This thesis investigates the electrochromic NixW1-x oxide thin film system, where 0 < x < 1. The thin films were deposited by reactive DC magnetron co-sputtering from one Ni and one W metal target. In addition, Ni oxide was deposited with water vapor added to the sputtering gas. The different compositions were structurally characterized by X-ray diffraction, X-ray photoelectron-, Rutherford backscattering- and Raman spectroscopy. Possible nanostructures were studied by ellipsometry together with effective medium theory. Optical and electrochemical properties were investigated by spectrophotometry and cyclic voltammetry in 1 M lithium perchlorate in propylene carbonate (Li-PC). Li-PC electrolyte was used as it is being compatible with both W and Ni oxides. Few studies have previously been made on Ni oxides in Li-PC. Films with high Ni content, 0.85 < x < 1, were polycrystalline and all other films were amorphous. W-rich films, x < 0.5, consisted of a mixture of W oxide and NiWO4 -phases, and the Ni-rich samples, x > 0.5, probably consisted of hydrated Ni oxide and NiWO4 -phases. Films with 0 < x < 0.3 showed electrochromic properties similar to W oxide, and films with 0.7 < x < 1 behaved as Ni oxide. For 0.4 < x < 0.7 no optical change was seen. At the border of cathodic electrochromic and non-electrochromic behavior, i.e. x ~ 0.4, the sample behaved as an optically passive intercalation material. The transmittance change was 0.45 and 0.15 for the W-rich and Ni-rich films, respectively. Ni addition to W oxide improved the coloration efficiency. For the Ni-rich films the charge insertion/extraction and optical modulation was low and an aging effect resulted in strong bleaching of the samples. The advantage of W addition to Ni oxide was that the transparency at the bleached state was enhanced. Moreover, it was found that the hydrous character of the Ni oxide had a large impact on the electrochromic performance, both when electrochemically cycled in KOH and in the non-aqueous Li-PC.

Orientador: Prof. Dr. Maurício Domingues Coutinho Neto / Tese (doutorado) - Universidade Federal do ABC. Programa de Pós-Graduação em Ciência e Tecnologia/Química, 2015. / The theoretical study of the interaction between biomolecules that interact with DNA has been growing in recent years. Understanding the mechanism of action of these biomolecules in the process of intercalation with DNA is of fundamental importance in the development of new drugs for the treatment of genetic and parasites diseases. Among these diseases, malaria is one of the most important worldwide and is caused by a protozoan parasite. The resistance of plasmodium P. falciparum, which causes the most severe form of the disease to antimalarial drugs, has become a growing problem and the search for more effective drugs is urgent. Many of these drugs interact with DNA by intercalation process mediated mainly by dispersion interactions that contribute significantly to the stability of the complex intercalator-DNA. With this idea, we propose to investigate theoretically the interactions that occur between an antimalarial drug, the cryptolepine and its derivatives, when intercalated between base pairs of DNA by means of first principles methods based on Density Functional Theory and classical molecular dynamics methods. The dispersion effects were included in the DCACP approach ( Dispersion Correct-Atom Centered Potentials). In the classical approach, we used specific force fields such as ff99bsc0 and GAFF for the treatment and quality of intercalation energy. The DCACP results showed that the cryptolepine interacts strongly with DNA, whose the interaction energy was -38.6 kcal/mol. Furthermore, the cryptolepine intercalation preference between non-alternating CG sites was confirmed by more stable configuration energy in the crystal. The free intercalation energy of drug calculated by molecular dynamics was about -30 kcal/mol showing that this process can be energetically favorable. The cryptolepine has a potent in vitro activity against malaria parasites in addition to being the first of a class of intercalating agents preferably having a intercalation sites of the DNA cytosine-guanine by a non-alternating and parallel intercalation mode. This suggests that this new intercalating process should lead to the development of new drugs against malaria and the theoretical study proposed in this work can assist in the design of experimental work.

