The diploma thesis is focused on the preparation and optimization of molecularly imprinted polymers (MIP) selective for chymotrypsinogen A as well as on the use of these MIP as recognition entities in the sensor. MIP was prepared by suspension polymerization using a mixture of functional methacrylate-based monomers. Prepared MIP was optimized (e.g. binding properties, selectivity and isolation of chymotrypsinogen from a complex matrix of human breath) by capillary electrophoresis with fluorescence detection ( = 532 nm). Finally, the combination of MIP with quartz microbalances was demonstrated as a promising sensor for the detection of proteins from human breath condensate.

No description available.

Thesis (MScEng)-- Stellenbosch University, 2013. / ENGLISH ABSTRACT: The simplified Perturbed-Chain Statistical Associating Fluid Theory (sPC-SAFT) is characterised by the dual advantages of decreased computational intensity, while remaining accurate for a variety of systems. Vapour-liquid equilibrium data are used to generate equation of state parameters. However, incorporating monomer fraction data into the parameter regression has long been advocated as a good, or even preferred, practice. Therefore, the monomer fraction data of dilute alcohol-acetone systems were analysed in this study. A small stainless steel sample vessel was constructed with temperature control, manual pressure control and a mechanism for liquid phase analysis via infrared spectroscopy. The performance of the spectrometer was verified by comparison with the ethanol – n-hexane data of von Solms et al. (2007), after which new monomer fraction data were obtained for dilute solutions (between 0.01 and 1.5 mol%) of methanol, ethanol, 1-propanol and 2-propanol in acetone near 23 °C. For dilute alcohol-acetone systems it was found that the propanols had the highest monomer fractions, and methanol the lowest. With increasing alcohol concentration, the monomer fractions decreased exponentially to values of 0.4 and 0.1 for methanol and the other alcohols respectively. The excess availability of hydrogen bond acceptors in the mixtures explains the equivalency observed for ethanol, 1-propanol and 2-propanol. For dilute acetone-alcohol systems it was found that, especially for methanol and ethanol, there was a pronounced trend towards acetone monomer fractions of 1 at infinite dilution. For the acetone – 2-propanol system, a previously unrecorded monomer peak was observed and quantified. Acetone monomer fractions tended to decrease as alcohol chain-length increased, showing that acetone could more easily penetrate the hydrogen bond network of the solvent when the solvent-solvent bonds were weaker. Monomer fraction data were compared to predictions for the sPC-SAFT scheme and parameters combinations published in the literature. The experimental data were accurately modelled using modified association parameters such that the solute associates strongly (εAB≈103 κ≈1), while the solvent parameters were decreased (εAB≈102 κ≈10˗3) to give a weakened solvent association effect. The difficulty for the dilute solute in penetrating the solvent bonding network appeared to be similar to the hydrophobic effect. Two new association schemes were proposed for acetone, assigning a single (N) or two (2N) negative association sites to represent the oxygen valence electron pairs. These schemes showed relative success in modelling acetone as the solvent in the mixture, while not being able to predict acetone monomer fractions when acetone was the solute. For dilute acetone-alcohol systems, the data were best described using the 2B model for acetone, while the best choice of scheme for the alcohol varied from system to system. For dilute alcohol-acetone mixtures it was generally found that a 2B-N model (with modified