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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
11

Pointillism in Plant Systems Biology: I. Proteomic Analysis of Plant Exosome-like Particles II. Amyloplast-binding Puroindoline Fusion Proteins for Recombinant Protein Expression.

Greenham, Trevor 24 September 2019 (has links)
Expanding upon our understanding of plant defense is critical, particularly with the perilous threats of climate change and overpopulation to our food security, health and well-being. In this study, we focused on plant defense using two distinct approaches. First, we performed a proteomic analysis of plant exosome-like nanoparticles in order to elucidate their defense related protein cargo. Secondly, we used a wheat antimicrobial protein, puroindoline, as a fusion partner for the expression of recombinant proteins in rice endosperm. Plant exosome-like nanoparticles (ELP) were isolated from fresh tomato and subjected to mass spectrometry (MS) analysis. The ELPs were compared to fresh pressed tomato juice, and the proteins that were significantly upregulated in the ELPs were analyzed for their defensive properties. Bioinformatic analysis identified 30 proteins upregulated in the ELPs, with a majority of these being involved in plant defense. Puroindoline is a protein found in soft wheat varieties. A unique feature of this protein is the presence of a tryptophan-rich domain, which causes it to localize and tether onto starch granule surfaces; a property we are seeking to exploit for recombinant protein isolation. We hypothesized that when expressed in a pin-null crop, such as rice, puroindoline along with its fusion partner will localize and adhere to starch granule surfaces. PIN fusions were expressed in rice, and their subcellular localization was determined by immunolocalization. It was observed that PIN localizes to rice starch ii granules in vitro and in planta, and retains its starch granule binding abilities as a fusion partner. To identify other possible starch granule binding fusion partners, an anhydrous cleavage method was developed that can scan dry biological materials for associated proteins, in this case the starch granule surface. Incubation of our cleavage reagent with isolated rice starch granules yielded several cleavage products as determined through SDS-PAGE. These cleavage products were compared with previous proteomic data of trypsin digested rice starch granules.
12

Treatment of Low Quality Forages by Hydrogen Peroxide and(or) Anhydrous Ammonia and Their Utilization in Ruminant Nutrition

Diouri, Mohammed 01 May 1993 (has links)
Three experiments were conducted to evaluate low quality forages treatment by anhydrous ammonia (NH3) and(or) hydrogen peroxide (H2O2). In experiment I, a control and three treatments of barley straw were compared: NH3, NH3 after rehydration of the straw with water (NH3+H2O), and NH3 after rehydration with a H2O2 solution (NH3+H2O2). Forages were fed, with a supplement, at two levels of intake (ad libitum and 75% of ad lib.). Treatments were administered in a split-plot in a Latin square design to 8 ewes. Total collections and rumen digesta measurements were made. Ammoniation, rehydration, and H2O2 increased primarily dry matter intake (DMI) but also digestibility of different nutrients. A similar trend was observed in rumen fermentation characteristics. Dry matter (DM) digestibility was slightly raised by limiting DMI. Digestible DMI (DDMI) was correlated with both the increase of forage CP content and the decrease of forage neutral detergent fiber. Water intake and output were highly correlated with fiber. Intake and digestibility better than acid detergent lignin insoluble ash (ADLIA). Both markers were adequate in determining hemicellulose digestibility. In experiment II, ten solutions were prepared to rehydrate wheat straw. Six solutions were adjusted (with NaOH) to a pH of 9, 11, or 13 and contained 2% H2O2. Four solutions had a pH of 7 or 11 and contained no H2O2. Half of the straws were treated with NH3. In situ DM disappearance (DMD) of the different straws was measured at different times in 10 Holstein cows and three periods (Incomplete block design). The evolution of DMD was slow and almost linear. The positive effect of ammoniation on DMD was consistently apparent at all pH levels though depressed at pH 11. The effect of H2O2 was minor, but was complementary with ammoniation. In experiment III, mature baltic rush (Juncus balticus Willd.) was either treated or not with NH3. Eight wethers had ad libitum access to the nonsupplemented forages in a cross-over design. total collections and rumen digesta measurements were made. DMI and DDMI were not affected by treatment, but DM digestibility was decreased by ammoniation.
13