Orientador: Oswaldo Luiz Alves / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-07T03:13:18Z (GMT). No. of bitstreams: 1 DeSantis_MarcoAurelioCulhari_M.pdf: 3832539 bytes, checksum: 536117264acf4225d0c02eb3b2150a00 (MD5) Previous issue date: 2006 / Resumo: O presente Trabalho trata da obtenção do óxido HTaWO6.H2O nas formas: bidimensional (trirrutilo lamelar) e tridimensional (pirocloro com canais). Os compostos foram preparados a partir de reações de troca iônica do metal alcalino pelo próton nas respectivas fases (Li ou K)TaWO6. A síntese das fases precursoras envolveu típicas reações de estado sólido. Neste processo, foi estudada a evolução das estruturas em função da variação da temperatura e do tempo de síntese, no intervalo entre 350 e 850°C. As fases cristalinas com as estruturas trirrutilo e pirocloro apresentam propriedades estruturais e eletrônicas que as habilitam a aplicações tecnológicas. Por exemplo, na forma de matrizes hospedeiras para a obtenção de nanocompósitos orgânico/inorgânicos, assim como na forma de eletrólitos sólidos. Ambos os sólidos, obtidos na forma de pó, foram funcionalizados por reações de troca iônica do próton por íons Ag, conduzindo à formação dos compostos do tipo H1-xAgxTaWO6.H2O com estrutura bi- e tridimensional. Adicionalmente, o composto apresentando a estrutura trirrutilo (lamelar) foi utilizado como matriz hospedeira para a reação de intercalação de duas aminas lineares (n-butilamina e n-dodecilamina). As reações conduziram à formação dos compostos de intercalação: HTaWO6.H2O@C4H11N e HTaWO6.H2O@C12H27N. Os materiais preparados foram caracterizados por diferentes técnicas, dentre elas: difratometria de raios X (XRD), fluorescência de raios X (XRF), espectroscopias Raman e infravermelho (FTIR) e termogravimetria (TG). Os resultados dos ensaios revelaram os comportamentos distintos das estruturas frente às reações de troca iônica e intercalação/inserção. No estudo da evolução das estruturas precursoras, os resultados revelaram a possibilidade de obtenção dos compostos (Li ou K)TaWO6, via reação no estado sólido, com reduções substanciais do tempo e da temperatura de síntese em relação aos procedimentos descritos na literatura / Abstract: The present work is about the preparation of the HTaWO6.H2O oxide with bidimensional (trirutile) and tridimensional (pyrochlore) structures. These compounds were prepared by ion-exchange reactions of the alkaline metal by the proton, starting from precursor (Li or K)TaWO6. The synthesis of the precursors compounds involved typical solid state reactions. In the process, the structural evolution of the materials was evaluated related to the temperature (350 ¿ 850 ºC) and time of synthesis. Trirutile and pyrochlore crystalline phases present structural and electronic properties that make technological applications become possible, such as host matrices for the preparation of organic/inorganic nanocomposites and as solid electrolytes. Both solids, obtained as powders, were functionalized by ion exchange reactions of the proton by Ag ions, leading to the formation of compounds H1-xAgxTaWO6.H2O, with bi- and tridimensional structure. In addition, the solid presenting trirutile (lamellar) structure was used as a host matrix for intercalation of two linear amines (n-butylamine and n-dodecylamine). Reactions yielded the following intercalation products: HTaWO6.H2O@C4H11N and HTaWO6.H2O@C12H27N. The ¿as prepared¿ materials were characterized by different techniques, such as X-ray difratometry (XRD), X-ray fluorescence (XRF), Raman spectroscopy, infrared spectroscopy (FTIR) and thermogravimetry (TG). The results revealed different behavior of the structures towards ion exchange and intercalation/insertion reactions. In the study of structural evolution of the precursors materials, results revealed the possibility of preparation of the compounds (Li or K)TaWO6 via solid state reactions, with substantial reduction of time and temperature of synthesis related to the procedures described in the literature / Mestrado / Quimica Inorganica / Mestre em Química

