No description available.

Single molecule wide-field polarization fluorescence imaging is an experimental method to determine the self-assembly of molecules dispersed in a thin film. Through a combination of wide-field imaging and confocal spectroscopy, the effect of synthetic structure of the oligomeric PPV-based materials was investigated to understand the effect of conjugation length, role of hydrogen bonding side chains, and influence of regioregularity on controlling chromophore folding. By studying alkoxy-linked and alkyl-linked bis(2-ethylhexyl)-p-phenylene vinylene (BEH-PPV) units of varying lengths (three, five, or seven), it was determined that conjugation length controlled the extent of molecular ordering and emission properties. Comparison of the experimental results to molecular dynamics simulations performed by collaborators confirmed that the materials became increasingly ordered as conjugation length increased. Further regulation of the assembly can be obtained through inclusion of hydrogen bonding side chains as seen in the altered amine and carboxylic acid alkoxy-linked trimer BEH-PPV in contrast to the bulky side chain tert-butyl trimer. The study of regio-regular (RR) and regio-random (RRa) alkoxy-linked pentamer poly(2-methoxy-5-(2’-ethylhexyloxy)-p-phenylenevinylene) (MEH-PPV) illustrates the limited effect of regioregularity of the side chains on self-assembly. Through synthetic structure, it is possible to design highly ordered materials through control of conjugation length and selection of side chains. / text

No description available.

Polímeros conjugados têm sido tema de várias pesquisas devido à sua potencial idade de aplicação em dispositivos optoeletrônicos. Esses materiais apresentam propriedades luminescentes que envolvem processos fotofísicos ainda pouco compreendidos devido à grande variedade morfológica assumida por suas cadeias poliméricas. Neste trabalho, apresentamos os resultados que evidenciam a influência da morfologia molecular (ordenamento e empacotamento) no estado final da polarização da luz emitida (luminescência) pelos filmes de poli(p-fenileno vinileno) (PPV). Foram preparados filmes de PPV com diferentes ordenamentos moleculares, obtidos a partir dos seguintes métodos e técnicas de montagem de filmes: Casting, Spin-Coating (SC), Langmuir-Blodgett (LB) e Self-Assembly (S.A). As propriedades ópticas dos filmes foram investigadas através das medidas de absorção (UV-VIS) polarizada, de fotoluminescência (PL) em diferentes temperaturas (10 K a 300 K) e da análise da polarização da luz emitida. As medidas ópticas de absorção e de emissão de luz polarizada revelaram que os filmes obtidos por Langmuir-Blodgett, Casting e SelfAssembly com estiramento mostraram-se anisotrópicos, emitindo luz com polarização na direção do estiramento ou de imersão (quando preparados por LB), independente da direção de polarização da luz de excitação. Os filmes obtidos por Casting e SpinCoating, por outro lado, mostraram-se isotrópicos, emitindo luz com polarização na direção da polarização da luz de excitação. Os resultados obtidos da medida da polarização da luz emitida evidenciaram a ocorrência de transferência de energia entre moléculas. Deste modo, utilizou-se a teoria de Forster (radiação dipolo-dipolo) para explicar os resultados obtidos para os diferentes filmes de PPV, permitindo correlacioná-la com as propriedades ópticas e com o ordenamento molecular dos filmes / Since the first report of polymer light-emitting diodes (PLEDs), there have been considerable efforts to understand the emission process in luminescent polymers. However, many aspects related to this process are still under investigation, as the influence of morphology assumed by the polymeric chains. In this work we studied the influence of the molecular morphology, as ordering and packing, on the polarized light emitting of poly(p-phenylenevinylene) - PPV films. It was obtained films with different molecular arrangements from different assembly techniques, as Casting, Spin-Coating (SC), Langmuir-Blodgett (LB), and Self-Assembly (S.A). The optical property was investigated by absorption spectroscopy (UV-VIS), photoluminescence spectra (PL), and polarized light-emitting. The optical measurements disclosed that LB-PPV films, Casting-PPV and S.A-PPV stretched films were optically anisotropic, where the direction of the light-emitting is the same of the stretched direction or dipping preparation. In the other hand, Casting-PPV and Spin-Coating did not have such behavior, i.e., the emitted polarized light propagated in the same direction of the polarization of the excitation light. These data acquired from the optical measurements indicate a relation between morphology and photophysical process involving energy transfer via Forster