Biophysical studies of anhydrous peptide structure

McLean, Janel Renee 15 May 2009 (has links)
Defining the intrinsic properties of amino acids which dictate the formation of helices, the most common protein secondary structure element, is an essential part of understanding protein folding. Pauling and co-workers initially predicted helical peptide folding motifs in the absence of solvent, suggesting that in vacuo studies may potentially discern the role of solvation in protein structure. Ion mobility-mass spectrometry (IMMS) combines a gas-phase ion separation based on collision cross-section (apparent surface area) with time-of-flight MS. The result is a correlation of collision cross-section with mass-to-charge, allowing detection of multiple conformations of the same ion. Most gas-phase peptide ions assume a compact, globular state that minimizes exposure to the low dielectric environment and maximizes intramolecular charge solvation. Conversely, a small number of peptides adopt a more extended (β-sheet or α-helix) conformation and exhibit a larger than predicted collision cross-section. Collision cross-sections measured using IM-MS are correlated with theoretical models generated using simulated annealing and allow for assignment of the overall ion structural motif (e.g. helix vs. chargesolvated globule). Here, two series of model peptides having known solution-phase helical propensities, namely Ac-(AAKAA)nY-NH2 (n = 3, 4, 5, 6 and 7) and Ac-Y(AEAAKA)nF-NH2 (n = 2, 3, 4, and 5), are investigated using IM-MS. Both protonated ([M + H]+) and metalcoordinated ([M + X]+ where X = Li, Na, K, Rb or Cs) species were analyzed to better understand the interplay of forces involved in gas-phase helical structure and stability. The data are analyzed using computational methods to examine the influence of peptide length, primary sequence, and number of basic (Lys, K) and acidic (Glu, E) residues on anhydrous ion structure.
14

Procedimentos de partida aplicados a uma coluna de destilação extrativa para obtenção de etanol anidro. / Starting procedures applied to an extractive distillation column to obtain anhydrous ethanol.

NUNES, Ícaro Cazé. 09 March 2018 (has links)
Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-03-09T21:26:45Z No. of bitstreams: 1 ÍCARO CAZÉ NUNES - DISSERTAÇÃO PPGEQ 2015..pdf: 1246845 bytes, checksum: 5fd8aea1ce8a8a07ece97288182d8814 (MD5) / Made available in DSpace on 2018-03-09T21:26:45Z (GMT). No. of bitstreams: 1 ÍCARO CAZÉ NUNES - DISSERTAÇÃO PPGEQ 2015..pdf: 1246845 bytes, checksum: 5fd8aea1ce8a8a07ece97288182d8814 (MD5) Previous issue date: 2015-03-30 / Devido a sua natureza de transição, a etapa de partida, para um processo de destilação, apresenta uma série de problemas operacionais. Esses problemas interferem quase sempre no tempo necessário para que se atinja o regime permanente e a planta comece a operar conforme desejado. A partir do desenvolvimento de um procedimento de partida adequado, é possível minimizar os transientes envolvidos nesta etapa, reduzindo dessa forma, o tempo empreendido para se alcançar o estado estacionário. O presente trabalho surgiu a partir da observação da literatura técnica consultada, o qual apresenta poucos relatos de estudos sistemáticos sobre estratégias para a redução do tempo de transição na partida de unidades de destilação, mais especificamente, à destilação extrativa. Portanto, este trabalho consistiu em desenvolver, implementar e avaliar procedimentos alternativos para a operação de partida aplicados a uma coluna de destilação extrativa, a qual faz parte do processo de produção de etanol anidro, a partir de uma mistura azeótropica originalmente composta por etanol-água utilizando o etilenoglicol como solvente. Este trabalho teve como objetivo minimizar o tempo necessario para que a coluna extrativa em estudo estabelecesse o regime estacionário. As simulações para representar o modelo de destilação multicomponente foram realizadas nos simuladores comerciais Aspen PlusTM e Aspen Plus DynamicsTM. O trabalho também contemplou a implementação de uma configuração de controle capaz de evitar a formação de transientes no processo, como também realizou o esvaziamento do sistema, resultando em um modelo de coluna vazia e fria a temperatura de 20º C e pressão de 1 bar. Analisaram-se três procedimentos para a operação de partida: alimentando a coluna com a mistura etanol-água e o solvente ao mesmo tempo, alimentando o solvente 0,5 horas após a alimentação da mistura etanol-água e alimentando o solvente 1,0 hora após a alimentação da mistura etanol-água. Como esperado, observa-se que ao alimentar a coluna de destilação com a mistura etanolágua e o solvente ao mesmo tempo, obteve como resultado um tempo para alcançar o estado estacionário menor que os demais. / Due to the nature of the transition the startup of a distillation process has a large number of operational problems. These problems often affect time undertaken for the attainment of the steady state and the plant begins to operate as desired. From the development of an appropriate starting, it is possible to minimize transients involved in this step, thereby reducing the time required to reach steady state. This work arose from the observation of technical literature consulted, which has few reports of systematic studies on strategies to reduce the transition time at the starting distillation units, particularly in terms of extractive distillation. Therefore, this study was to develop, implement and evaluate alternative procedures for starting operation applied to an extractive distillation column which is part of anhydrous ethanol production process, from an originally composed by azeotropic mixture ethanol- water using ethylene glycol as solvent. This study aimed to minimize the time required for the extraction column under study to establish the steady state. The simulations to represent the model of multicomponent distillation were carried out in the commercial simulator Aspen PlusTM and Aspen Plus DynamicsTM. The work also contemplated to implement a control configuration can avoid the formation of transients in the process, but also made the evacuation system, resulting in an empty column model and cold temperature of 20 C and pressure of 1 bar. Three procedures were analyzed for starter operation: feeding the column with the ethanol-water mixture and the solvent while feeding after 0.5 hours the solvent power of ethanol-water mixture, and feeding the solvent 1.0 hours after feeding the ethanol-water mixture. As expected, it was observed that feeding the distillation column with the ethanol-water mixture and the solvent at the same time, the time obtained as a result of transient lower than the others.
15

Cristais anidros das bases do ADN são semicondutores de Gap largo / Anhydrous cristals of DNA bases are wide gap semiconductors

Maia Júnior, Francisco Franciné January 2011 (has links)
MAIA JÚNIOR, Francisco Franciné. Cristais anidros das bases do ADN são semicondutores de Gap largo. 2011. 243 f. Tese (Doutorado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2011. / Submitted by francisco lima (admir@ufc.br) on 2014-03-18T13:34:36Z No. of bitstreams: 1 2011_Tese_ffmaiajunior.pdf: 27698119 bytes, checksum: f4553d0bed3b17a38cc9b90fb8e55c88 (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2014-05-19T19:27:28Z (GMT) No. of bitstreams: 1 2011_Tese_ffmaiajunior.pdf: 27698119 bytes, checksum: f4553d0bed3b17a38cc9b90fb8e55c88 (MD5) / Made available in DSpace on 2014-05-19T19:27:28Z (GMT). No. of bitstreams: 1 2011_Tese_ffmaiajunior.pdf: 27698119 bytes, checksum: f4553d0bed3b17a38cc9b90fb8e55c88 (MD5) Previous issue date: 2011 / Guanine (G), adenine (A), cytosine (C), and thymine (T) nucleotide bases are the essential building blocks of DNA (deoxyribonucleic acid), which contains the genetic information used to build living cells. DNA strands are also promising candidates to fabricate molecular nanodevices, since they are stable polymers easy to replicate. Despite the early suggestion of the possibility of using DNA as a nanoscale conductor almost ten years after the elucidation of its helical structure, charge carrier transport through DNA-based structures is still a matter of debate. Here, we present the structural, electronic and optical properties of anhydrous crystals of DNA nucleobases found after DFT (Density Functional Theory) calculations, as well as experimental measurements of optical absorption for powders of these crystals. Experimental measurements of the UV absorption spectra for the anhydrous crystals were carried out on these pellets using a Varian Cary 5000 UV-visible NIR spectrophotometer. The absorption spectrum of the samples was recorded in the wavelength range between 200 and 800 nm (50000-12500 cm-1). The computational simulations of the present work were performed using the CASTEP code, which is based in the DFT approach. The Local Density Approximation (LDA) exchange-correlation potential developed by Ceperley and Alder and parametrized by Perdew and Zunger was adopted as well. With respect to our choice of functional, a note of caution must be made: in anhydrous DNA bases crystals, van der Waals interactions along the molecular stacking axis and hydrogen bonding between molecules in the same stacking plane are relevant to explain their structural features, and it is well known that pure DFT methods are unable to give a good description of dispersive forces. Besides, the LDA approximation is not the best option to provide an accurate account of hydrogen bonds. However, some DFT studies of layered crystals such as graphite as well as guanine hydrated crystals have shown that the LDA gives reasonable values for atomic distances, notwithstanding the limitations of this functional. This and the relatively low cost of LDA computations have motivated us to its adoption instead of more sophisticated (and computationally expensive) means. Guanine and cytosine (adenine and thymine) anhydrous crystals are predicted from the DFT simulations to be direct (indirect) band gap semiconductors, with values 2.68 eV and 3.30 eV (2.83 eV and 3.32 eV), respectively, while the experimentally estimated band gaps we have measured are 3.7 eV and 3.8 eV (3.5 eV and 4.0 eV), in the same order. Our LDA figures for the energy gaps are smaller than experimental values, as expected, and the gaps