Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-10-08T14:50:19Z No. of bitstreams: 1 TÂNIA LÚCIA LEAL - TESE (PPGEP) 2007.pdf: 1662597 bytes, checksum: 3b9ecad3c331d148a824d574cd4ac35c (MD5) / Made available in DSpace on 2018-10-08T14:50:19Z (GMT). No. of bitstreams: 1 TÂNIA LÚCIA LEAL - TESE (PPGEP) 2007.pdf: 1662597 bytes, checksum: 3b9ecad3c331d148a824d574cd4ac35c (MD5) Previous issue date: 2007-02-22 / CNPq / Membranas obtidas por sinterização de partículas de PEUAPM foram desenvolvidas visando sua aplicação no tratamento de efluentes. As membranas foram sinterizadas em diferentes tempos e temperaturas e o seu desempenho na remoção de partículas presentes em efluentes aquosos foi investigado. Utilizou-se o planejamento experimental fatorial e análise de superfície de resposta para avaliar os efeitos do tempo e temperatura de sinterização no desempenho das membranas. Este estudo foi conduzido com as amostras que apresentaram menor tamanho de partículas, isto é, passantes em peneira de malha 200. Os resultados evidenciam que quanto maiores os tempos e temperaturas de sinterização, menores os fluxos do permeado através das membranas e que os efeitos da temperatura foram mais acentuados do que os do tempo de sinterização. A compactação das membranas após a sinterização provocou reduções no fluxo e na porosidade, enquanto o tamanho médio dos poros permaneceu inalterado. Dois procedimentos foram utilizados para modificar a superfície interna das membranas: a) deposição de um filme de PEAD e b) modificação por plasma de metano. Estas modificações foram realizadas nas membranas manufaturadas com pó de PEUAPM como recebidos do fabricante e com os passantes em peneira de malha 200. Ambas as modificações de superfície levaram a reduções no tamanho de poros na superfície das membranas. O tratamento por plasma minimizou o fenômeno de “fouling”, enquanto que maior eficiência na remoção de partículas sólidas em suspensão na água foi obtida com membranas recobertas internamente com filme de PEAD. Melhor desempenho global foi obtido para as membranas manufaturadas com PEUAPM de código 3041 passante em peneira de malha 200, superficialmente modificadas ou não. Este estudo indica que o PEUAPM pode ser usado na produção de membranas de microfiltração de baixo custo para remoção de partículas sólidas presentes em efluentes aquosos. / Membranes obtained by sintering of UHMWPE powders were manufactured aiming at their use in effluent treatment. The membranes were sintered at different times and temperatures and their performance in aqueous effluent particle removal were investigated. An factorial experimental planning and response surface analysis was employed to evaluate the effects of sintering time and temperature in the performance of the membranes. This study was conducted on samples having the smallest particles size, i.e., with powders that passed through a 200 mesh sieve. Higher sintering times and temperatures led to smaller permeate flow through membranes and temperature effects were more significant than those of time. Membranes compaction after sintering leads to lower permeate flows and porosities, although the average pore sizes do not change. Two routes were used to modify the internal surface of the membranes: a) HDPE film deposition and b) methane plasma modification.These modifications were made with membranes prepared with UHMWPE powder as received from supplier and passed through a 200 mesh sieve. Both treatments caused reductions on the membranes superficial pore sizes. Plasma treatment minimized the “fouling” phenomenon, while the best efficiency in solid particle removal from water dispersions was found for the membrane internally coated with a HDPE film. Best overall performances were displayed by the membranes prepared with UHMWPE grade 3041 sieved though a 200 mesh sieve. The results indicate that the UHMWPE can be used to prepare low cost micro-filtration membranes to remove solid particles present in aqueous effluents.

