Ce travail de thèse propose une nouvelle approche pour la préparation de membranes à matrice mixte basée sur l’utilisation de copolymères à blocs et de nanoparticules inorganiques disposant de propriétés magnétiques. Des aggrégats de copolymères ont été préparés avec une morphologie variée (sphères, cylindres et vésicules) à partir du copolymère poly(acide méthacrylique)-b-poly(méthacrylate de méthyle). Ce dernier a été synthétisé par polymérisation radicalaire contrôlée par transfert de chaîne réversible par addition-fragmentation (RAFT) dans l’éthanol à 70°C. Des particules d’oxyde de fer ont, quant à elles, été préparées en présence de différents stabilisants à température variée pour permettre d’atteindre la charge de surface et les propriétés magnétiques recherchées. La structure des copolymères à bloc a permis d’obtenir à la fois des membranes hydrophobes via le procédé de séparation de phase induite par un non-solvant, ainsi que des membranes hydrophiles lorsque que la technique de spin-coating était appliquée aux aggrégats formés par auto-assemblage induit lors de la polymérisation. Grâce à l’étude détaillée des propriétés de filtration des membranes obtenues, la relation structure-propriété a été discutée sous l’action d’un champ magnétique externe. Enfin, la sensibilité au colmatage a été vérifiée via la filtration de solutions de protéines. Il a ainsi été démontré une diminution notable du colmatage sous champ magnétique, ouvrant de belles perspectives pour ces nouvelles membranes. / This thesis presents a new approach to produce mix matrix membranes using block copolymers and inorganic nanoparticles having magnetic properties. The polymeric nanoparticle with different morphologies (linear, Spheres, worms, and vesicles), from poly (methacrylic acid)-b-(methyl methacrylate) diblock copolymer, were synthesized using Reversible addition−fragmentation chain transfer polymerization (RAFT) in ethanol at 70 ֠C. The inorganic counterpart, iron oxide nanoparticles were prepared using different stabilizers at various temperatures to acquire the necessary surface charge and magnetic properties. The chemistry of the particles leads to form both hydrophobic membranes using non-solvent induced phase separation as well as a hydrophilic membrane by using the simple spin coating technique with the particles from polymerization induced self-assembly. By a detailed experimental study of the membrane filtration, the influence of different parameters on the process performance has been investigated with and without magnetic field. Finally, membrane fouling has been studied using protein solution. Also, the membrane performance was examined under magnetic field revealing the successful reduction in the fouling phenomenon making them new performant membranes in the area of membrane technology.

Orientador: Ana Flávia Nogueira / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T23:28:35Z (GMT). No. of bitstreams: 1 Freitas_IvoBernardide_M.pdf: 1962051 bytes, checksum: f313acbe4cbb5d4065bb7bb26e42e3ac (MD5) Previous issue date: 2013 / Resumo: Neste trabalho foram estudados filmes finos multicamadas baseados em nanopartículas inorgânicas e um polieletrolito inerte, depositados pela técnica layer-by-layer (LbL). O trabalho está dividido em três partes: 1) Síntese e caracterização de nanopartículas de CdSe; 2) Montagem de filmes LbL baseados no cloreto de poli(diallildimetilamônio) (PDDA) e nanopartículas de CdSe e TiO2; e 3) Estudos fotoeletroquímicos dos filmes. As nanopartículas sintetizadas foram caracterizadas por espectroscopia de absorção no ultravioleta-visível (UV-vis), espectroscopia de fluorescência, microscopia eletrônica de alta resolução (HRTEM) e difração de raios-X (DRX). As partículas sintetizadas não apresentaram a mesma qualidade daquelas reportadas pela literatura, apresentando grande número de defeitos e larga distribuição de tamanhos. Como não foi possível a separação adequada de nanopartículas de diferentes tamanhos, optou-se por dar continuidade ao trabalho com somente um tamanho obtido. Foram fabricados