Luminescent conjugated polymers are widely used in organic optoelectronics. The device is fabricated by spin coating the polymer solutions into thin films. It is important to understand the chain conformation in the solution phase, which is mainly determined by the solubility properties of the solutes and the solvents. The purpose of this study is focused on the aggregate structures of MDMO-PPV polymer in the solution mixing of toluene, heptanes, and decahydronaphthalene. Compared to the polymer in toluene solution, the absorption and fluorescence spectra in the mixing solutions are red-shifted, which indicates the aggregation between polymer chains. In order to identify the aggregation is inter-chain or intra-chain effect, we perform concentration dependent measurements of the fluorescence spectra down to 10-10 M. Our results suggest that inter-chain aggregation is the major influence in the concentration. Since the intra-chain aggregation is strongly influenced by polymer concentration, we carry out the experiments to identify how the inter-chain effect influences at even lower concentrations. Fluorescence correlation spectroscopy (FCS) is used to determine the particle size at 10-12M concentration, which relates directly to the aggregation size. The results show that particle size in the poor solution is larger than that in the good solution. Therefore, we conclude that the change of the fluorescence spectra is caused by the inter-chain aggregation even at the concentration to 10-12M.

No description available.

No description available.

Orientador: Teresa Dib Zambon Atvars / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-10T13:29:22Z (GMT). No. of bitstreams: 1 Cossiello_RafaelDiFalco_D.pdf: 19466365 bytes, checksum: 4613f44ad7300b66e793fa6de43b2c82 (MD5) Previous issue date: 2007 / Resumo: O copolímero SAA (poli(estireno-co-ácido acrílico-co-1-metacrilato de pirenilmetila)) foi sintetizado por via radicalar em agua e caracterizado por analises termicas (DSC, TGA), espectroscopicas (NMR C e H, UV-VIS, FTIR, fluorescência estacionária e resolvida no tempo) e elétricas (eletroluminescência). As blendas com poli[2-metóxi-5-(2¿-etilóxi)-p-fenilenovinileno] MEH-PPV foram estudadas desde 0,01; 0,05; 0,10; 0,50; 1,0; 10,0; 25; 50; 75 e 90 (% em massa) de MEH-PPV em SAA para ánalise da evolucao da morfologia por microscopia óptica, de fluorescência e eletrônica de varredura em espessuras de 70 mm (fratura criogênica) e 70 nm (espessura do dispositivo). Em baixas concentracões os domínios de MEH-PPV se apresentam em forma de núcleos dispersos e empacotados e conforme se aumenta a concentracao de MEH-PPV, observa-se que há a coalescência destes núcleos até a formação de uma fase interconectada de uma rede tridimensional. As medidas de difração à altos angulos mostram que há uma preferência de orientação do MEH-PPV ao longo do substrato e nao influencia a isotropia do SAA devido a baixa miscibilidade entre estes polímeros. As unidades de 1-pirenil metila foram utilizadas para avaliar a polaridade do microambiente e o mecanismo de transferencia de energia entre o doador (SAA) e o receptor (MEH-PPV). A dependência do tempo de fluorescência das unidades 1-pirenilmetila com a concentracao do MEH-PPV fornece subsídios para concluir que ocorre interpenetração de cadeias e, portanto uma baixíssima solubilidade entre os dois polímeros. O melhor desempenho de eletroluminescência foi do dispositivo preparado a partir da mistura 50:50 de MEH-PPV:SAA, cuja corrente elétrica foi aumentada em 2,5 vezes e a luminância em 4 vezes se comparado com o dispositivo de MEH-PPV puro. A morfologia de fase interconectada se mostrou importante para um melhor processo de transporte de cargas. O copolímero de SAA permitiu uma melhor injeção de cargas devido aos grupos carboxila presentes das unidades de ácido acrílico / Abstract: The copolymer SAA poly(styrene-co- acrylic acid -co-1-pyrenylmethyl methacrylate) was synthesized by radical emulsion in water and characterized by thermal analyses (DSC, TGA), spectroscopic (NMR 13C and 1:00, UV-VIS, FTIR, stationary and time-resolved fluorescence) and electric (electroluminescence). The blends with poly[2-methoxy-5(2'ethylhexyloxy)-p-phenylenevinylene] (MEH-PPV) were studied from 0. 01; 0. 