Neste trabalho, filmes híbridos produzidos pela técnica da automontagem eletrostática camada-por-camada foram preparados usando-se Polioxometalatos do tipo Keggin, ácido fosfotúngstico (HPW) e o complexo monolacunar K(TPA)4[PW11O39Mn(OH2)] alternados via um polímero catiônico, poli(cloreto de alilamônio) (PAH). O filme que continha uma pré-camada de adsorção de PDMS, juntamente com 5 bicamadas de PAH e HPW apresentou um melhor comportamento eletroquímico em filmes formados sobre óxido de índio e estanho (ITO). Em função disso, este filme foi caracterizado através de Espectroscopias de Absorção na região do Ultra-Violeta Visível (UV-vis), de Absorção-Reflexão na Região do Infra-vermelho (FT-IRRAS) e de Ressonância de Plásmons de Superfície (SPR). Foi constatado por FT-IRRAS que parte da camada de PDMS está se difundindo para a superfície quando as bicamadas de PAH e HPW vão sendo preparadas. Imagens de Microscopia Eletrônica de Varredura com Emissão de Campo (MEV-EC) confirmam esta hipótese. Espectroscopia de SPR indicou que tanto a adsorção de PAH quanto a de HPW ocorrem em tempos curtos. Experimentos de Voltametria Cíclica com [Fe(CN)6]3-mostraram que este filme é poroso. Resultados de Espectroscopia de Fotoelétrons Excitados por Raios X (XPS) comprovaram que PDMS protege o substrato contra corrosão. Esse mesmo filme pôde ser utilizado numa aplicação de caráter ambiental. Ele foi capaz de detectar melamina e atrazina em concentrações 4.10-8 mol.L-1 e 1.10-6 mol.L-1 respectivamente. Filmes contendo 5 bicamadas de PAH e K(TPA)4[PW11O39Mn(OH2)] mostraram comportamentos similares referentes à queda da eletroatividade para arquiteturas iniciadas com PAH e PDMS. O filme com 5 bicamadas de PAH e K(TPA)4[PW11O39Mn(OH2)] iniciado com PAH não mostrou comportamento eletrocatalítico para a oxidação de triazinas. / In this work, self-assembled hybrid layer-by-layer films were prepared using Keggin type polyoxometalates, phosphotungstic acid (HPW) and the monolacunary complex K(TPA)4[PW11O39Mn(OH2)] alternated by a cationic polymer, poly(allylamine hydrochloride) (PAH). The film containing 5 bilayers of PAH and HPW deposited on a PDMS cushion exhibited better electrochemical behavior onto indium tin oxide (ITO) electrodes. So, this film was characterized by UV-vis spectroscopy, Fourier transformed infrared reflection adsorption spectroscopy (FT-IRRAS) and Surface Plasmon Resonance Spectroscopy (SPR). FT-IRRAS results showed that PDMS is going to the top of the bilayers of PAH and HPW when the film is prepared. Images of the Scanning Electronic Microscopy with field emission guns (FEG-SEM) confirm this fact. SPR spectroscopy results showed adsorption times of PAH and HPW short. Cyclic Voltammetry experiments with [Fe(CN)6]3- for the film confirm that it is porous. X-Ray Photoelectron spectroscopy (XPS) proved that in this film PDMS is present and it is responsible by protection against corrosion of substrate. This film can be used for environmental application. It was able to detect melamine and atrazine in concentrations of 4.10-8 and 1.10-6 mol.L-1 respectively. Films containing 5 bilayers of PAH and K(TPA)4[PW11O39Mn(OH2)] exhibited similar electrochemical behaviors for the decrease in the electroactivity for cushions of PAH and PDMS. The film with 5 bilayers of PAH and K(TPA)4[PW11O39Mn(OH2)] with PAH cushion does not exhibited electrocatalytic behavior for oxidation of triazines.

Orientador: José Alberto Fracassi da Silva / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-20T05:22:01Z (GMT). No. of bitstreams: 1 Campos_RichardPifferSoaresde_M.pdf: 3349460 bytes, checksum: 5efdb4dd4409b9d1b6771593c8874edf (MD5) Previous issue date: 2012 / Resumo: Os micro sistemas de análise total consistem de dispositivos da ordem de centímetros que tem como objetivo a integração de várias etapas analíticas em um único chip, tais como etapas de tratamento de amostra, separação por eletroforese capilar, ou mesmo a integração de sensores em canais microfluídicos. O poli(dimetilsiloxano), PDMS, é um dos polímeros mais adotados para a fabricação destes microdispositivos, devido a suas propriedades elastoméricas, transparência óptica, permeabilidade gasosa, biocompatibilidade, fácil moldagem, relativa alta resistência química e baixo custo de fabricação, além de poder ser facilmente moldado e selado, resultando em microcanais com boa resolução. Além disso, é possível a fabricação de canais por ablação a laser sobre o polímero curado. Entretanto, a característica altamente hidrofóbica do PDMS faz com que sua aplicação para soluções aquosas seja problemática e analitos pouco polares possam sofrer forte adsorção nas paredes do canal, tornando pobre a reprodutibilidade do processo. Neste sentido, estratégias para modificar o material nativo ou mesmo a superfície dos canais vêm sendo estudadas. Neste trabalho, foi inicialmente estudada a modificação estrutural do PDMS, que consiste na utilização de um reticulante (contendo função orgânica polar metacrilato ou amina) na formação do substrato. Também foi realizada a modificação da superfície do substrato de PDMS por reação topológica, com a introdução de polietileno glicol, além da modificação do processo convencional de reticulação do PDMS Sylgard 184, pela adição do surfactante Silwet-L77 a este processo. O PDMS modificado foi avaliado quanto a sua hidrofobicidade, por medida do ângulo de contato com a água, em relação às propriedades do fluxo eletrosmótico gerado no microcanal e as modificações foram estudadas por métodos espectroscópicos. A reação de modificação de superfície do PDMS com divinil éter de polietileno glicol apresentou as melhores características