source of contamination of the ecosystem we live in. In order to deal with this current situation, it is necessary to improve metallic cation removal techniques from water what may have a positive impact on Public Health and other areas. Therefore, as a feasible and alternative solution to current metal removal techniques, the present project proposes the production and study of polymeric materials based on partially hidrolised polymethacrylamide with different characteristic for the capture of heavy metals in aqueous solutions. Free radical polymerization techniques were used to synthesize the polymers followed by hydrolysis for the copolymers generation, in order to improve the removal capacity. The amide functional group and, after hydrolysis, the carboxylic group when combined have a high cation adsorption capacity. At the same time, a cation removal system that uses polymers entrapped in a dialysis membrane was improved. The influence of the average molar mass, degree of hydrolysis and the presence of the carboxylic acid functional group was studied. Finally, a study of the maximum Cu (II) removal capacity was carried out, in which the parameters of temperature, solution pH, speed and agitation time were fixed. The maximum removal capacity of Cu (II) ions ranged from 1.55-1.71 mmol/g for the copolymers synthesized and hydrolyzed in the laboratory, the commercial copolymer yielded a value of 2.17 mmol/g, and for the copolymer directly synthesized by PRL from the methacrylamide and methacrylic acid monomers the maximum capacity was 3.87 mmol/g. From the results it was possible to observe a positive relation between the average molar mass of the chains and the ability to connect to the metal cations. It has also been proven that the presence of methacrylic acid in the polymer chain is fundamental for increasing the copper bonding capacity. From these studies it was possible to conclude that both polymers synthesized and immobilized in dialysis bags are efficient in the removal of Cu (II), Cd (II) and Pb (II) ions from aqueous solutions, and the study of the ability to remove the other two cations Cd (II) and Pb (II) are perspectives to future studies. In the work, it is highlighted, besides the efficiency, the convenience of the developed method.

Un (bio)capteur classique est principalement composé de deux éléments essentiels : une couche réceptrice sensible à l’analyte à laquelle on s’intéresse et un transducteur qui permet de convertir une stimulation chimique / biologique en un signal physique mesurable. Dans le cas idéal, un capteur ne doit pas nécessiter de marquage de la cible, doit posséder de très grandes sensibilité et sélectivité envers elle, ne requiert qu’une faible quantité de cette dernière et doit présenter un temps de réponse très court. Au vu de ces critères, les microsystèmes électromécaniques (MEMS) sont des candidats très prometteurs dans le développement de capteurs. Les polymères fonctionnels, tels que les polymères à empreinte moléculaire (MIPs), sont une approche très intéressante dans l’utilisation des MEMS car ils peuvent être intégrés dans des technologies existantes de MEMS à base de silicium ou complètement remplacer ces technologies. Le but de cette thèse porte sur le développement d’un capteur MEMS composé de polymères (fonctionnels). Un chapitre initial (chapitre 2) introduit des nouveaux systèmes de fabrication de polymères fonctionnels. Des biopuces composées de MIPs imprimés par jet d’encre sont présentées ainsi qu’une technique basée sur la polymérisation radicale contrôlée qui permet le dépôt d’un fin enrobage de MIPs sur des microstructures. La deuxième partie de ce chapitre présente la fabrication de polymères à empreinte moléculaire par stéréolithographie deux-photons, qui peut être vue comme une extension de l’impression 3D. Afin d’illustrer cette technologie de prototypage rapide, deux capteurs composés de MIPs sont présentés : un capteur à grille de diffraction et un capteur en microlevier. Les deux principaux chapitres de ce manuscrit (chapitre 3 et 4) se focalisent sur le développement d’un nouveau concept de fabrication pour les capteurs MEMS. Ce concept est basé sur la polymérisation d’une poutre à fort ratio de forme à l’extrémité d’une fibre optique de télécommunication. Cette poutre a été mise en vibration à sa résonnance et a ainsi pu être utilisée comme un capteur à base de levier. Le capteur en polymère a permis l’intégration de MIPs comme élément récepteur et la reconnaissance sélective de l’antibiotique enrofloxacine. De plus, un nouveau système de mesure intégré est présenté dans le chapitre 4. Ce système de mesure intègre la fibre optique en guidant un rayon laser à travers elle ainsi qu’à travers le levier qui y est attaché.Le rayon lumineux sortant est ensuite focalisé sur une photodiode sensible à la position du rayon lumineux, permettant ainsi la mesure du spectre de résonance de la poutre en polymère. Ce système de mesure est caractérisé et ses performances sont présentées au travers de la détection de masse du levier en polymère et de mesures faites en milieu liquide. / A classical (bio)sensor consists of two key components: A receptor layer that detects the analyte of interest and the transducer which converts the chemical / biological stimuli into a physical measurable signal. Ideally a sensor is label-free, highly sensitive and selective towards the target, requires low sample amount and shows a fast response time. Regarding these criteria microelectromechanical systems (MEMS) offer great potential for the sensor development. One interesting approach for this development are functional polymer materials, such as molecularly imprinted polymers (MIPs), that can be either integrated to existing MEMS based on silicon or completely replace the silicon technology. The emphasis of this thesis is focused on the development of a MEMS sensor based on (functional) polymers. In an initial chapter (chapter 2) new fabrication schemes for functional polymers are introduced. Inkjet-printed biochips based on MIPs are presented and a technique based on controlled radical polymerization is shown that allows the deposition of thin MIP shells on a microfabricated pattern. In the second part of this chapter the fabrication of molecularly imprinted polymers by two-photon stereolithography is shown which can be seen as an extension of 3dimensional printing. As possible application of this rapid prototyping technology two sensors based on MIPs are introduced a diffraction grating sensor and a microcantilever sensor. The two main chapters of this manuscript (chapter 3 and chapter 4) report the development of a new fabrication concept for MEMS sensors. It is based on the polymerization of a high aspect ratio beam on the extremity of an optical telecommunication fiber which was actuated at resonance and thus could be used as a cantilever sensor. The polymer sensor allowed the integration of MIPs as sensing element and the selective recognition of the antibiotic enrofloxacin. Furthermore, is a new, integrated read-out scheme presented in chapter 4. This read-out scheme integrates the optical fiber, by guiding a probe laser beam through it and attached cantilever beam. The output light beam is then focused on a position sensitive photodiode and thus enabled to monitor the resonance spectra of the polymer beam. The read-out scheme is characterized and its performance is shown by demonstrating the mass sensitivity of the polymeric cantilever beam and by measurements in liquid environments.

This thesis contains investigations in the area of polymers herein propellants binders are modified functionally to meet the requirements of future energetic propellants. Chapter 1 contains a broad introduction to the area of recent advances in solid propellants and the numerous applications of ‘Click Chemistry’. Chapters 2 details the materials, characterization tools and the experimental techniques employed for the studies. This is followed by Chapter 3, 4, and 5 which deals with functional modification of various propellants binders, their characterisation and evaluation in propellant formulations. Chapter 6 details with the thermal decomposition of diazides and its reaction with alkenes. The advent of modern rockets has opened a new era in the history of space exploration as well as defence applications. The driving force of the rocket emanates from the propellant – either solid or liquid. Composite solid propellants find an indispensable place, in today’s rockets and launch vehicles because of the inherent advantages such as high reliability, easy manufacturing, high thrust etc. The composite propellant consisting of inorganic oxidiser like ammonium perchlorate, (AP), ammonium nitrate (AN) etc), metallic fuel (aluminium powder, boron etc) and polymeric fuel binder (hydroxyl terminated polybutadiene-HTPB, polybutadiene-acrylic acid-acrylonitrile PBAN, glycidyl azide polymer (GAP), polyteramethylene oxide (PTMO) etc. is used in igniters, boosters, upper stage motors and special purpose motors in large launch vehicles. Large composite solid propellant grains or rocket motors in particular, demand adequate mechanical properties to enable them to withstand the stresses imposed during operation, handling, transportation and motor firing. They should also have a reasonably long ‘potlife’ to provide sufficient window for processing operations such as mixing and casting which makes the selection of binder with appropriate cure chemistry more challenging. In all composite solid propellants currently in use, polymers perform the role of a binder for the oxidiser, metallic fuel and other additives. It performs the dual role of imparting dimensional stability to the composite, provides structural integrity and good mechanical properties to the propellant besides acting as a fuel to impart the required energetics. Conventionally, the terminal hydroxyl groups in the binders like GAP, PTMO and HTPB are reacted with diisocyanates to form a polyurethane network, to impart the necessary mechanical properties to the propellant. A wide range of diisocyantes such as tolylene diisocyanate (TDI) and isophorone diisocyanate (IPDI) are used for curing of these binders. However, the incompatability of isocyanates with energetic oxidisers like ammonium dinitramide (ADN), hydrazinium nitroformate (HNF), short ‘potlife’ of the propellant slurry and undesirable side