05; 0.10; 0.50; 1.0; 10.0; 25; 50; 75 and 90 (% in mass) of MEH-PPV in SAA to analyze the morphology evolution by optical, epifluorescence and electronic microscopy. The films were prepared in two thicknesses: one around 70 mm to be analyzed by cryogenic fractures and 70 nm, to be comparable with the device thickness. In low concentrations the domains of MEH-PPV appears dispersed nuclei and accrete when the concentration of MEH-PPV is increased forming an interconnected phase. The diffraction measures (WAXD) show a preference orientation of MEH-PPV along the substrate plane and it do not influences the SAA due the low miscibility between each other. The increase of the MEH-PPV concentration showed a redshift on electroluminescence spectrum due the inner filter and auto-absorption and re-emission effects. The units of 1-pyrenylmethyl were used to evaluate the polarity of the microenvironment and the mechanism of energy transfer of among the donor (SAA) and the acceptor (MEH-PPV). The timedependence of fluorescence with the increase of MEH-PPV concentration show that occurs an chain interpenetration following the fluorescence non-radiative energy transfer model. The best electroluminescent device was prepared using the mixture 50:50 of MEH-PPV:SAA. The interconnected phases are important for a better process of charge transport. The copolymer SAA allowed for a dilution effect avoiding the aggregation process and facilitating the charge injection processes. This technology of polymeric blends gave good results the increase of the luminance intensity and reduction of the voltage operation / Doutorado / Físico-Química / Doutor em Ciências

Polímeros conjugados têm sido tema de várias pesquisas devido à sua potencial idade de aplicação em dispositivos optoeletrônicos. Esses materiais apresentam propriedades luminescentes que envolvem processos fotofísicos ainda pouco compreendidos devido à grande variedade morfológica assumida por suas cadeias poliméricas. Neste trabalho, apresentamos os resultados que evidenciam a influência da morfologia molecular (ordenamento e empacotamento) no estado final da polarização da luz emitida (luminescência) pelos filmes de poli(p-fenileno vinileno) (PPV). Foram preparados filmes de PPV com diferentes ordenamentos moleculares, obtidos a partir dos seguintes métodos e técnicas de montagem de filmes: Casting, Spin-Coating (SC), Langmuir-Blodgett (LB) e Self-Assembly (S.A). As propriedades ópticas dos filmes foram investigadas através das medidas de absorção (UV-VIS) polarizada, de fotoluminescência (PL) em diferentes temperaturas (10 K a 300 K) e da análise da polarização da luz emitida. As medidas ópticas de absorção e de emissão de luz polarizada revelaram que os filmes obtidos por Langmuir-Blodgett, Casting e SelfAssembly com estiramento mostraram-se anisotrópicos, emitindo luz com polarização na direção do estiramento ou de imersão (quando preparados por LB), independente da direção de polarização da luz de excitação. Os filmes obtidos por Casting e SpinCoating, por outro lado, mostraram-se isotrópicos, emitindo luz com polarização na direção da polarização da luz de excitação. Os resultados obtidos da medida da polarização da luz emitida evidenciaram a ocorrência de transferência de energia entre moléculas. Deste modo, utilizou-se a teoria de Forster (radiação dipolo-dipolo) para explicar os resultados obtidos para os diferentes filmes de PPV, permitindo correlacioná-la com as propriedades ópticas e com o ordenamento molecular dos filmes / Since the first report of polymer light-emitting diodes (PLEDs), there have been considerable efforts to understand the emission process in luminescent polymers. However, many aspects related to this process are still under investigation, as the influence of morphology assumed by the polymeric chains. In this work we studied the influence of the molecular morphology, as ordering and packing, on the polarized light emitting of poly(p-phenylenevinylene) - PPV films. It was obtained films with different molecular arrangements from different assembly techniques, as Casting, Spin-Coating (SC), Langmuir-Blodgett (LB), and Self-Assembly (S.A). The optical property was investigated by absorption spectroscopy (UV-VIS), photoluminescence spectra (PL), and polarized light-emitting. The optical measurements disclosed that LB-PPV films, Casting-PPV and S.A-PPV stretched films were optically anisotropic, where the direction of the light-emitting is the same of the stretched direction or dipping preparation. In the other hand, Casting-PPV and Spin-Coating did not have such behavior, i.e., the emitted polarized light propagated in the same direction of the polarization of the excitation light. These data acquired from the optical measurements indicate a relation between morphology and photophysical process involving energy transfer via Forster