hidrofílicas dentre as modificações estudadas e mobilidade do fluxo eletrosmótico com valor de 3,6x10 cm V s. Em adição, as modificações puderam ser caracterizadas por métodos de espectroscopia (IR e Raman), que se mostraram eficientes na avaliação tanto da rota de modificação quanto do produto final / Abstract: The micro total analysis systems consist of devices in the order of centimeters that aim to integrate several analytical steps on a single substrate, such as sample treatment, injection, or even integrated sensors on microfluidic channels. Poly(dimethylsiloxane), PDMS, is one of the most used polymers for microfabrication due to its elastomeric properties, optical transparency, gas permeability, biocompatility, relatively high chemical resistance and low fabrication costs. PDMS can also be easily cast and sealed, resulting in microchannels with good resolution. On top of that, it is possible to fabricate the microchannels using the lase ablation technique on the cured PDMS. However, the highly hydrophobic characteristic of PDMS makes its aqueous applications problematic. Moreover, non-polar analytes can adsorb on the channel walls, leading to poor reproducibility. In this sense, strategies to modify the raw material or channel surface have been proposed. In this work, the structural modification of PDMS, involving the use of a crosslinking agent (containing the methacrylate or amine polar functions) was studied. In addition, the surface modification of PDMS by topologic reaction with polyethylene glycol and the modification of the conventional PDMS Sylgard 184 crosslinking by the addition of Silwet-L77 surfactant were also performed. The hydrophobicity of modified PDMS was evaluated by water contact angle measurements and the modifications were studied by spectroscopic methods. The electroosmotic flow (EOF) generated in the microchannels was also evaluated. The best hydrophilic characteristic among the studied modifications were obtained with the polyethylene glycol divinyl ether PDMS modification. This device presented an EOF of 3,6x10 cm V s. In addition, the modifications could be characterized by spectroscopic methods (Raman and IR) and those techniques were efficient in the evaluation of the reaction routes as well as the final products / Mestrado / Quimica Analitica / Mestre em Química

Nerve injury is a very common trauma affecting 300,000 people in Europe every year. Although autografts are currently the gold standard in surgery, they can cause loss of sensation and scar tissue formation. Artificial nerve conduits are a valid alternative for peripheral nerve repair. They can provide a confined environment during the regeneration process, enabling axons sprouting from the proximal to the distal nerve segments as well as reducing scar tissue formation. Poly-e-caprolactone (PCL) is a biocompatible and biodegradable polymer suitable for the fabrication of nerve guidances. In particular, previous works demonstrated that neural cells are able to adhere and proliferate on micropitted PCL films obtained through solvent casting. Also, short term studies showed that axons were able to bridge 1cm injury gap. In this work a 18 weeks long term in vivo experiment using a rat model was performed to investigate the reinnervation of end organ skin and muscle. PCL conduits were compared to autografts, with no significant differences in terms of regeneration and reinnervation. However, Schwann cells (SCs), the most important glial cells in the peripheral nervous system, showed poor attachment in vitro on PCL scaffolds; hence, surface modification was carried out in order to improve the material biocompatibility. The effect of both hydrophilicity and functional groups on SCs was first investigated. PCL films were then hydrolysed and aminolysed to modify the surface with carboxylic and amino groups respectively. Hydrolysed films increased remarkably the surface hydrophilicity, although topography and mechanical properties were not affected. Conversely, the tensile modulus and strength were significantly reduced by aminolysis, but still suitable for the desired application. The two treatments influenced also the morphology of SCs. It was demonstrated that cell elongation was induced by hydrophilic surfaces, whilst cells preferred cell-cell interaction when cultured on aminolysed films. However, cell proliferation was remarkably increased on the latter surfaces, confirming previous results obtained on substrates characterised by amino groups. These results confirmed that a good balance between hydophilicity and surface chemistry is necessary to guarantee the best cell response. In order to enhance both proliferation and morphology of SCs, arg-gly-asp (RGD) sequences were immobilised on the PCL film surface using two different reaction mechanisms. Carbodiimide chemistry was compared to a new mechanism developed in the present study based on the Thiol chemistry. Biological tests performed on these modified films demonstrated the improvement of SC response after the peptide immobilisation using the novel approach. Cell attachment and proliferation were three times higher compared to untreated PCL films. It was also observed that the presence of peptides on the film surface induced the formation of focal adhesion plaques by SCs, important for the perception of cellular signals when in contact with a particular substrate. Hence, a good balance between focal adhesion and adhesion forces was achieved after peptide immobilisation. Overall the results of this study showed that material functionalisation is very important for SC response and it will be fundamental for the production of artificial nerve conduits.