association parameters) provided the best fit to those experimental data. Accurate modelling below 0.1 mol% was difficult to attain with average errors decreasing to the order of 10% when this area was excluded. In this highly dilute region, not one of the models could describe the rapid change in (monomer fraction) gradient sufficiently while simultaneously offering accurate predictions over the entire experimental range. / AFRIKAANSE OPSOMMING: Die sPC-SAFT of simplified Perturbed-Chain Statistical Associating Fluid Theory toestandsvergelykings word wyd gebruik as gevolg van sy goeie akkuraatheid vir ‘n wye reeks sisteme, ten spyte van verminderde berekeningsintensiteit. Die parameters vir dié toestandsvergelyk word afgelei van faseewewig data, maar monomeer fraksie data word voorgestel vir die verbetering van (veral) die assosiasie parameters. Ten opsigte hiervan, was alkohol-asetoon sisteme bestudeer en hul monomeer fraksies gemeet. ‘n Staal reaktor was ontwerp (met ‘n temperatuurbeheerstelsel sowel as drukbeheer) om vloeistof monsters voor te berei vir analise d.m.v. infrarooi-spektroskopie. Die akkuraatheid van die eksperimentele apparaat is bewys deur nabootsing van etanol – n-heksaan data van von Solms et al. (2007), waarna nuwe monomeer fraksie data gegenereer is vir verdunde mengsels (0.01 tot 1.5 mol%) van metanol, etanol, 1- en 2-propanol met asetoon by 23 °C. Metanol monomeer fraksies het eksponensieël afgeneem na 0.4, terwyl etanol en propanol fraksies afgeneem het na ‘n gemene waarde van ongeveer 0.1. Hierdie tendens word toegeskryf aan ‘n oormaat van toeganklike waterstofbindingontvangers in hierdie mengsels. Vir verdunde asetoon-alkohol sisteme is daar ‘n tendens, (veral vir verdunnings met metanol en etanol) vir die monomer fraksies om te neig na 1 by oneindige verdunning. ‘n Monomeer piek is ook waargeneem vir die asetoon – 2-propanol sisteem. Hierdie piek is nie voorheen gesien in ander studies nie en dit is ook die eerste keer wat sulke data gekwantifiseer is. Daar is bevind dat asetoon monomeer fraksies afneem soos alkohol kettinglengte toeneem. Die gegenereerde monomeer fraksie data word vergelyk met verskeie sPC-SAFT parameterstelle vanuit die literatuur. Oor die algemeen, is die beraamde fraksie veel hoër as die eksperimentele data wanneer die 2B/3B/2C skemas met ‘n nie-assosiërende asetoon molekuul gemodelleer word. Wanneer die 2B parameters van von Solms et al. (2004) gebruik word, toon die beraming ‘n drastiese onderskatting van die data. Om ‘n akkurate beraming van die monomeer fraksie data te kry, moet die assosiasie parameters van die opgeloste stof vermeerder word (met εAB≈103 κ≈1) terwyl die oplosmiddel s’n drasties verswak moet word (met εAB≈102 κ≈10-3). Hierdie patroon kan vergelyk word met die hidrofobiese effek waar die kragte binne die oplosmiddel ‘n netwerk vorm wat die opgeloste stof uitstoot. Twee nuwe assosiasie skemas word ook voorgestel vir asetoon waar onderskeidelik een (N) en twee (2N) negatiewe sones, wat die valenselektroonpare op die suurstofatoom voorstel, aan asetoon geheg word. Hierdie twee skemas het relatiewe sukses getoon in die modellering van verdunde alkohol-asetoon sisteme terwyl dit ‘n swak beskrywing van die verdunde asetoon-alkohol mengsels voorspel het. ‘n Gewysigde 2B asetoon skema gee ‘n goeie beskrywing van die eksperimentele data. In hierdie geval, is die keuse van alkohol skema minder belangrik, terwyl die waardes van die assosiasie parameters verminder moet word. Vir verdunde alkohol-asetoon mengels word daar bevind dat ‘n 2B-N model met nuwe assosiasie parameters die beste passing van die eksperimentele data gee. Daar was ook bevind dat die modelle se akkuraatheid drasties afneem (met fout vermeerdering in die orde van 10%) wanneer die konsentrasie van die opgeloste stof minder as 0.1 mol% is.

L'étude de la fusion par confinement inertiel du mélange deutérium + tritium (DT) est une problématique depuis longtemps abordée par le CEA. Les expérimentations liées à cette thématique, effectuées prochainement au sein du laser mégajoule (LMJ), nécessitent l'utilisation de matériaux aux propriétés particulières. Cela concerne entre autres les mousses de polymères (aérogels organiques) composant les cibles de pré-ignition. De tels matériaux doivent notamment associer une importante porosité à une forte teneur métallique (1% atomique de Ti), tout en étant compatible avec les procédés de préparation utilisés. Dans ce contexte, un nouveau complexe polymérisable de titane a été préparé et caractérisé par plusieurs techniques d'analyses. Ce monomère dispose d'une forte teneur métallique tout en présentant une bonne stabilité vis-à-vis l'air et l'humidité. Sa copolymérisation radicalaire selon différentes conditions suivie d'un séchage en condition supercritique a permis l'obtention d'une série d'aérogels organiques. Les caractérisations chimiques (RMN, infrarouge et analyses élémentaires) ainsi que les caractérisations structurales (MEB-EDS, MET, mesure des isothermes d'adsorption/désorption de l'azote et SAXS) de ces polymères ont permis de valider les critères mentionnés dans notre cahier des charges. En outre, ces données ont permis de déterminer les mécanismes de formation de la nanostructure des mousses. / Inertial Confinement Fusion (ICF) is a technique widely studied by the French atomic commission (CEA). Experiments will be performed within the Laser Megajoule (LMJ). They require innovative materials like organic aerogels that constitute laser targets. Such polymeric material must provide both a high porosity and a significant titanium percentage (1 atom %). Moreover, the monomers developed must be compatible with the synthesis procedure already in use. According to these specifications, a new polymerizable titanium complex was synthesized and fully characterized. This air and moisture-stable monomer provides a high metal percentage. Its free-radical cross-linked copolymerization affords several titanium-containing polymers. These gels were dried under supercritical conditions and organic aerogels were obtained. The chemical compositions of these materials were investigated by NMR, IR and elemental analysis while their structure was characterized by MEB-EDS, MET, N2 adsorption/desorption isotherms measurements and SAXS. The data collected fit the specification requirements. Moreover, the mechanisms responsible of the foam nanostructure formation were discussed.

Les objectifs du travail présenté ici sont de comprendre les procédés de formulation des gouttelettes et des particules afin de faire des hybrides polymère-polymère de qualité en dispersions aqueuses et d’utiliser notre compréhension fondamentale de ces procédés pour : 1. Augmenter le taux de conversion de(s) monomère(s) autant que possible. 2. Comprendre l’impact de ces procédés sur les propriétés des films hybrides. Des cas particuliers ont été étudiés dans des conditions commercialement viables (taux de solide de 50% en masse) basés sur deux systèmes appelés alkyde-acryliques et polyuréthane-acrylique. La préparation des miniémulsions, la polymérisation en miniémulsion et la caractérisation des latex hybrides, l’incorporation chimique d’alkyde et de polyuréthane dans les monomères acryliques ont été étudiés en détails. Nous sommes parvenus à synthétiser et caractériser des latex hybrides avec de haut taux de solides (50% en masse) composés de particules de 100nm de diamètre utilisables dans des applications de revêtement et d’adhésifs / The objectives of work presented in this thesis are to understand droplet and particle formulation processes in order to make useful polymer-polymer hybrids in aqueous dispersions and use our fundamental understanding of these processes to: 1. Improve monomer conversion as much as possible. 2. Understand impact of these processes on hybrid film properties. Specific case studies of interest under commercially feasible conditions (i.e. solids content of 50wt %) were done based on two systems namely alkyd-acrylic and polyurethane-acrylic. Miniemulsification, miniemulsion polymerisation and characterisation of hybrid latex, chemical incorporation of alkyd and polyurethane to acrylic monomers were studied in detail. We have been able to successfully synthesise and characterise hybrid latex of about 100nm in particle diameter and high solids content (50wt %) to be used in coating and adhesive applications

Este trabalho está dividido em duas partes: (i) estudo da adsorção da enzima horseradish peroxidase (HRP) sobre substratos planos (lâminas de Si/SiO2, filmes ASP/Si/SiO2, filmes CABads/Si/SiO2, filmes CABspin/Si/SiO2 e filmes CMCABspin/Si/SiO2) seguida de testes da atividade enzimática da HRP imobilizada sobre estes substratos e (ii) obtenção de oligômeros divinílicos mediada pela HRP. Na primeira parte, a imobilização da HRP sobre substratos planos foi estudada através de elipsometria, microscopia de força atômica (AFM) e medidas de ângulo de contato. As isotermas de adsorção da HRP sobre Si/SiO2, APS/Si/SiO2 e CABads/Si/SiO2 apresentaram um aumento contínuo da quantidade de material adsorvido ΓHRP em função da concentração da solução de enzima até atingir um patamar de adsorção no qual verificou-se a formação de uma monocamada de HRP adsorvida. Nestes casos, o processo de adsorção da HRP pode ser descrito pelo modelo de adsorção aleatória (RSA). Para filmes HRP/CABspin/Si/SiO2 e HRP/CMCABspin/Si/SiO2 observou-se adsorção cooperativa de moléculas de HRP e formação de multicamadas. A adsorção da HRP sobre Si/SiO2, filmes APS, CABads e CMCABspin é um processo irreversível. Ao contrário, HRP adsorve reversivelmente sobre filmes CABspin, fato evidenciado pelo decréscimo de ~30% na espessura dos filmes de enzima. A atividade catalítica dos filmes de HRP imobilizados sobre substratos planos foi verificada na reação de oxidação do ABTS. Os testes de atividade catalítica mostraram que os substratos com a HRP adsorvida podem ser reutilizados 3 vezes sem dessorção ou perda da atividade catalítica da enzima, com exceção dos filmes HRP/CABspin/Si/SiO2 que se tornam inativos após a primeira catálise. A condição de máxima atividade catalítica de HRP imobilizada foi correlacionada com grau de cobertura de ~55%. O emprego do monômero etileno glicol dimetacrilato (EGDMA) em reações de polimerização catalisadas por filmes HRP/Si/SiO2 ou pela HRP livre em solução à temperatura ambiente revelou a formação de partículas cristalinas com geometria poligonal. Com objetivo de compreender a formação das estruturas cristalinas, a segunda parte do trabalho focou a formação de oligômeros de EGDMA e trietileno glicol dimetacrilato (TEGDMA) em meio aquoso catalisada pela HRP na presença H2O2 a temperatura ambiente. Os oligômeros de EGDMA e/ou TEGDMA foram caracterizados por gravimetria, cromatografia de permeação em gel, espectroscopia vibracional na região do infravermelho e espectroscopia 1H RMN. A auto-associação dos oligômeros originou partículas cristalinas com ângulos retos, como evidenciado pelas imagens de microscopia eletrônica de varredura. As medidas de calorimetria exploratória diferencial e difração de raio-x confIrmaram a cristalinidade das amostras. Os oligômeros de EGDMA, TEGDMA e EGDMA-co-TEGDMA sintetizados na presença do sistema HRP-H2O2 apresentaram grupos vinila pendentes, boa solubilidade em clorofórmio e ponto de fusão bem definido, evidenciando pouca reticulação ou ciclização e mostrando que as propriedades catalíticas da HRP propiciam um ambiente reacional apropriado para produzir materiais poliméricos com novas características. / This work is divided into two parts: (i) study on the adsorption of the enzyme horseradish peroxidase (HRP) onto flat substrates (silicon wafers, ASP/Si/SiO2 films, CABads/Si/SiO2 films, CABspin/Si/SiO2 films, and CMCABspin/Si/SiO2 films) followed by enzymatic catalytic tests of HRP immobilized onto these substrates, and (ii) formation of divinyl-based oligomers mediated by HRP. In the first part, the HRP immobilization onto flat substrates was investigated by means of ellipsometry, atomic force microscopy (AFM), and contact angle measurements. Adsorption isotherms of HRP onto silicon wafers, APS/Si/SiO2, and CABads/Si/SiO2 presented the continuous increase of HRP adsorbed amount ΓHRP as a function of enzyme solution concentration until an adsorption plateau, which evidenced monolayer formation. In these cases, the HRP adsorption process can be described by the random sequential adsorption model (RSA). For HRP/CABspin/Si/SiO2 and HRP/CMCABspin/Si/SiO2 cooperative adsorption of HRP molecules and multilayer formation were evidenced. The HRP adsorption onto silicon wafers, APS, CABads, and CMCABspin films is an irreversible process. Contrarily, HRP adsorbed reversibly onto CABspin films, since desorption of ~30% could be detected. The catalytic activity of HRP films immobilized onto flat substrates was verified by oxidation reaction of ABTS. Catalytic tests showed that substrates with adsorbed HRP can be reused three times without desorption or catalytic activity lost, except for HRP/CABspin/Si/SiO2 films, which became inactive after first use. The emulsion polymerization of ethylene glycol dimethacrylate (EGDMA) in mediated by HRP/Si/SiO2 films or by free HRP at room temperature revealed the formation of crystalline particles with polygonal geometry. In order to understand the formation of such crystalline structures, the second part of this thesis focused on EGDMA and/or triethylene glycol dimethacrylate (TEGDMA) oligomers formation in aqueous medium catalyzed by HRP in the presence of H2O2 at room temperature. EGDMA and/or TEGDMA oligomers were characterized by means of gravimetry, gel permeation chromatography, infrared vibrational spectroscopy and 1H NMR spectroscopy. Self-assembling of oligomers led to right-angled crystalline particles, as evidenced by scanning electron microscopy images. Differential scanning calorimetry and X-ray diffractometry measurements ratified the samples crystallinity. EGDMA, TEGDMA and EGDMA-co-TEGDMA oligomers synthesized in the presence of HRP-H2O2 system presented pendant vinyl groups along the chains, good solubility in chloroform, and well defined melting point. These features evidenced few crosslinking or cyclization and revealed that the catalytic properties of HRP provide an appropriate environrnent for production of materials with new characteristics.