filmes contendo TiO2 e PDDA, filmes contendo CdSe e PDDA e filmes contendo TiO2, CdSe e PDDA. Estes foram caracterizados por espectroscopia de absorção no UV-vis, espectroscopia de fluorescência, microscopia de força atômica (AFM) e espectroscopia Raman. Os filmes apresentaram um crescimento linear a cada bicamada realizada. Visando melhorar a qualidade dos filmes fabricados um tratamento com brometo de hexadeciltrimetilamonio (CTAB) foi utilizado. Os filmes de nanopartículas de CdSe com tratamento apresentaram uma quantidade de defeitos menor em relação aos filmes sem tratamento. Os fotoeletrodos foram caracterizados por medidas de fotocorrente em função do tempo (fotocronoamperometria). Os filmes contendo TiO2 e PDDA apresentaram valores de fotocorrente, entre 2 e 50 mA cm, exibindo comportamento de semicondutor do tipo-n. Ja os filmes contendo CdSe e PDDA apresentaram valores baixos de fotocorrente (2 mA cm). Mesmo após a realização do tratamento com CTAB e a incorporação de nanopartículas de TiO2 nos filmes não observou-se uma significante alteração nestes valores / Abstract: In this work, multilayered thin films based on inorganic nanoparticles and an inert polyelectrolyte deposited by the layer-by-layer technique were studied. The work was divided in three parts: 1) Synthesis and characterization of CdSe nanoparticles; 2) Assembly of LbL films based in poly(diallyldimethylammonium chloride) (PDDA) , CdSe and TiO2 nanoparticles; 3) Photoelectrochemical studies of the films. The nanoparticles synthetized were characterized by absorption spectroscopy, fluorescence spectroscopy, high resolution electron microscopy (HRTEM) and X-ray diffraction. The synthesized nanoparticles didn¿t show the same quality of those reported in literature. They presented a large number of defects and a broad size distribution. As it was not possible to obtain nanoparticles of different sizes, we decided to continue the work with only one nanoparticle size. Films were fabricated using CdSe and PDDA, TiO2 and PDDA, and CdSe, PDDA and TiO2. They were characterized by absorption spectroscopy, fluorescence spectroscopy, atomic force microscopy (AFM) and Raman spectroscopy. The films showed a linear increase to each bilayer performed. In order to improve the films quality containing CdSe nanoparticles, a treatment using hexadecyltrimethylammonium bromide (CTAB) was performed. As a result, the treated films showed a smaller number of defects compared to the films without treatment. The photoelectrodes were characterized by measurements of photocurrent versus time (photochronoamperometry). The films containing TiO2 and PDDA showed appreciable values of photocurrent, between 2 and 50 mA cm, exhibiting an n-type semiconducting behavior. However, the films containing CdSe and PDDA showed low photocurrent values (2 mA cm). Even after the treatment with CTAB and the incorporation of the TiO2 nanoparticles in the films, no remarkable improvement in the photocurrent values was observed / Mestrado / Quimica Inorganica / Mestre em Química

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24074号 / 理博第4841号 / 新制||理||1692(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 寺西 利治, 教授 島川 祐一, 教授 倉田 博基 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

This work studies various properties of polymer layers and hybrid layers containing inorganic nanoparticles. MEH-PPV and Polythiophene films are characterized by different experimental techniques. Dark J-V characteristics were measured at different temperatures and the mobility of holes was evaluated in a few cases. Photovoltage spectra are used for a determination of the exciton diffusion length and the SPV method is discussed. The influence of the inorganic nanoparticles CdS and ZnO incorporated into the polymer layers is studied by various experimental methods and the applications of these layers in the inorganic-organic hybrid solar cells are discussed. The inorganic nanoparticle size distributions are obtained by several experimental techniques and the results correspond with the assumptions.

Orientadores: Ana Flavia Nogueira, Jonas Gruber / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-14T17:00:59Z (GMT). No. of bitstreams: 1 Freitas_JilianNeide_D.pdf: 8511541 bytes, checksum: 16cafd5a8e1e1563c206ffa381e7c35a (MD5) Previous issue date: 2009 / Resumo: Este trabalho consistiu no desenvolvimento e caracterização de materiais para aplicação em células fotovoltaicas híbridas. No Capítulo I, uma introdução geral sobre o funcionamento e estado da arte de células solares, e sobre as propriedades de polímeros condutores e nanopartículas inorgâncias é apresentada. O Capítulo II contém os objetivos deste trabalho. No Capítulo III, foram investigados novos polímeros condutores, baseados na combinação de unidades fluoreno com unidades tiofeno e/ou benzeno. As propriedades fotofísicas, eletroquímicas e de transporte de cargas foram caracterizadas, e esses polímeros foram então combinados com um derivado solúvel de fulereno (PCBM) e os compósitos formados (heterojunção) foram aplicados em células solares com configuração ITO | PEDOT:PSS | Heterojunção | LiF | Al. A seguir, foram sintetizadas nanopartículas de CdSe com diferentes tamanhos, usando um método descrito na literatura. Essas partículas foram caracterizadas por medidas de absorção e emissão, voltametria cíclica (VC), difração de Raios-X (DRX) e microscopia eletrônica de transmissão (TEM), conforme apresentado no Capítulo IV. Os polímeros investigados inicialmente foram combinados com as nanopartículas de CdSe, e esses materiais foram utilizados na montagem de células solares híbridas. De modo geral, os dispositivos apresentaram valores baixos de fotocorrente, o que foi atribuído ao fato de as nanopartículas inorgânicas não transportarem elétrons de forma efetiva nesses dispositivos. A seguir, propôs-se um novo sistema, em que a heterojunção constitui na mistura ternária polímero/CdSe/PCBM. Esses dispositivos foram caracterizados por curvas de corrente-potencial e pela resposta espectral do sistema, mostrando resultados extremamente promissores. Os sistemas ternários foram então investigados por diversas técnicas, como absorção, emissão, DRX, VC, TEM e microscopia de força atômica, a fim de determinar a atuação de cada componente da mistura ternária quando aplicados nas células solares. Esses resultados são apresentados no Capítulo V. No Capítulo VI, novos polímeros condutores derivados do polifluoreno, contendo unidades funcionais como grupos piridina, ou compostos aromáticos do tipo "push-pull", foram sintetizados pelo método de Gilch. A estrutura desses polímeros foi desenhada visando sua aplicação nas células híbridas, combinandoos com as nanopartículas de CdSe previamente sintetizadas. Esses materiais foram caracterizados por ressonância magnética nuclear de hidrogênio, espectroscopia no Infravermelho com transformada de Fourier. cromatografia por permeação em gel, análises térmicas e medidas eletroquímicas e de fotofísica. No Capítulo VII, propôs-se a introdução de um corante orgânico comercial (Disperse Red 1), como terceiro componente em uma mistura de poli(fluorenilenovinileno) e PCBM, visando aumentar a absorção de luz pela camada ativa do dispositivo. Foi realizado um extenso estudo usando técnicas fotofísicas e eletroquímicas para investigar o efeito da adição do corante, bem como determinar quais os tipos de processos (transferência de elétrons ou energia) ocorrem no sistema ternário. Finalmente o Capítulo VIII contém as principais conclusões deste trabalho e perspectivas de continuação para esta linha de pesquisa. / Abstract: This PhD Thesis investigated the development and characterization of new materials aiming at the application in hybrid solar cells. In Chapter I, a general introduction on the working principles and state-of-the-art of the organic solar cells, properties of the conducting polymers and the inorganic nanoparticles are presented. Chpater II highlights the aims of this work. In Chapter III, new conducting polymers based on the combination of fluorene, thiophene and/or benzene units are investigated. The photophysical and electrochemical characteristics, and charge mobility, are discussed. The polymers were also combined with a soluble fullerene derivative (PCBM) and these composites were used as active layer in bulk-heterojunction solar cells with the following configuration: ITO | PEDOT:PSS | Heterojunction | LiF | Al. Then, CdSe nanoparticles with different sizes were synthesized using a well-established method, and characterized using absorption and emission measurements, cyclic voltammetry (CV), X-ray diffraction (XRD) and transmission electron microscopy (TEM), as presented in Chapter IV. The previously characterized polymers were combined with the CdSe nanoparticles, and the nanocomposites were used to assemble hybrid solar cells. The devices showed very low photocurrent values, which were attributed to a poor electronic transport in the nanoparticles phase. Thus, a new system was suggested, based on a mixture of polymer/CdSe/PCBM. The photocurrent-potential curves and spectral response of the devices assembled with the ternary systems were evaluated, leading to very promising results. The absorption, emission, XRD, CV, TEM and atomic force microscopy measurements of the films were also performed to investigate/elucidate the role of each component in the ternary systems, as discussed in Chapter V. In Chapter VI, new conducting polymers based on poly(fluorenylenevinylene) containing functional units, such as pyridine or push-pull type aromatic units, were synthesized via the Gilch route. The structures of these materials were designed aiming at their application in hybrid solar cells, in combination with the previously synthesized CdSe nanoparticles. The polymers were characterized by magnetic nuclear resonance, Fourier transform infrared spectroscopy, gel permeation chromatography, and thermal, electrochemical and photophysical measurements. These polymers were combined with CdSe and/or PCBM and used as active layer in solar cells. In Chapter VII the addition of the commercial organic dye Disperse Red 1 in the mixture of poly(fluorenylenevinylene)/PCBM to enhance the light absorption in the active layer was investigated. A systematic study using photophysical and electrochemical measurements was performed in order to elucidate the effect of the dye addition, as well as the energy or electron transfer processes in this new ternary system. Finally, Chapter VIII summarizes the main conclusions of this work and highlights some perspectives for this exciting research filed. / Doutorado / Quimica Inorganica / Doutor em Ciências

Yes / In recent years, tremendous progress has been made in the treatment of acute myocardial infarction (AMI), but pathological ventricular remodeling often causes survivors to suffer from fatal heart failure. Currently, there is no effective therapy to attenuate ventricular remodeling. Recently, nanoparticles-based drug delivery system is widely applied in biomedicine especially in cancer and liver fibrosis, owing to its excellent physical, chemical, and biological properties. Therefore, using nanoparticles as delivery vehicles of small molecules, polypeptides, etc to improve post-infarct ventricular remodeling are expected. In this review, we summarized the updated researches in this fast-growing area and suggested further works needed.

Recent research demonstrated that polymer based nanocomposites (PNCs) have been engineered in order to improve the arc interruption capability of the circuit breakers. PNCs are the combination of nano-sized inorganic nanoparticles (NPs) and polymers, opened up new developments in materials science and engineering applications. Inorganic NPs are selected based on their physical and chemical properties which could make multifunctional PNCs in order to interrupt the electrical arcs effectively. In particular, we presented the PNCs fabricated by using CuO, Fe3O4, ZnO and Au NPs in a poly (methyl methacrylate) (PMMA) matrix via in-situ polymerization method, recently developed method to avoid NPs agglomeration, leading to good spatial distribution in the polymer matrix. Thus, several samples with various wt% of NPs in PMMA matrix have been fabricated. These PNCs have been characterized in detail for the morphology of NPs, interaction between NPs and polymer matrix, and radiative/thermal energy absorption properties. In the next stage, PNCs are tested to determine their arc interruption performance and impact on the electrical arcs of current 1.6 kA generated using a specially designed test set-up. When PNCs interact with the electrical arcs, they generate ablation of chemical species towards core of the electrical arc, resulting in cooling-down the arc due to strong temperature and pressure gradient in the arc quenching domain. This thesis demonstrates for the first time that these engineered PNCs are easily processed, reproducible, and can be used to improve the arc interruption process in electrical switching applications. / Ny forskning har visat att polymerbaserade nanokompositer (PNCs) har utformats för att förbättra strömbrytares förmåga att undvika ljusbågar vid överslag. PNCs är en kombination av nanostora oorganiska nanopartiklar (NP) och polymerer, som har öppnat upp för ny utveckling inom materialvetenskap och tekniska tillämpningar. Oorganiska NP väljs baserat på deras fysikaliska och kemiska egenskaper som kan hjälpa PNCs att motverka elektriska ljusbågar effektivt. I synnerhet, presenterade vi PNCs tillverkade genom användning av CuO, Fe3O4, ZnO och Au NP i en poly (metylmetakrylat) (PMMA)-matris via in situ-polymerisationsmetod, nyligen utvecklad för att undvika NP-agglomerering, vilket leder till god rumslig fördelning i polymermatrisen. Därför har flera prover med olika vikt% av NP i PMMA-matris tillverkats. Dessa PNCs har utvärderats i detalj för NP-morfologi, interaktion mellan NP och polymermatris, och strålnings- och värmeenergiabsorption. I nästa skede testas PNCs för att bestämma deras förmåga att undvika ljusbågar och påverkan på de elektriska ljusbågarna av 1,6 kA strömstyrka, genererade med hjälp av en specialdesignad test-set-up. När PNCs interagerar med de elektriska ljusbågarna, genererar de ablation av kemiska ämnen mot kärnan i den elektriska ljusbågen, vilket resulterar i nedkylning av ljusbågen på grund av starka temperatur- och tryckgradienter i området. Denna avhandling visar för första gången att dessa konstruerade PNCs är lätta att framställa, reproducerbara, och kan användas för att förbättra avbrottsprocessen för ljusbågen i elektriska kopplingstillämpningar. / <p>QC 20170303</p>

Abstract This thesis presents a novel method for fabricating quantum dot light-emitting devices (QDLEDs) based on colloidal inorganic light-emitting nanoparticles incorporated into an organic semiconductor matrix. CdSe core/ZnS shell nanoparticles were inkjet-printed in air and sandwiched between organic hole and electron transport layers to produce efficient photon-emissive media. The light-emitting devices fabricated here were tested as individual devices and integrated into a display setting, thus endorsing the capability of this method as a manufacturing approach for full-colour high-definition displays. By choosing inkjet printing as a deposition method for quantum dots, several problems currently inevitable with alternative methods are addressed. First, inkjet printing promises simple patterning due to its drop-on-demand concept, thus overruling a need for complicated and laborious patterning methods. Secondly, manufacturing costs can be reduced significantly by introducing this prudent fabrication step for very expensive nanoparticles. Since there are no prior demonstrations of inkjet printing of electroluminescent quantum dot devices in the literature, this work dives into the basics of inkjet printing of low-viscosity, relatively highly volatile quantum dot inks: piezo driver requirements, jetting parameters, fluid dynamics in the cartridge and on the surface, nanoparticle assembly in a wet droplet and packing of dots on the surface are main concerns in the experimental part. Device performance is likewise discussed and plays an important role in this thesis. Several compositional QDLED structures are described. In addition, different pixel geometries are discussed. The last part of this dissertation deals with the principles of QDLED displays and their basic components: RGB pixels and organic thin-film transistor (OTFT) drivers. Work related to transistors is intertwined with QDLED work; ideas for surface treatments that enhance nanoparticle packing are carried over from self-assembled monolayer (SAM) studies in the OTFT field. Moreover, all the work done in this thesis project was consolidated by one method, atomic force microscopy (AFM), which is discussed throughout the entire thesis.

Proteins are a diverse category of biomolecules with great therapeutic potential. Intracellular delivery of proteins can augment the deficient activities of dysfunctional or poorly expressed innate proteins and therefore represents a promising strategy to treat the associated diseases. One major barrier to intracellular protein delivery is the translocation of the protein across the cellular membrane. Endocytosis provides an important pathway for protein nanocarriers to enter cells across the plasma membrane. However, the cargo protein must then promptly escape from the endosomes to avoid degradation in the lysosome and to exert its cellular function. Previously, we reported a cationic lipid-coated magnesium phosphate nanoparticle (LPP) system for intracellular protein delivery. The intracellular delivery of catalase, an antioxidant enzyme, by LPP protected MCF-7 cells from a lethal level of exogenous H2O2 and lowered the reactive oxygen species (ROS) levels in EA.hy926 cells. These findings prompted us to further develop LPP to evaluate its protein delivery in animals. Two categories of LPP formulations, catalase-encapsulated (CE) LPP and catalase-complexed (CC) LPP, were successfully prepared by a modular approach. Catalase-encapsulated liposomes (CE LP) were prepared by hydrating a thin-film of lipids with catalase solution followed by extrusion. However, extrusion of CE LP resulted in substantial loss of catalase activity. Catalase-complexed liposomes (CC LP) were prepared by first extruding cationic liposomes with a LIPEX extruder and then mixing with catalase solution. The resultant CC LP was much smaller than CE LP and preserved all the catalase activity. Magnesium phosphate nanoparticles (MgP NP) were prepared by the microemulsion precipitation technique. CE LP or CC LP were mixed with MgP NP to yield LPP formulations (CE LPP or CC LPP, respectively). The formulations were then rendered isotonic with glucose (5% w/v). Transmission electron microscopy (TEM) confirmed the proposed structure of LPP comprising a shell of lipid bilayers with a core of MgP NP. Furthermore, TEM showed drastic morphological changes of LPP formulations at acidic pH, consistent with an osmotic explosion. The LPP formulations were administered by intravenous or intranasal routes to CD-1 mice. LPP formulations of fluorescently labeled catalase distributed substantially into the lung following intranasal administration, whereas intravenous administration of the same formulations caused catalase distribution mainly into the liver. In addition, intranasal administration of both the LPP formulations yielded higher pulmonary catalase activity and lowered the ROS levels in the healthy lung compared to free catalase solution. Based on these results, LPP’s antioxidant effects were further evaluated in mice with lipopolysaccharide-induced acute lung injury (ALI). Lack of LPP distribution into the lung following intranasal administration indicated that intranasal dosing did not deliver catalase substantially into inflamed lungs. In corroboration, the inflammatory biomarker tumor necrosis factor-alpha (TNF-α) remained unchanged after intranasal dosing of LPP formulations. Intratracheal dosing of LPP formulations delivered the fluorescently labeled catalase deep into the lung and significantly reduced TNF-α production in the inflamed lungs compared to free catalase solution. CC LPP, which was smaller and which better preserved catalase activity than CE LPP, showed greater intrapulmonary catalase activity compared to CE LPP in both healthy and inflamed lungs. Taken together, LPP represents a promising nanocarrier for intracellular protein delivery.

There are many challenges in materializing the applications utilizing inorganic nanoparticles. The primary drawback is the degradation of properties due to aggregation and sintering either due to elevated temperatures or prevailing chemical/electrochemical conditions. In this thesis, various wet chemical synthesis methods are developed to obtain metal nanostructures with enhanced thermal stability. The thesis is organized as below: Chapter 1 presents the problems and challenges in materializing the application of nanomaterials associated with the thermal stability of nanomaterials. A review of the existing techniques to improve the thermal stability and the scope of the thesis are presented. Chapter 2 gives a summary of the various materials synthesized, the method adopted for the synthesis and the characterization techniques used in the material characterization. Chapter 3 presents a general template-less strategy for the synthesis of nanoporous alloy aggregates by controlled aggregation of nanoparticles in the solution phase with excellent control over morphology and composition as illustrated using PdPt and PtRu systems as examples. The Pt-based nanoporous clusters exhibit excellent activity for methanol oxidation with good long term stability and CO tolerance. Chapter 4 presents a detailed study on the thermal stability of spherical mesoporous aggregates consisting of nanoparticles. The thermal stability study leads to a general conclusion that nanoporous structures transform to hollow structures on heating to elevated temperatures before undergoing complete densification. Chapter 5 presents a simple and facile method for the synthesis of single crystalline intermetallic PtBi hollow nanoparticles. A mechanism is proposed for the formation of intermetallic PtBi hollow structures. The intermetallic PtBi hollow structures synthesised show excellent electrocatalytic activity for formic acid oxidation reaction. Chapter 6 presents a robust strategy for obtaining a high dispersion of ultrafine Pt and PtRu nanoparticles on graphene. The method involves the nucleation of a metal precursor phase on graphite oxide surfaces and subsequent reduction with a strong reducing agent. The electrocatalytic activity of the composites is investigated for methanol oxidation reaction. Chapter 7 presents a microwave-assisted synthesis method for selective heterogeneous nucleation of metal nanoparticles on oxide supports leading to the synthesis of high activity catalysts. The catalytic activity of the hybrids synthesized by this method for investigated for H2 combustion. Chapter 8 presents thermal stability studies carried out on nanostructures by in-situ heating in transmission electron microscope. The microstructural changes during the sintering process are observed in real time and the observations lead to the understanding of the mechanism of particle growth and sintering. At the end, the results of the investigations were summarized with conclusions drawn.