Cancer is the second leading cause of death in the world. It is therefore critically important to detect cancer in its early stage to significantly increase the survival rate of cancer patients. Circulating tumour cells (CTCs) are cancer cells that peel off from primary tumour and enter bloodstream in early stage of a cancer, and thus it has been established that these CTCs are reliable targets for early cancer diagnosis. However, background signal reduction and optimization of CTC capturing mechanisms are still significant challenges in CTC detections with high sensitivities and accuracies. To this end, we have developed an aptamers and dendrimers based ultra non-fouling microfluidic detection system for sensitive detections of circulating tumour cells. More specifically, we demonstrate a simple strategy to bind PDMS and SU-8 surfaces in order to prepare a hybrid microfluidic device and subsequently modify both surfaces simultaneously using poly(amidoamine) (PAMAM), a highly hydrophilic dendrimer to improve non-fouling properties of the hybrid microfluidic channel. The resulting hybrid microfluidic system shows a remarkable non-specific adsorption suppression of 99.7% when tested with hydrophobic microbead suspension, an ultra non-fouling performance that has not been reported before. This is significantly important for detections with high sensitivities. X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and water contact angle are used to characterize and confirm surface modifications. In addition, we investigate the combined effects of surface properties on surface non-fouling performance to both live and dead cells. (3-aminopropyl)-trimethoxysilane (APTMS), carboxyl functionalized PAMAM dendrimer (PAMAM-COOH) and amino functionalized PAMAM dendrimer (PAMAM-NH2) are used to provide different surfaces with various surface hydrophilicity, electric charge and roughness. We show that electric charge of a surface is the most important factor influencing non- specific adsorption of live cells to the surface while hydrophilicity/hydrophobicity of a surface is the most important factor for dead cells. Atomic force microscopy, water contact angle and microscopy are used to characterize and confirm surface modifications. To further exploit and improve capturing efficiency of target cancer cells, we investigate the effect of the length of spacers that tether capturing aptamer to the microfluidic surfaces on capturing performance of CCRF-CEM circulating tumour cells. Aptamers with different lengths of thymine base spacers are immobilized onto PAMAM dendrimer modified surfaces in microfluidic channels. We demonstrate that ten thymine bases spacer has the best length for sgc8 aptamer to form its secondary structure for CCRF-CEM cell capture. Water contact angle, and microscopy are used to characterize and confirm surface modifications. Taken together, the results of this study significantly highlight the importance of different considerations on surface modification and its optimizations when designing a microfluidic system for high sensitivity detection and biosensing applications.