reactions with moisture are limiting factors which adversely affect the mechanical properties of curing binders through this route. The objective of the present study is to evolve an alternate approach of curing these binders is to make use of the 1,3 dipolar addition reactions between azide and alkyne groups which is a part of ‘Click chemistry’. This can be accomplished by the reaction of azide groups of GAP with triple bonds of alkynes and reactions of functionally modified HTPB/PTMO (azide/alkyne) to yield 1,2,3 -triazole based products. This offers an alternate route for processing of solid propellants wherein, the cured resins that have improved mechanical properties, better thermal stability and improved ballistic properties in view of the higher heat of decomposition resulting from the decomposition of the triazole groups. GAP is an azide containing energetic polymer. The azide groups can undergo reaction with alkynes to yield triazoles. In, Chapter 3 the synthesis and characterisation of various alkynyl compounds including bis propargyl succinate (BPS), bis propargyl adipate (BPA), bis propargyl sebacate (BPSc.) and bis propargyl oxy bisphenol A (BPB) for curing of GAP to yield triazoles networks are studied. The mechanism of the curing reaction of GAP with these alkynyl compounds was elucidated using a model compound viz. 2-azidoethoxyethane (AEE). The reaction mechanism has been analysed using Density Functional Theory (DFT) method. DFT based theoretical calculations implied marginal preference for 1, 5 addition over the 1, 4 addition for the uncatalysed cycloaddition reaction between azide and alkyne group. The detailed characterisation of these systems with respect to the cure kinetics, mechanical properties, dynamic mechanical behaviour and thermal decomposition characteristics were done and correlated to the structure of the network. The glass transition temperature (Tg), tensile strength and modulus of the system increased with crosslink density which in turn is, controlled by the azide to alkyne molar stoichiometry. Thermogravimetic analysis (TGA) showed better thermal stability for the GAP-triazole compared to GAP based urethanes. Though there have been a few reports on curing of GAP with alkynes, it is for the first time that a detailed characterisation of this system with respect to the cure kinetics, mechanical, dynamic mechanical, thermal decomposition mechanism of the polymer is being reported. To extent the concept of curing binders through 1,3 dipolar addition reaction, the binder HTPB as chemically transformed to propargyloxy carbonyl amine terminated polybutadiene (PrTPB) with azidoethoxy carbonyl amine terminated polybutadiene (AzTPB) and propargyloxy polybutadiene (PTPB). Similarly, PTMO was convnerted to propargyloxy polytetramethylene oxide (PTMP). Triazole-triazoline networks were derived by the reaction of the binders with alkyne/azide containing curing agents. The cure characteristics of these polymers (PrTPB with AzTPB, PTPB with GAP and PTMP with GAP) were studied by DSC. The detailed characterisations of the cured polymers for were done with respect to the, mechanical, dynamic mechanical behaviour and thermal decomposition characteristics were done. Propellant level studies were done using the triazoles derived from GAP, PrTPB-AzTPB, PTPB and PTMP as binder, in combination with ammonium perchlorate as oxidiser. The propellants were characterised with respect to rheological, mechanical, safety, as well as ballistic properties. From the studies, propellant formulations with improved energetics, safety characteristics, processability and mechanical properties as well defect free propellants could be developed using novel triazole crosslinked based binders. Chapter 6, is aimed at understanding the mechanism of thermal decomposition of diazido compounds in the first section. For this, synthesis and characterisation of a diazido ester 1,6 –bis (azidoacetoyloxy) hexane (HDBAA) was done. There have been no reports on the thermal decomposition mechanism of diazido compounds, where one azide group may influence the decomposition of the other. The thermal decomposition mechanism of the diazido ester were theoretically predicted by DFT method and corroborated by pyrolysis-GC-MS studies. In the second section of this chapter, the cure reaction of the diazido ester with the double bonds of HTPB has been investigated. The chapter 6B reports the mechanism of Cu (I) catalysed azide-alkene reaction validated using density functional theory (DFT) calculations in isomers of hexene (cis-3-hexene, trans-3-hexene and 2-methy pentene: model compound of HTPB) using HDBAA. This the first report on an isocyanate free curing of HTPB using an azide. Chapter 7 of the thesis summarizes the work carried out, the highlights and important findings of this work. The scope for future work such as development of high performance eco-friendly propellants based on triazoles in conjunction with chlorine-free oxidizer like ADN, synthesis of compatible plasticisers and suitable crosslinkers have been described. This work has given rise to one patent, three international publications and four papers in international conferences in the domain.