Orientador: Heloise de Oliveira Pastore / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-16T00:58:08Z (GMT). No. of bitstreams: 1 Quites_FernandoJunior_M.pdf: 5104737 bytes, checksum: f5fb8d7a9b43d3881aa0cc1477b348f5 (MD5) Previous issue date: 2010 / Resumo: Na primeira parte deste trabalho, novos materiais híbridos foram desenvolvidos com a intercalação dos polieletrólitos poli(cloreto de dialildimetilamônio) PDDA e poli(cloreto de alilamina) PAH no espaço interlamelar do pentóxido de vanádio (V2O5) e do trióxido de molibdênio (MoO3) usando tratamento hidrotérmico. Um estudo sistemático da síntese dos materiais híbridos pela reação direta dos policátions PDDA e PAH com V2O5 e com MoO3 mostrou que o espaço interlamelar destes óxidos expande significativamente após a intercalação destas espécies convidadas. Foi também mostrado que a intercalação dos polieletrólitos ocorre apenas quando alguns íons metálicos da rede inorgânica são reduzidos, ou seja, íons V são reduzidos a V e íons Mo são reduzidos a Mo. Sendo assim, os polieletrólitos atuam como entidades contrabalanceadoras de cargas, pois com a redução são geradas cargas negativas na lamela inorgânica e os polieletrólitos entram nos espaços lamelares destes óxidos para contrabalancear estas cargas e ao mesmo tempo, como esses polímeros possuem alta densidade de carga, eles carregam pares iônicos para dentro do espaço interlamelar. Estes sítios podem ser usados como trocadores aniônicos. Os materiais híbridos produzidos [PDDACl]0.24[PDDA]0.29V2O5 e [PAHCl]0.28[PAH]0.47V2O5 exibiram aproximadamente 45,0 e 38,0% de íons cloretos trocáveis e os materiais híbridos [PDDACl]0.26[PDDA]0.24MoO3 e [PAHCl]0.18[PAH]0.38MoO3apresentaram 52,9 e 32,0%, respectivamente de íons cloretos trocáveis que podem ainda ser usados para a troca aniônica. Na segunda parte deste trabalho, os materiais híbridos produzidos baseados em V2O5 e MoO3, foram usados para ocluir o corante aniônico cianina Iris 3.5b. Neste caso, os pares iônicos ocluídos no espaço interlamelar foram usados como sítios de troca iônica pela saída de íon cloreto e entrada de cianina. A presença do corante foi evidenciada nos materiais obtidos através de bandas de absorção na região de 520- 580 nm e por uma fluorescência significante relacionada à molécula de corante com uma emissão na região de 600-617nm / Abstract: In the first part of this work, novel hybrid materials were developed by insertion of poly(diallymethylammonium chloride) PDDA and poly(allylamine hydrochloride) PAH polyelectrolytes into V2O5 and MoO3 interlayer spaces using hydrothermal treatment. A systematic study of the synthesis of hybrids materials by direct in situ reaction of PDDA and PAH polycations with V2O5 and MoO3 powders showed that the interlayer space of V2O5 and MoO3 expands significantly upon intercalation using PDDA and PAH polyelectrolytes. Reduction of V to V and Mo to Mo intercalation of the polyelectrolytes as charge balancing entities possible and, consequently, the generation of anionic exchange sites in theses oxides layers. The hybrid materials produced, [PDDACl]0.24[PDDA]0.29V2O5 and [PAHCl]0.28[PAH]0.47V2O5 exhibited approximately 45.0 % and 38.0 % of chloride ions still available for anionic exchange, respectively. The hybrids [PDDACl]0.26[PDDA]0.24MoO3 and [PAHCl]0.18[PAH]0.38MoO3 presented approximately 52,9 % and 32,0 % of chloride ions anionic exchange, respectively. In the second part of this study, these materials were used to encapsulate the cyanine anionic dye. The presence of the dye was evidenced by significant fluorescence, with emission band centered at 605-620 nm regions / Mestrado / Quimica Inorganica / Mestre em Química

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / A presente dissertaÃÃo investiga a relaÃÃo entre fatores extralingÃÃsticos (sexo, idade e registro) e a sÃnclise pronominal no PORCUFORT. A partir da anÃlise desse corpus foi constatado que tais fatores em nada influenciam o comportamento dos substantivos clÃticos. à tambÃm preocupaÃÃo desse trabalho fazer uma revisÃo das diversas opiniÃes de importantes estudiosos sobre os traÃos que marcam um grupo especÃfico de vocÃbulos denominado pelos gramÃticos tradicionais e por vÃrios lingÃistas de pronome. Procuramos analisar um bom nÃmero de opiniÃes para vermos em que medida se caracteriza a classe pronominal em especial a dos chamados pronomes pessoais. Ponto a objetar à a utilizaÃÃo da dÃixis como marca pronominal, isto Ã, considerar que todos os vocÃbulos dessa classe se comportam como sinais, entidades discursivo-pragmÃticas. ConcluÃmos ser a dÃixis insuficiente para englobar toda uma classe. Adotamos, assim, uma nova perspectiva com base em Lhorach que desfaz a idÃia de existÃncia de uma classe de pronomes autÃnoma, redistribuindo os vocÃbulos pertencentes tradicionalmente a esta em substantivo e adjetivo. Os pronomes pessoais seriam nesta abordagem, substantivos pessoais. / This dissertation investigates the relation between extra linguistic factors (sex, age and register) and the intercalation of a pronoun in a word in PORCUFORT. From this analysis of this corpus was evident that such factors do not influence the personal substantivesâ behavior. This work is also about a review of many opinions from studies about features that mark a specific group of words named pronouns by traditional grammarians and many linguists. We tried to analyze a great number of opinions to make sure in which measurement the pronominal class is characterized, especially personal pronouns. A point to emphasize is the use of deixis as a pronominal mark, that is, we consider that all the words that belong to this class works as signals, of discursive and pragmatic entities. We adopted, then, a new perspective with base in Lhorach, who undoes the idea of the existence of an autonomous class of pronouns, redistributing the terms that belongs traditionally to this class into noun and adjective. The personal pronouns would be personal substantives in this approach.

Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2017-07-12T19:19:51Z No. of bitstreams: 1 2015 - Matheus Gomes Ferreira.pdf: 3047516 bytes, checksum: 3232f27bdf2c2fd0b3942a410158e76e (MD5) / Made available in DSpace on 2017-07-12T19:19:51Z (GMT). No. of bitstreams: 1 2015 - Matheus Gomes Ferreira.pdf: 3047516 bytes, checksum: 3232f27bdf2c2fd0b3942a410158e76e (MD5) Previous issue date: 2015-07-10 / CAPES / In this work were prepared by coprecipitation and characterized by powder XRD and FTIR compounds of the hydrotalcite type, known as Layered Double Hydroxides (LDH), intercalated with the glyphosate anion (GLYP), and the conditions of preparation and the stoichiometric ratio Mg:Al:GLYP were studied. The best condition observed was under reflux for 30 hours and stoichiometric ratio 2: 1: 1 for Mg+2, Al+3 and GLYP, as indicated by the characteristic bands of LDH intercalated with glyphosate and no other bands present, which could be assigned to other intercalated ions or to free glyphosate. Under those preparation conditions the LDH interlamellar spacing was 0.62 nm, compatible with the intercalation of glyphosate. The controlled release of glyphosate was studied using ion exchange reactions of Layered Double Hydroxides containing glyphosate with an aqueous medium containing carbonate, chloride or nitrate anions. In those cases the glyphosate was quantified spectrophotometrically by Ruhemann's purple method (?max = 570 nm), and the initial releasing rates of 0.65 mg/ml/h (carbonate), 0.14 mg/ml/h (nitrate) and 0.08 mg/ml/h (chloride) were measured. Regarding the XRD patterns of the ion-exchanged products, it was observed that the structure of HDL was maintained, but with the reduction of the interlayer spacing in all cases, having a sufficient size for the anion of the involved ion exchange, but not enough for the presence of GLYP, demonstrating so that the exchange was successful. / Neste trabalho foram preparados por coprecipita??o e caracterizados por DRX de p? e FTIR compostos do tipo hidrotalcita, conhecidos como Hidr?xidos Duplos Lamelares (HDL), intercalados com o ?nion glifosato (GLYP), e foram estudadas as melhores condi??es de prepara??o e a raz?o estequiom?trica Mg:Al:GLYP. A melhor condi??o foi sob refluxo por 30 horas e raz?o estequiom?trica 2:1:1 para Mg+2, Al+3, e GLYP, a partir da observa??o das bandas caracter?sticas no espectro de FTIR de um HDL intercalado com glifosato, sem outras bandas presentes que pudessem ser atribu?das a outros ?ons intercalados ou ao glifosato livre. Nessas condi??es de preparo o espa?amento interlamelar do HDL foi de 0,62 nm, compat?vel com a intercala??o do glifosato. A libera??o controlada do glifosato foi estudada atrav?s de rea??es de troca i?nica dos Hidr?xidos Duplos Lamelares contendo glifosato com um meio aquoso contendo os ?nions carbonato, cloreto ou nitrato. Nestes casos o glifosato foi quantificado espectrofotometricamente pelo m?todo do p?rpura de Ruhemann (?max = 570 nm), e foram obtidas as taxas de libera??o iniciais de 0,65 mg/ml/h para carbonato, 0,08 mg/ml/h para cloreto e 0,14 mg/ml/h para nitrato. Nos difratogramas de raios-X dos produtos das trocas i?nicas, em todos os casos foram observadas a manuten??o da estrutura do HDL e a diminui??o do espa?o interlamelar, de 0,62 nm para valores entre 0,33 e 0,35 nm, tamanho suficiente para o ?nion da troca i?nica envolvido, mas n?o suficiente ainda para a presen?a de GLYP, demonstrando assim que a troca foi bem sucedida.

We sought to investigate the role of the Planar Cell Polarity (PCP) pathway in neuronal positioning along the Anterior-Posterior (AP) axis of C. elegans, and chose the worm’s DD-type motor neurons as a model. The six DD neurons (DD1-DD6) are evenly spaced in the ventral nerve cord of wild type animals. Here we showed that mutations in core PCP genes caused DD neuron spacing and positioning defects. prkl-1 double mutant combinations with vang-1 and fmi-1 showed a suppression of the more severe prkl-1 single mutant defects, which was evidence of genetic interactions between these PCP components. We also conducted a candidate screen of Frizzled, Dishevelled, Wnt, and ROCK genes, and found that dsh-1/Dishevelled, mom-2/Wnt and let-502/ROCK also played roles in DD neuronal positioning. Both vang-1 and prkl-1 were found to function within the nervous system to guide DD neuronal positioning, and prkl-1 was further identified as playing a cell autonomous role. The origins of observed DD neuron anterior positioning defects were investigated during embryogenesis, in which 1.5 fold stage prkl-1(ok3182) embryos displayed delayed intercalation of the DD neurons. This represents a novel role for the PCP pathway in mediating DD neuronal intercalation.

Efficient and economic treatment of low concentration organic pollutants in water, wastewater or industrial process streams is normally very difficult to achieve. Activated carbon has been widely used for contaminant adsorption, but there are problems associated with its regeneration. In this work, a novel, non-porous, highly-conducting graphite intercalation compounds material (GIC) is used. The use of such an adsorbent can significantly reduce the time required to achieve both equilibrium and electrochemical regeneration. This character allows the design of an innovative treatment process that can adsorb contaminants and electrochemically regenerate itself simultaneously within a single unit. A novel liquid-lift reactor for water treatment by an adsorption and electrochemical regeneration process is developed in this work. Batch experiments are carried out to determine the adsorption kinetics and equilibrium isotherm of adsorption Acid Violet 17 onto the GIC adsorbent. The experimental kinetic data are analyzed using the pseudo-first order, pseudo-second order, intra-particle diffusion and three-stage kinetic models. The linear pseudo-second order model offers the highest r2 correlation coefficient. The experimental isotherm data are analyzed using Langmuir, Freundlich and Tempkin isotherm models. The non-linear Langmuir model gives the highest r2 correlation coefficient. High regeneration efficiency (more than 90%) over a number of cycles is obtained by passing a charge of 6.4 C g-1 of the GIC adsorbent, at a current density of 5 mA cm-2 using a batch, sequential adsorption (60 min) and electrochemical regeneration (30 min) process. The simultaneous adsorption and regeneration process indicates that 100 % AV 17 can be removed in 60 min (4L of 100 mg L-1 AV 17 solution, 140g of the GIC adsorbent, current density of 5mA cm-2). The flow behaviour in the electrochemical reactor has been studied using a pulse tracer technique. The residence time distribution shows that the flow behaviour in the liquid-spouted reactor can be regarded as a plug flow in series with a continuous stirred tank reactor. For the batch adsorption system, a “parallel adsorption barren well hypothesis” is proposed in this thesis. For the batch simultaneous adsorption and electrochemical regeneration system, a multi-parameter model is proposed in this thesis.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22456号 / 工博第4717号 / 新制||工||1737(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 作花 哲夫, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

The continued growth of the optoelectronics industry and the emergence of wearable and flexible electronics will continue to place an ever increasing pressure on replacing ITO, the most widely used transparent conducting electrode (TCE). Among the various candidates, graphene shows the highest optical transmittance in addition to promising electrical transport properties. The currently available large-scale synthesis routes of graphene result in polycrystalline samples rife with grain boundaries and other defects which limit its transport properties. Chemical doping of graphene is a viable route towards increasing its conductivity and tuning its work function. However, dopants are typically present at the surface of the graphene sheet, making them highly susceptible to degradation in environmental conditions. Few-layers graphene (FLG) is a more resilient form of graphene exhibiting higher conductivity and performance stability under stretching and bending as contrasted to single-layer graphene. In addition FLG presents the advantage of being amenable bulk doping by intercalation. Herein, we explore non-covalent doping routes of CVD FLG, such as surface doping, intercalation and combination thereof, through in-depth and systematic characterization of the electrical transport properties and energy levels shifts. The intercalation of FLG with Br2 and FeCl3 is demonstrated, showing the highest improvements of the figure of merit of TCEs of any doping scheme, which results from up to a five-fold increase in conductivity while maintaining the transmittance within 3% of that for the pristine value. Importantly the intercalation yields TCEs that are air-stable, due to encapsulation of the intercalant in the bulk of FLG. Surface doping with novel solution-processed metal-organic molecular species (n- and p-type) is demonstrated with an unprecedented range of work function modulation, resulting from electron transfer and the formation of molecular surface dipoles. However, the conductivity increases compared modestly to intercalation as the electron transfer is limited to the uppermost graphene layers. Finally, a novel and universal multi-modal doping strategy is developed, thanks to the unique platform offered by FLG, where surface and intercalation doping are combined to mutually achieve high conductivity with an extended tunability of the work function. This work presents doped-FLG as a prospective and versatile candidate among emerging TCEs, given the need for efficient and stable doping routes capable of controllably tuning its properties to meet the criteria of a broad range of applications.