Defect passivation and surface modification of perovskite semiconductors play a key role in achieving highly efficient and stable perovskite solar cells (PSCs) and light-emitting diodes (LEDs). This dissertation describes three novel strategies for such defect passivation and surface modification. In the first strategy, we demonstrate a facile approach using inorganic perovskite quantum dots (QDs) to supply bulk- and surface-passivation agents to combine high power conversion efficiency (PCE) with high stability in CH3NH3PbI3 (MAPbI3) inverted PSCs. This strategy utilizes inorganic perovskite QDs to distribute elemental dopants uniformly across the MAPbI3 film and attach ligands to the film’s surface. Compared with pristine MAPbI3 films, MAPbI3 films processed with QDs show a reduction in tail states, smaller trap-state density, and an increase in carrier recombination lifetime. The strategy results in reduced voltage losses and an improvement in PCE from 18.3% to 21.5%, which is among the highest efficiencies for MAPbI3 devices. The devices maintain 80% of their initial PCE under 1-sun continuous illumination for 500 h and show improved thermal stability. In the second strategy, we reduce the efficiency gap between the inverted PSCs and regular PSCs using a trace amount of surface-anchoring, long-chain alkylamine ligands (AALs) as grain and interface modifiers. We show that long-chain AALs suppress nonradiative carrier recombination and improve the optoelectronic properties of mixed-cation mixed-halide perovskite films. These translate into a certified stabilized PCE of 22.3% (23.0% PCE for lab-measured champion devices). The devices operate for over 1000 hours at the maximum power point (MPP), under simulated AM1.5 illumination, without loss of efficiency. Finally, we report a strategy to passivate Cl vacancies in mixed halide perovskite (MHP) QDs using non-polar-solvent-soluble organic pseudohalide (n-dodecylammonium thiocyanate (DAT)), enabling blue MHP LEDs with enhanced efficiency. Density-function-theory calculations reveal that the thiocyanate (SCN-) groups fill in the Cl vacancies and remove deep electron traps within the bandgap. DAT-treated CsPb(BrxCl1-x)3 QDs exhibit near unity (~100%) photoluminescence quantum yields; and their blue (~470 nm) LEDs are spectrally stable with an external quantum efficiency (EQE) of 6.3% – a record for perovskite LEDs emitting at the 460-480 nm range relevant to Rec. 2020 display standards.

付記する学位プログラム名: 充実した健康長寿社会を築く総合医療開発リーダー育成プログラム / 京都大学 / 新制・課程博士 / 博士(医科学) / 甲第23116号 / 医科博第127号 / 新制||医科||8(附属図書館) / 京都大学大学院医学研究科医科学専攻 / (主査)教授 藤田 恭之, 教授 渡邊 直樹, 教授 岩田 想 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

Since the discovery of carbon nanotubes (CNTs), they have gained much interest in many science and engineering fields. The modification of CNTs by introducing different functional groups to their surface is important for CNTs to be tailored to fit the need of specific applications. This dissertation presents several CNT-based systems that can provide biomedical and environmental advantages. In this research, polyethylenimine (PEI) and polyvinyl alcohol (PVA) were used to coat CNTs through hydrogen bonding. The release of doxorubicin (DOX, an anticancer drug) from this system was controlled by temperature. This system represents a promising method for incorporating stimuli triggered polymer-gated CNTs in controlled release applications. To create an acid responsive system CNTs were coated with 1,2-Distearoyl-snglycero- 3-Phosphoethanolamine-N-[Amino(Polyethylene glycol)2000]-(PE-PEG) and Poly(acrylic acid) modified dioleoy lphosphatidyl-ethanolamine (PE-PAA). An acidlabile linker was used to cross-link PAA, forming ALP@CNTs, thus making the system acid sensitive. The release of DOX from ALP@CNTs was found to be higher in an acidic environment. Moreover, near infrared (NIR) light was used to enhance the release of DOX from ALP@CNTs. A CNT-based membrane with controlled diffusion was prepared in the next study. CNTs were used as a component of a cellulose/gel membrane due to their optical property, which allows them to convert NIR light into heat. Poly(Nisopropylacrylamide) (PNIPAm) was used due to its thermo-sensitivity. The properties of both the CNTs and PNIPAm’s were used to control the diffusion of the cargo from the system, under the influence of NIR. CNTs were also used to fabricate an antibacterial agent, for which they were coated with polydopamine (PDA) and decorated with silver particles (Ag). Galactose (Gal) terminated with thiol groups conjugated with the above system was used to strengthen the bacterial targeting ability. The antibacterial activity of Ag/Gal@PDA@CNTs was examined on Escherichia coli. NIR was used to enhance the antibacterial activity of Ag/Gal@PDA@CNTs. Finally, CNTs were used as a support for methyl orange (MO) and palladium catalysts (Pd). MO was used due to its ability to enhance the catalyst activity. Pd@CNTs composites were used to test the reduction rate of nitrite with and without the addition MO. The results showed that over repeated cycles of nitrite reduction, the activity enhancement was lost. In summary, CNTs are promising building blocks for preparation of smart and stimuli responsive systems that have potential for a wide range of applications. The methods presented are simple and can be scaled up for industrial processing purposes.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18289号 / 工博第3881号 / 新制||工||1595(附属図書館) / 31147 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 岩田 博夫, 教授 木村 俊作, 教授 秋吉 一成 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20574号 / 工博第4354号 / 新制||工||1677(附属図書館) / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 今堀 博, 教授 秋吉 一成, 教授 白川 昌宏 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM