Orientador: Carlos Kenichi Suzuki / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-06T16:36:19Z (GMT). No. of bitstreams: 1 Tomazi_RodrigoGuevara_M.pdf: 828846 bytes, checksum: 4932ee70e0a24f3445ebebdf1bfefa80 (MD5) Previous issue date: 2006 / Resumo: As preformas nanoestruturadas de sílica produzidas pelo método de aerosol em chama constituem-se em precursores estratégico para aplicações tecnológicas em fotônica, tais como fibras óticas especiais e lentes com elevada transmissividade ótica na região ultravioleta. Para conseguir tais propriedades torna-se de fundamental importância o controle das características nanoestruturais nas preformas de sílica, tais como a distribuição de tamanho de partículas e a nanoporosidade. Neste sentido, a técnica de SAXS foi utilizada no presente trabalho para a caracterização nanoestrutural das preformas de sílica, com o auxílio das técnicas de ARX, BET, MEV e FRX. Com o tratamento matemático dos dados de SAXS pelo método GNOM, foram obtidas curvas de distribuição de tamanhos de heterogeneidades com dimensões entre 1 e 100 nm e, através dos efeitos observados nestas heterogeneidades com: (i) variação da carga em amostras de preformas prensadas uniaxialmente, (ii) variação das condições de temperatura em preformas tratadas termicamente e (iii) incorporação de íons de érbio foi possível estabelecer um entendimento efetivo da nanoestrutura da sílica produzida por aerosol em chama sob o aspecto tanto quantitativo, quanto qualitativo. Este resultado possibilita a determinação e o controle da distribuição de tamanhos de nanopartículas e nanoporos, condições essenciais para o desenvolvimento e a produção de dispositivos avançados de sílica para fotônica / Abstract: The nanostructured silica preform made by the flame aerosol method represents a strategical precursor for technological applications in photonics, such as special optical fibers and high optical transmissivity lenses for ultraviolet radiation. In order to attain such a properties, it becomes particularly important to control the nanostructured characteristics of silica preforms, such as nanoporosity and particle size distribution. In this sense, SAXS technique has been used for the characterization of silica preforms in conjunction of several other techniques, ARX, BET, MEV and FRX. Using the mathematical treatment of SAXS data by the GNOM method, structural heterogeneities in the range 1-100 nm were measured. Additional nanoscale information was observed through various effects induced by: (i) impinging a mechanical stress, (ii) thermal treatment in controlled atmosphere and precise temperature control, (iii) erbium ions doping. It was then possible to attain an effective understanding of nanostructure properties of the high purity flame aerosol silica, both on qualitative and quantitative aspects. The present result allows the control of size and size distribution of nanoparticles and nanopores, that is essential for the development and the production of advanced silica devices for photonics / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The development of techniques that minimizes the effects caused by the corrosive processes, associated with the cost benefit of ecologically viable alternatives, is replaced by more relevant to society. The objective of this work was to prepare microemulsion systems (SME) as steel corrosion inhibitors AISI 4142 from the oil of Annona muricata (Annonaceae) (Am) (Soursop), and NaCl in an aqueous solution with a concentration of 3.5%, as aqueous phase, simulating the corrosive medium. In order to stabilize the system Tween 80 was used as surfactant (T) and ethanol as a cosurfactant (TOC). The rheological properties were evaluated, the structure and the potential inhibition were analyzed by small angle X-ray scattering and electrochemical tests, respectively. Rheological measurements showed that all systems showed typical Newtonian behavior of SME and confirmed by SAXS. From application models, the results demonstrate that the microemulsions showed ellipsoidal shape "core-shell" for all SME except for samples with 70% aqueous phase, 27% oil phase and 3% surfactant which showed structures elongated cylindrical. Electrochemical tests polarization by extrapolation of Tafel plots were performed and demonstrate that all EMS had good corrosion resistance. The efficiency obtained for the samples show a percentage inhibition of 14.7% ME1, ME2 14.7%, 13.4% ME3, ME4 12.2% and 10.7% for ME5, and also evidenced an offset the most positive potential compared with curves for the solution without microemulsion. The results showed that obtained from EMS of Annona muricata (Annonaceae) oil are potential corrosion inhibitors, ME2 and 14.7% inhibition and a bend located at higher current density values, the sample showing be best inhibitor. / O desenvolvimento de técnicas que possam ajudar a minimizar os efeitos causados pelos processos corrosivos, associados ao custo benefício de alternativas ecologicamente viáveis, passa a ter maior relevância para a sociedade. O objetivo deste trabalho foi preparar sistemas microemulsionados (SME) como inibidores de corrosão em aço AISI 4142 a partir do óleo da Annona muricata (Annonaceae) (Am) (Graviola), tendo NaCl em uma solução aquosa com concentração de 3,5%, como fase aquosa, simulando o meio corrosivo. Para estabilização do sistema foram utilizados o Tween 80 como tensoativo (T) e etanol como cotensoativo (COT). As propriedades reológicas foram avaliadas, a estrutura e o potencial de inibição foram analisados por espalhamento de Raios X a baixo ângulo e ensaios eletroquímicos, respectivamente. As medidas reológicas mostraram que todos os sistemas apresentaram comportamento newtoniano típico de SME e confirmados por SAXS. A partir de aplicação de modelos, os resultados demonstraram que as microemulsões apresentaram formato elipsoidal “casca-caroço” para todas as amostras com exceção de SME com 70% de fase aquosa, 27% de fase oleosa e 3% de tensoativo que apresentou formato cilíndrico alongado. Ensaios eletroquímicos de polarização por extrapolação das curvas de Tafel foram realizados e demonstram que todos os SME apresentaram boa resistência à corrosão. Os valores de eficiência obtidos para as amostras apresentam percentual de inibição de 14,7% ME1, 14,7% ME2, 13,4% ME3, 12,2% ME4 e 10,7% para a ME5, sendo também evidenciado um deslocamento das curvas para potenciais mais positivos em comparação com a solução sem microemulsão. Os resultados mostraram que SME obtidos a partir do óleo da Annona muricata (Annonaceae) são potenciais inibidores de corrosão, sendo a ME2 com 14,7% de inibição e com uma curva localizada em maiores valores de densidade de corrente, a amostra que apresentou ser a melhor inibidora.

Orientador: Iris Concepción Linares de Torriani / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-15T22:30:16Z (GMT). No. of bitstreams: 1 Silva_JulioCesarda_D.pdf: 7791031 bytes, checksum: 5711654f743b7d6fb045861e9239ad8c (MD5) Previous issue date: 2010 / Resumo: As técnicas de caracterização estrutural de macromoléculas tradicionais se baseiam no fato de uma macromolécula possuir uma conformação compacta e estruturada. Partes flexíveis ou regiões desordenadas têm sido sempre consideradas como grandes obstáculos para técnicas como a cristalografia de raios-X e a ressonância magnética nuclear (RMN). A necessidade de entender a atividade funcional de proteínas nativamente desenoveladas e de proteínas flexíveis com múltiplos domínios tem adquirido grande importância recentemente, mesmo porque essas proteínas desafiam o paradigma de que uma proteína precisa de uma estrutura bem definida para ser funcional. É bem nesse ponto que a técnica de espalhamento de raios-X a baixos ângulos (SAXS) surge oferecendo ferramentas únicas para realizar estudos de macromoléculas flexíveis ou parcialmente desestruturadas, com aplicações muito bem sucedidas em polímeros, matéria mole e macromoléculas em solução. Neste trabalho de tese decidimos enfrentar o desafio de caracterizar proteínas que não possuem uma estrutura bem definida. A teoria do espalhamento mereceu especial cuidado para se adequar tanto aos métodos experimentais da técnica quanto aos tratamentos matemáticos em cálculos usados para estudar esse tipo de proteínas. Apresentamos aqui o estudo de duas proteínas pertencentes à classe das proteínas nativamente desenoveladas: (1) a proteína FEZ1, que é necessária para o crescimento de axônios; (2) a proteína Ki-1/57, que é encontrada em diversas células com câncer principalmente em tumores do sistema linfático. Estudamos também algumas proteínas com múltiplos domínios conectados por regiões flexíveis e que são: (1) duas chaperonas da classe das HSP40 (proteínas Sis1 e Ydj1) juntamente com construções onde alguns domínios dessas proteínas foram cortados; (2) a proteína ribonucléica heterogênea hnRNP-Q que está envolvida em importantes funções do RNA. Experiências de SAXS foram realizadas, fornecendo parâmetros dimensionais e informações de forma dessas proteínas em solução. Modelos de baixa resolução das possíveis conformações foram calculados a partir das curvas de SAXS usando métodos de modelagem ab initio combinados com modelagem de corpos rígidos. Os resultados forneceram informações importantes para elucidar as funções biológicas dessas proteínas. É importante ressaltar que, para realizar os estudos com proteínas em solução, é necessário contar com uma instrumentação adequada e devidamente montada para a aplicação da técnica de SAXS. Para isso, durante o período de desenvolvimento deste doutorado houve um grande investimento na montagem, teste e caracterização de instrumentos, junto à equipe de profissionais do Laboratório Nacional de Luz Síncrotron (LNLS), completando o comissionamento da estação experimental SAXS2 do LNLS / Abstract: The traditional techniques for structural characterization of macromolecules are based on a compact and structured conformation of the macromolecule. Flexible or disordered regions have usually been regarded as a great hindrance to techniques like X-ray protein crystallography and nuclear magnetic resonance (NMR). The need to study functional activity of natively unfolded proteins and flexible multidomain proteins came to the light rather recently, defying the classical structure¿function paradigm where a protein must have a well-defined 3-D structure to be functional. In this type of situation, the small-angle X-ray scattering (SAXS) technique appears as a unique tool to deal with this problem. Indeed, the application of SAXS methods to the characterization of soft matter (e.g. polymers) and macromolecules in solution has already succeeded during the last years. In this work we decided to face the challenge of characterizing proteins that do not have a well defined structure. The SAXS experimental technique as well as the mathematical methods and calculations needed special attention in order to be correctly applied to study the specific problem of unstructured proteins in solution. Thus, it was possible to find evidence of the structural details of these proteins and obtain a low resolution 3-D average structure. Here we present the study of two proteins that belong to the group of natively unfolded proteins: (1) The FEZ1 protein, which is necessary for axon growth, and (2) the proteins indentified as Ki-1/57, which is found in diverse cancer cells mainly in lymphatic systems tumors. We also studied some flexible multidomain proteins: (1) two chaperones from the groups of HSP40 (the proteínas Sis1 e Ydj1), and two mutant constructions where some domains were deleted; (2) the heterogeneous ribonucleoprotein hnRNP-Q which is related to an array of important functions of RNA. Several SAXS experiments were performed providing overall parameters and important shape information about those proteins in solution. Low resolution models for the possible conformations of these proteins were restored from the SAXS curves using ab initio modeling methods combined with rigid body modeling. The SAXS results provided a unique structural background for the biologists to deal with the function of these proteins. SAXS experiments with proteins in solution demand the use of a specific instrumentation properly developed for those studies. So, it is important to mention that, throughout the duration of this doctorate, specific instrumentation development and testing was done together with the technical staff of the Brazilian Synchrotron Light Laboratory (LNLS, Campinas, SP, Brazil), collaborating with the commissioning of the new SAXS2 workstation, completed in 2008 / Doutorado / Física / Doutor em Ciências

The main objective of this study was the formulation of food-grade water-in-oil (W/O) nano-dispersions based mainly on medium or long-chain triglycerides. Two types of dispersions were formulated and structurally compared, namely emulsions and microemulsions. The systems were used as matrices for encapsulating targeted bioactive molecules with specific characteristics such as antioxidants or peptides. The structural characterization of the formulated systems was investigated using techniques such as Electron Paramagnetic Resonance (EPR) spectroscopy, Dynamic Light Scattering (DLS), Cryogenic Transmission Electron Microscopy (Cryo-TEM) and Small Angle Xray Scattering (SAXS). The existence of swollen inverse micelles was revealed for the case of microemulsions whereas larger droplets still at the nano-scale were observed for the case of emulsions. Structural differences in the presence of the bioactive molecules or induced by the alteration of components were also observed. In order to study the efficacy of the formulations, the proposed loaded systems were assessed either using EPR spectroscopy or Well Diffusion Assay (WDA) depending on the bioactive molecule. It was found that the encapsulated molecules retained their claimed characteristics when encapsulated to the proposed matrices. Finally, some of the formulated dispersions were investigated for their behavior under gastrointestinal (GI) conditions. A two-step digestion model using recombinant Dog Gastric Lipase (rDGL) and Porcine Pancreatic Lipase (PPL) was proposed to simulate lipid hydrolysis in humans. The studies revealed significant decrease of the rDGL specific activity in the presence of the microemulsion while in the presence of lower percent of surfactants (case of emulsion) no alterations were observed.

La poudre de boehmite, précurseur de l’alumine utilisée pour la production de supports catalytiques variés, est produite suite à une étape de séchage par atomisation. Cet oxyhydroxyde d’aluminium est composé de particules anisotropes chargées. Ces dernières années, il a été ont montré que les propriétés physico-chimiques des suspensions avaient une influence sur les caractéristiques des poudres. La morphologie des grains (sphère creuse, tore…) ainsi que les propriétés des poudres (dispersibilité, résistance mécanique…) peuvent être modifiées en jouant sur les caractéristiques des suspensions.Ce travail de thèse porte sur la compréhension des liens entre les propriétés physico-chimiques et rhéologiques de suspensions de deux boehmites industrielles et les propriétés des grains obtenus après séchage. Dans une première partie, nous avons caractérisé les particules en suspension de ces deux boehmites grâce à une approche multi-technique (SAXS, DLS, MET). Une étude rhéologique des suspensions obtenues par stress osmotique a ensuite permis de construire précisément le diagramme de phase de ces deux boehmites dans le plan force ionique – fraction volumique. La diffusion des rayons X aux petits angles et la diffusion dynamique de la lumière ont été utilisées pour déterminer l’organisation structurale des suspensions. Enfin, des expériences de séchage suivies optiquement et par micro-tomographie X ont été réalisées sur des suspensions de boehmite afin d’étudier l’impact de la concentration et de la force ionique sur l’évolution de la goutte au cours du séchage. / In the catalyst supports industry, one important step of alumina powder production is the spray-drying of boehmite suspensions. This aluminium oxyhydroxyde is often used as precursor for various types of alumina catalyst supports. Boehmite is composed of anisotropic particles bearing an electric charge. In the past decade, it has been shown that the properties of the dry powder depend not only on the drying conditions but on physico-chemical properties of the sprayed suspensions. For instance, different grains morphologies (doughnut-shaped grains, hollow spheres,…) as well as various dry grains properties (textural properties, mechanical resistance,…) may be obtained by tuning the physico-chemical properties of the suspension.This study focus on the understanding of the links between the physico-chemical properties of suspensions of two industrial boehmites and the characteristics of the final dry grain. Since these two boehmites were not well-known, the first step of the study was to characterize boehmite particles present in suspension thanks to a multi-technical approach. A rheological study was performed on boehmite suspensions obtained thanks to osmotic stress to build precisely the phase diagrams of the both boehmites according to the system of ionic strength vs. volume fraction. Small angle X ray scattering and dynamic light scattering were used to investigate the existence of an orientational order of boehmite particles in suspension. Finally, drying experiments of boehmite suspensions were conducted on an optical set-up and on fast micro-tomography X, to examine the impact of both concentration and ionic strength on the evolution of the droplet during drying.

No description available.

Le domaine de recherche concerne l’endommagement par cavitation des élastomères exposés à de fortes pressions de gaz diffusant. Ce phénomène résulte de l’expansion locale du gaz préalablement absorbé, lorsque la désorption hors du polymère est trop lente par rapport au chargement imposé. Dans le cas de l’hydrogène qui nous intéresse ici, l’enjeu est le développement de matériaux polymères performants pour les structures de stockage et de distribution d’hydrogène gazeux hyperbare. En conditions d’usage, ces matériaux sont exposés à de fortes pressions d’hydrogène qui diffuse en leur sein et génèrent ensuite de forts endommagements lorsque la pression hydrostatique est relâchée. Les études de laboratoire sur ce sujet restent peu nombreuses, a fortiori sous environnement hydrogène. Sur le plan expérimental, ceci s’explique par la délicate manipulation de l’hydrogène et par le contexte des fortes pressions. Sur le plan de la simulation numérique, un verrou important est lié aux couplages forts entre diffusion et mécanique dans la résolution de l’équilibre de la cavité à chaque instant de son évolution. Cette thèse vise à mieux comprendre le mécanisme élémentaire de formation, puis de croissance et de coalescence des cavités, isolées ou en proche voisinage. Dans ce dernier cas, une éventuelle interaction doit effectivement être caractérisée pour éclairer la coalescence et la transition vers des fissures macroscopiques. Le travail a été mené sur série d’Ethylène Propylène Diène Monomer (EPDM) non-renforcés, avec une densité de points de réticulation variable, exposés à des pressions allant jusqu’à 30 MPa. Le volet expérimental s'appuie sur deux des techniques expérimentales in situ les plus récentes. La diffusion des rayons X aux petits angles (SAXS) vise à caractériser les hétérogénéités du système réseau élastomère – hydrogène à l'échelle submicronique, et éventuellement à détecter les premiers stades de cavitation. Dans la gamme des faibles pressions accessible sous environnement hydrogène, les hétérogénéités ne sont pas assez marquées pour définir plus qu'une distance de corrélation, qui varie très peu comparativement au matériau non exposé. Après exposition à une pression plus élevée (30 MPa), une augmentation de la distance de corrélation est observée, révélant une modification de l'hétérogénéité de la matrice, irréversible même après désorption complète de l'échantillon. À l’échelle micronique, des expériences de tomographie X in-situ (sous des pressions allant jusqu’à 12 MPa) fournissent des vues 3D résolues en temps des cavités, pendant et après décompression. Ces expériences ont permis de mieux comprendre la cinétique de croissance des cavités dans différentes conditions aux limites locales (dans le volume de l’échantillon, à proximité d'autres cavités, près d'une surface libre) et de les interpréter en regard des propriétés de diffusion de l'échantillon lui-même. Plusieurs populations de cavités, présentant des comportements différents, ont ainsi pu être distinguées en fonction de leur distance à la surface libre de l'échantillon, en lien avec la désorption globale de l’échantillon. Comparativement à cet effet de bord libre, la présence d’une autre cavité en proche voisinage (i.e. à une distance bord à bord supérieure ou égale à 30μm) n’a qu’une influence minime. Les résultats suggèrent que la croissance de la cavité est un processus très local. Dans un contexte diffuso-mécanique fortement couplé, l’interprétation des mécanismes se heurte à l’impossibilité d’accéder expérimentalement aux champs mécaniques et de concentration de gaz. Les codes éléments finis existants rencontrent des problèmes de convergence que le code interne Foxtrot développé à l’Institut Pprime tente de surmonter. Dans une dernière partie exploratoire de la thèse, il a été mis à profit pour comparer les gradients générés par une paire de cavités comparativement à une cavité isolée. / The optimum design and formulation of seals used in hydrogen transport system is crucial for the purposes of safety of operation and well as economic sustainability of hydrogen as energy carrier. The exposure of the sealing materials to hydrogen and subsequent decompression causes cavitation damage. The studies so far on this subject have been few due to the strong limitations arising from the safety issues related to hydrogen testing in laboratory conditions. This study addresses the cavitation in Ethylene Propylene Diene Rubber (EPDM) due to pressure release after exposure to high-pressure hydrogen up to 30 MPa. Three different unfilled EPDM with variable cross-link density were investigated. The study was based on some of the newest in-situ experimental techniques which allow a time-resolved tracking of the evolution of damage. On one side, in-situ SAXS (Small Angle X-ray Scattering) tests of hydrogen-exposed EPDM were aimed at the characterisation of EPDM at submicron scale as a function of network heterogeneity and for tracking the possible onset of distinguishable cavities. At the low pressure range accessible with the device, heterogeneities were not marked enough to define more than a correlation length that was significantly changed compared the unexposed material, whatever the cross-link density. After the exposure at higher pressure (30 MPa) a change in correlation length was observed corresponding to the change in heterogeneity of the matrix which was found to be non-reversible even after full desorption of the sample. At a higher scale, in-situ X-ray tomography was used to provide time-resolved 3D views of damage during and after hydrogen pressure release. These experiments provided insight into the growth kinetics of cavities in different local boundary conditions (within the bulk, close to other cavities, close to a free surface) correlated with the diffusion characteristics of the sample itself. Classification of cavities as bulk and edges cavities was possible with respect with different kinetics depending on their proximity to the free surface of the sample. This could be correlated with the diffusion characteristics of the material. The dependence of kinetics of cavities on the proximity of another cavity was found to be trivial at the scale investigated (above 30 μm between cavity borders) suggesting that growth is a very local process. The previous studies have clarified that the cavitation in rubber is a coupled diffuso-mechanical phenomenon and so far, the numerical tools available have not addressed the problem as such. Therefore, the development of a numerical tool aimed at solving such coupled problems has also been addressed in the present work. This numerical tool called Foxtrot, developed at Institut PPRIME, is in the early stages of development but is a crucial step towards the more realistic simulation of this phenomenon of cavitation. In this fully coupled diffuso-mechanical context, the interpretation of mechanisms is highly limited by the lack of experimental access to the mechanical and gas content fields. Commercial Finite Element codes face convergence problems that the internal code developed at the Pprime Institute (Foxtrot) is trying to overcome. In the last exploratory part of the thesis, the code was used to as a step towards a more realistic simulation of the phenomenon. In particular, gradients around a pair of cavities were compared to those obtained around an isolated cavity.

5 Abstract Ca2+/calmodulin-dependent protein kinase kinase 2 (CaMKK2) belongs to the serine/ threonine protein kinase family, which is involved in the calcium signaling pathway. The increase of intracellular calcium concentration induces the activation of calmodulin (CaM), which then activates its binding partners including CaMKII, CaMKIII, CaMKK1 and CaMKK2. CaMKK2 activates CaMKI, CaMKIV and AMP-dependent kinase, AMPK, by phosphorylation. CaMKK2 is naturally present in cells in an autoinhibited state, which is caused by the steric hindrance of the active site by the autoinhibitory domain. When calmodulin binds to the calmodulin-binding domain, the autoinhibitory domain is removed and the active site becomes accessible. Upon activation, CaMKK2 undergoes autophosphorylation, which increases its enzyme activity. Negative regulation of CaMKK2 is mediated by cAMP-dependent protein kinase A (PKA)- and GSK3-dependent phosphorylation. Sites phosphorylated by PKA have been identified for both CaMKK1 and CaMKK2. Two of them are also motifs recognized by scaffolding 14-3-3 proteins. Previous studies have shown that the 14-3-3 protein binding maintains phosphorylated CaMKK2 in an inhibited state by blocking the dephosphorylation of S495, which prevents the binding to calmodulin. However, it is unclear if it is the...

Lactobacillus kunkeei is the most common and dominant bacterium in the honey stomach of honeybees. L. kunkeei has been isolated from honeybees all over the world. Genome sequencing has identified 5 genes for exceptionally large proteins in the genome of L. kunkeei. These proteins do not show any similarity to sequences of proteins with a known structure. These giant proteins all have a conserved region of 60 amino acids in their C-terminus. This conservation led to the hypothesis that the C-terminal domains of the giant proteins are important for their function with possibly a role in the attachment to the cell wall. In this study, a total of eight different constructs were made for two of these giant proteins. The boundaries for the constructs were determined based on bioinformatic predictions. The eight constructs all have different start positions and all end at the very C-terminal end of the protein. These constructs were cloned into an expression vector. One of the full-length giant protein was cloned into an expression vector as well.  The C-terminal constructs and the full-length proteins were recombinantly produced in Escherichia coli. Expression of six C-terminal constructs was observed and an attempt was made to purify two of the C-terminal constructs. Expression of the full-length giant protein was observed as well and purification was attempted. Neither the C-terminal constructs nor the full-length giant protein could be purified at full length. The results for the C-terminal constructs show that no folded C-terminal domain has been found for the giant proteins. A purified protein construct of the N-terminal of one of the giant proteins was available. This protein was analyzed using biophysical techniques. Circular dichroism was used to test the thermal stability. The construct did not refold after being thermally denatured. Circular dichroism measurements indicated that the N-terminal construct is composed of a mixture of α-helices and ß-sheets. Small-angle X-ray scattering data indicated that the N-terminal construct had an elongated shape with knot-like parts. Protein crystals have been obtained for the N-terminal construct and these will be analyzed using X-ray diffraction.

This thesis is focused on synthesis and polymerization of caprolactone and its derivatives by living ring opening polymerization (LROP), Self-assembly in aqueous solutions produced nanoaggregates comprised of amphiphilic block copolymers or telechelic polymers with incorporated boron compounds (phenyl boronic acids and boron clusters). Incorporation of boron compounds was facilitated either by covalent or non-covalent bonding. Obtained complex nanoparticle structures manifested stimuli-responsive behaviour and were investigated under varying conditions by combination of light scattering, fluorescence spectroscopy and electron microscopy. The obtained results on solution behaviour of polymers in combination with added value of boron compounds, yield general aspects of nano aggregate morphology, responsive character tuning and practical aspects of synthesis and self-assembly overcame in the preparation process. The publications wrote during this thesis are therefore adding valuable information to researchers engaged in biomedical utilization of such nano assemblies.