Objetivos: o presente estudo teve como objetivo determinar a aplicabilidade e eficácia adesiva de diferentes monômeros ácidos quando aplicados em formulações de cimentos resinosos autoadesivos experimentais sob o grau de conversão, propriedades físico-químicas e resistência de união à dentina e à zircônia tetragonal policristalina estabilizada por ítrea (Y-TZP), após um período de 3 meses de armazenamento em água. Material: dois tipos de cimentos do tipo pasta-pasta foram formulados contendo monômeros convencionais UDMA, HEMA, BISGMA, TEGDMA e monômeros ácidos 2MP e GDMAP como matriz orgânica. Um grupo contendo apenas monômeros convencionais foi formulado como grupo controle. Os componentes canforoquinona/EDMAB e peróxido de benzoíla/DHPT foram empregados como sistema de ativação dual. O sal sódico do ácido benzenosulfônico 98% (BAS) foi incorporado nos grupos experimentais. Partículas de carga foram incorporadas na proporção ±55% em peso final. Método: A técnica de espectroscopia no infravermelho (FT-IR) foi empregada para análise do grau de conversão (n=3) imediato e após 24 h. A avaliação do pH (n=3) foi feita através do emprego de um equipamento medidor de pH. Os corpos de provas foram imersos em água destilada e o pH foi analisado de forma imediata e após 5 min, 24 h e 48 h. Os testes de sorção e solubilidade (n=6) e espessura de película (n=5) seguiram as recomendações da ISO 4049. A análise de resistência de união (n=12) foi realizada em dentina e Y-TZP, através do teste de cisalhamento em área reduzida após um protocolo de envelhecimento em água destilada por 3 meses. No caso da Y-TZP, metade dos espécimes receberam um tratamento superficial cojet (30 ?m), associado a aplicação de um agente de união silano. O padrão de fratura foi analisado com o auxílio de um estereomicroscópio. Resultados: O grupo controle (91,7%) e o grupo formulado com 2MP (92%) apresentaram superiores valores de grau de conversão em relação ao grupo GDMAP (77,7%). O pH dos grupos experimentais 2MP e GDMAP se apresentou mais ácido após 48 h em comparação ao grupo controle. Em contrapartida, esses grupos experimentais apresentaram uma maior sorção e solubilidade em relação ao grupo controle. A espessura da película formada foi semelhante em todos os grupos testados (p=0,266). Em dentina o grupo controle (27,0 MPa) e GDMAP (24,1 MPa) não apresentaram diferença estatística após 3 meses de estocagem. O grupo 2MP (13,7 MPa) apresentou resultados inferiores aos demais grupos. O tratamento de superfície empregado não foi capaz de manter ou de elevar os valores de resistência de união à Y-TZP após o período de envelhecimento em água. Todos os grupos experimentais apresentaram falhas precoces ou baixos valores de resistência de união após 3 meses, independente da presença ou não do tratamento de superfície. Conclusão: os grupos experimentais 2MP e GDMAP apresentaram resultados promissores. Entretanto, a adesão dos CRAs experimentais testados em Y-TZP ainda se apresenta frágil e instável. / Objectives: the purpose of this study was to evaluate the applicability and adhesive efficiency of different acid monomers utilized in formulations of experimental self-adhesive resin cement under degree of conversion, physico-chemical properties and bond strength to dentin and Y-TZP after 3 months aging period. Materials: two paste-paste luting agents were formulated containing UDMA, HEMA, BISGMA, TEGDMA and acid adhesive monomers 2MP and GDMAP as organic matrix. The control group was formulated containing only conventional monomers. Camphoroquinone/EDMAB and benzoyl peroxide/DHPT were used as dual activation system. BAS salt was incorporated into the experimental groups. Filler particles were added in a proportion of ±55% final weight. Method: Infrared spectroscopy technique (FTIR) was employed for degree of conversion analysis (n=3) immediately and after 24 hours. The pH assessment (n=3) was made using a pH meter. All the specimens were immersed in distilled water and pH assessment was performed immediately and after 5 min, 24 h and 48 h. Tests for sorption and solubility (n=6) and thickness (n=6) were carried out according to ISO 4049 recommendations. Bond strength analysis (n=12) was performed in dentin and Y-TZP through microshear after an aging 3 months protocol in distilled water. Regarding Y-TZP, half of the specimens were submitted to a cojet surface treatment (30 ?m) in association to silane bonding agent application. Fracture toughness standard was evaluated with the assistance of a stereomicroscope. Results: The control (91,7%) and 2MP (92%) groups presented higher degree of conversion than GDMAP group (77,7%). The 2MP and GDMAP experimental groups showed the highest pH compared to control group. In contrast, experimental groups showed a high hydrolytic degradation. The thickness of the formed film was similar among all the tested groups (p=0,266). Regarding the dentin, control and GDMAP groups had statistically similar bond strength (27,0 and 24,1 MPa respectively) after 3 months storage. While 2MP group (13,7 MPa) showed lower results compared the other groups. The surface treatment employed was not capable to maintain or elevate bond strength to Y-TZP results after the aging period in water. All experimental groups showed low bond strength values and even early failures after 3 months, regardless the surface treatment or its abscence. Conclusion: the experimental groups 2MP and GDMAP presented promising results. However, chemical adhesion to Y-TZP still remains weak and instable.

Two diazonium perfluoroalkyl arylsulfonimide (PFSI) zwitterionic monomers, 4-diazonium perfluoro(3-oxapent-4-ene)benzenesulfonimide (I) and 4-(trifluoromethyl)-2-diazonium perfluoro(3-oxapent-4-ene)benzenesulfonimide (II) have been synthesized from perfluoro(3-oxapent-4-ene) sulfonyl fluoride (POPF) for proton exchange membrane fuel cells. PFSI polymers are proposed as new electrolytes due to their better thermal stability, inertness to electrochemical conditions, and lower susceptibility to oxidative degradation and dehydration. For a better integration between the electrode and the electrolyte, the PFSI polymers are expected to be grafted onto the carbon electrode via the diazonium moiety. All the reaction intermediates and the final product were characterized with 1H NMR, 19F NMR and IR spectroscopies.

The present work describes a selection of strategies for the synthesis of functional aliphatic polycarbonates. Using an end-group functionalization strategy, a series of DNA-binding cationic poly(trimethylene carbonate)s was synthesized for application as vectors for non-viral gene delivery. As the end-group functionality was identical in all polymers, the differences observed in DNA binding and in vitro transfection studies were directly related to the length of the hydrophobic poly(trimethylene carbonate) backbone and the number of functional end-groups. This enabled the use of this polymer system to explore the effects of structural elements on the gene delivery ability of cationic polymers, revealing striking differences between different materials, related to functionality and cationic charge density. In an effort to achieve more flexibility in the synthesis of functional polymers, polycarbonates were synthesized in which the functionalities were distributed along the polymer backbone. Through polymerization of a series of alkyl halide-functional six-membered cyclic carbonates, semicrystalline chloro- and bromo-functional homopolycarbonates were obtained. The tendency of the materials to form crystallites was related to the presence of alkyl as well as halide functionalities and ranged from polymers that crystallized from the melt to materials that only crystallized on precipitation from a solution. Semicrystallinity was also observed for random 1:1 copolymers of some of the monomers with trimethylene carbonate, suggesting a remarkable ability of repeating units originating from these monomers to form crystallites. For the further synthesis of functional monomers and polymers, azide-functional cyclic carbonates were synthesized from the bromo-functional monomers. These were used as starting materials for the click synthesis of triazole-functional cyclic carbonate monomers through Cu(I)-catalyzed azide–alkyne cycloaddition. The click chemistry strategy proved to be a viable route to obtain structurally diverse monomers starting from a few azide-functional precursors. This paves the way for facile synthesis of a wide range of novel functional cyclic carbonate monomers and polycarbonates, limited only by the availability of suitable functional alkynes.