Dissertation work deals with the evaluation of the selected characters of promising peach varieties grown in the genepool collection and pilot testing block. The evaluation took place between year 2011 to 2013. The work can be divided into three thematical units. The first part deals with the health condition, specifically monitoring of the occurrence of European stone fruit yellows phytoplasma (ESFY) and the plum pox virus (PPV). The second part focuses on the physiological events occurring in flower buds (dormancy, microsporogenesis, frost resistance) and the third unit deals with pomological characteristics of varieties and the economic evaluation of varieties which are already introduced in the commercial cultivation. In the literature section the origin and the spread, world production of peaches and the current situation in the Czech Republic are descibed and a chapter about peach breeding is included as well. Further, chapters characterizing dormancy, microsporogenesis and frost hardiness are described in the work. Literature section also includes content substances and health-promoting substances in peach fruit. The last chapter describes the diseases causing economically significant losses in peaches. In the experimental part the incidence and symptoms of phytoplasma ESFY and synergism between PPV and ESFY was evaluated. The effect of the PPV infection on content of the total polyphenols and the antioxidant activity of fruits was investigated. Further, the termination of dormancy, microsporogenesis and frost resistance of flower buds was evaluated. Significant part of work was the pomological evaluation of selected varieties from genepool collection and evaluation of varieties in pilot testing block conditions. The results show that in peach orchards trees infected by phytoplasma ESFY show various symptoms of the disease which depend on host genotype. Synergism between Plum pox virus (PPV) and European stone fruit yellows phytoplasma (ESFY) has not been confirmed. PPV infection results in increased amount of the antioxidant activity and total polyphenols in peach fruits.Varieties can be divided into 3 groups by the term of termination of endogenous dormancy, paticulary, varieties with early termination, varieties with medium termination and varieties with late termination of dormancy. Evaluated varieties differ, either, in duration and date of occurence of phases of microsporogenesis. The process of dormancy and microsporogenesis of individual varieties is different and is influenced by the weather conditions of the year. There are differences in frost resistance between peach varieties. The highest degree of frost hardiness was set by the 'Lesiberian'. Studied peach varieties show differences in pomological, biological and economic characters. From the evaluated group of varieties the promising are 'Venus', 'Fantasia', 'Fidelia', 'Neve' and 'W 14', where the highest assessment had the variety 'Venus'. Based on evaluation of peach varieties grown in commercial orchards the best variety was 'Symphonie', which achieved consistently high yields and is characterized by good health. 'Fidelia' and 'Orion' were chosen as a mediumly suitable varieties for commercial orchards.