Die vorliegende Arbeit befasst sich mit der Inkorporation von Metall-/ Metalloxidnanopartikeln in organisch-anorganischen Hybridmaterialien, dargestellt durch Zwillingspolymerisation. Dabei wurden verschiedene Lösungsansätze bearbeitet. Zum einen wurden Metalcarboxylate oder Metallocene verwendet, zum anderen konnten durch Variation der anorganischen Komponente des Zwillingsmonomeres entsprechende Nanopartikel erzeugt werden. Um die Nanopartikel stabilisierenden Eigenschaften, der aus Zwillingspolymeren zugänglichen porösen Kohlenstoffmatrix zu erhöhen sollten mittels Zwillingspolymerisation N-Donoren eingeführt werden Neben der Inkorporation von Nanopartikeln wurden auch Silber und Goldnanopartikel in einer porösen Kohlenstoffmatrix verkapselt. Dabei wurde gezeigt, dass der Verwendete Templatdurchmesser einen entscheidenden Einfluss auf die späteren Hohlkugeln hat. Es konnte ebenso mit Hilfe von einfachen Benchmarkreaktionen die Zugänglichkeit und katalytische Aktivität der eingekapselten Nanopartikel nachgewiesen werden. Es wird gezeigt, dass durch Verwendung von Triphenylphosphan-stabilisierten Silber(I)-carboxylaten eine Funktionalisierung von Zwillingspolymeren möglich ist. Außerdem sind aus dem so modifizierten Hybridmaterialien nach Karbonisierung sowie dem Herauslösen der anorganischen SiO2-Komponete entsprechende mikroporöse, silberhaltige Kohlenstoffmaterialien zugänglich, während durch oxidativen Abbau der organischen Polymermatrix mesoporöse mit Ag-Nanopartikeln infiltrierte SiO2-Materialien dargestellt werden können. Es werden spezifische Oberflächen von 1034 m2/g (Kohlenstoff) und 666 m2/g (SiO2) erhalten. Das Wachstum der Silbernanopartikel konnte mittels Temperatur abhängiger Röntgenpulverdiffraktometrie beobachtet werden, und es wurde gezeigt, dass ein Wachstum erst während des Karbonisationsprozesses einsetzt. Mittels der HAADF-STEM-Technik wurden die gebildeten Nanopartikel im porösen Kohlenstoff bzw. SiO2 nachgewiesen, dabei liegen die Nanopartikel-durchmesser unterhalb von 5nm. Darüber hinaus konnte eine Vielzahl von neuen Zwillingsmonomeren dargestellt und charakterisiert werden. Darunter finden sich Zirkonium- und Hafnium-haltige Verbindungen, die analog der bekannten Si-Zwillingsmonomere ein ähnliches Polymerisationsverhalten zeigen und aus den resultierenden Hybridmaterialien poröse Oxide mit spezifischen Oberflächen unter 100 m2/g erhalten wurden. Eine Ausnahme bildet hierbei die SBS-Analoge Hafniumverbindung zur Phasenseparation während der Zwillingspolymerisation neigt, ebenso konnte für diese Verbindung kein vollständiger Umsatz erzielt werden. Durch Copolymerisation dieser neuen Zr- und Hf-haltigen Monomeren mit 2,2‘-Spirobi[4H-1,2,2-benzodioxasilin] wurden ZrO2- und HfO2-reiche SiO2-Mischoxide dargestellt. Dabei wurde das thermische Verhalten dieser Mischoxide mittels DSC weiter untersucht und es zeigte sich das ab 1000°C die ZrO2 sowie HfO2-Phasen beginnen zu Kristallisieren. Die so gebildeten hochkristallinen Nanopartikel konnten mittels TEM beobachtet werden. Ein weiteres erhitzen auf über 1200 °C führte dann noch zur Kristallisation der SiO2-Matrix. Ein weiteres Beispiel zur Synthese von oxidische Nanopartikeln mittels Zwillingspolymerisation wurde am ersten Metallocenhaltigen Zwillingsmonomer gezeigt. Dieses war aus der Reaktion von SiCl4 und Ferrocenylmethanol zugänglich. Neben der standardmäßigen Charakterisierung wurde auch die elektrochemischen Eigenschaften hin untersucht und dabei zeigte anders als es zu erwarten war eine Redox-Separation zwischen den einzelnen Ferrocengruppen. Weiterführende spektroelektrochemischen Experimente zeigten, dass diese Aufspaltung durch elektrostatische Abstoßung hervorgerufen wird. Das Zwillingspolymerisationsverhalten wurde zunächst mittels DSC untersucht und dabei konnte bei 210 °C eine exotherme Reaktion beobachtet werden, die mittels TG-MS als Kondensationsreaktion identifiziert wurde. Aufgrund dieser Ergebnisse konnte das Ferrocen-haltige Zwillingsmonomer thermisch polymerisiert werden. HAADF-STEM Abbildungen zeigten den typischen Aufbau eines Zwillingspolymeres, jedoch ist die Anzahl der zu beobachtenden Siliziumdioxidnanocluster geringer als bei bekannten Si-basierten Monomeren. Durch Copolymerisation mit 2,2‘-Spirobi[4H-1,2,2-benzodioxasilin] konnte dieser Nachteil ausgeglichen werden und nach karbonisierung und herauslösen der SiO2-Komponente bzw. Oxidation wird poröser Kohlenstoff (858 m2/g) bzw. Siliziumdioxid (555 m2/g) erhalten. Die Natur der eingebettet Eisenhaltigen Nanopartikel konnte mithilfe von Mössbauerspektroskopie untersucht werden. Dabei wurde im Kohlenstoffmaterial eine Mischung aus Fe2O3 und Fe3C gefunden während im SiO2 aufgrund der oxidierenden Bedingungen, während der Darstellung, von Fe2O3-Nanopartikeln ausgegangen wird. Die durchgeführten Mössbauerexperimente lieferten auch Indizien dafür, dass die gebildeten Nanopartikel sehr klein sind, dies wurde auch mittels HAADF-STEM bestätigt, jedoch kann kein genauer Zahlenwert fehlerfrei angegeben werden. Die geringe Größe spiegelt sich auch im magnetischen Verhalten der porösen Materialien wieder so verhält sich das SiO2 Material superparamagnetisch während der Kohlenstoff paramagnetisch ist. Abschließend konnten Pyrrol-basierte Siliziumalkoxide durch die Reaktion von SiCl4 und den entsprechenden Alkoholen dargestellt werden. Das Zwillingspolymerisation verhalten wurde mittels DSC charakterisiert. Dabei konnten wie schon zuvor beschrieben exotherme Reaktionen detektiert werden und diese liegen deutlich unter den Initiierungstemperaturen der bekannten Zwillingsmonomere (140 °C für N-Methylpyrrol und 93 °C für Pyrrol). Mittels TG-MS konnten auch hier Kondensationsreaktionen identifiziert werden. Daraufhin wurde die Hybridmaterialien aus den thermisch induzierten Polymerisationsversuchen beider Verbindungen untersucht. Es zeigte sich, dass das N-Methyl substituiertes Monomer sich nur in schlechten Ausbeuten polymerisieren lässt während das Pyrrolderivat ausgezeichnete Ausbeuten liefert. Auch die spezifischen Oberflächen sind mit bis zu 633 m2/g beträchtlich höher als mit vergleichbaren und bekannten Zwillingsmonomeren erzielt werden können. Auch zeigen sich beim einfachen Pyrrolbasierten Monomer Unterschiede zwischen thermischer und säure initiierter Zwillingspolymerisation. Während im ersten Fall hauptsächlich das 2-5-Substituierte Polymer erhalten wird kommt es bei säure Initiierung auch zur Bildung einer N-Alkyliertenspezies. Aus den Dargestellten Hybridmaterialien konnten poröse Kohlenstoffe mit Stickstoffgehalten zwischen 5.0-9.1 % erhalten werden. Auch hier zeigte sich das die Kohlenstoffe abgeleitet von dem N-methylierten Pyrrol einen höheren Stickstoffgehalt aufweisen als die aus der unmethylierte Spezies.