estimated from the optical absorption measurements presented in this work are in general smaller than experimental data available in the literature (except for guanine). The LDA ordering of increasing band gaps is G < A < C < T, while the ordering of gaps obtained experimentally is not settled: our work finds (from optical absorption measurements) A < G < C < T in contrast with the X-ray measurements, that indicate the energy gap sequence G < C < A < T. For electrons and holes moving along selected hydrogen bonds (parallel to the molecular plane of a given nucleobase), effective masses are in general large, exception made to thymine. When the same electrons move along the pi-stacking axis, however, effective masses stay between 4.0 and 6.3 free electron masses (m0), which suggests that stackings of nucleobases behave like wide gap semiconductors for electrons. The perpendicular transport of holes is also favored for nucleobase stackings without thymine. Finally, the complex dielectric function was calculated for each anydrous DNA base crystal, and a very pronounced anisotropy was observed for polarized incident light in the cases of guanine, adenine, and thymine, but not for cytosine. / As bases nucleotídicas guanina (G), adenina (A), citosina (C) e timina (T) são bases nucleotídicasos blocos essenciais da molécula do ácido desoxiribonucleico (ADN), que contém a as informações genéticas usadas pelas células vivas. Filamentos de ADN são também candidatos promissores para fabricação nanodispositivos moleculares, visto que polímeros estáveis e de fácil replicação. Apesar desta sugestão inicial da possibilidade de usar o ADN como condutor em nanoescala apenas dez anos após a elucidação da estrutura helicoidal do ADN, o transporte de portadores de cargas através de estruturas baseadas no ADN ainda são matéria de debate. Aqui, são apresentadas as propriedades estruturais, eletrônicas e ópticas dos cristais anidros das bases do ADN obtidas após cálculos baseados na teoria do funcional da densidade (DFT, do inglês Density Functional Theory), assim como medidas de absorção ótica para o pó desses cristais. Os experimentos do espectro absorção UV para os cristais foram realizadas sobre pastilhas usando o espectrometro Varian Cary 5000 UV-visible NIR, considerando o intervalo de 200 and 800 nm (50000-12500 cm-1). Os cálculos teóricos da presente tese foram desenvolvidos usando o pacote CASTEP, baseado na teoria DFT. Na descrição do potencial de troca e correlação, foi utilizada aproximação local da densidade (LDA, do inglês Local Density Approximation) desenvolvida por Cerpeley e Alder e parametrizado por Perdew e Zunger (CA-PZ). Sobre a escolha do funcional, uma observação deve ser feita: nos cristais anidros das bases do ADN, interações de van der Waals ao longo do eixo de empilhamento molecular e as ligações de hidrogênio entre as moléculas do mesmo plano são relevantes na explicação das suas características, e é bem conhecido que os métodos de DFT puro são incapazes de uma boa descrição das forças dispersivas. Além disso, a aproximação LDA não é a melhor opção para cálculos precisos das ligações de hidrogênio. Entretanto, alguns trabalhos DFT de cristais formados por camadas tais como grafite e o cristal hidratado da guanina mostraram que o funcional LDA fornece valores razoáveis para as distâncias atômicas, contrariando as limitações desse funcional. Isso e o baixo custo computacional foram as motivações que levaram a sua escolha em vez da adoção de funcionais mais sofisticados (e computacionalmente mais pesados). Os cristais de guanina e citosina (adenina e timina) são previstos terem gaps diretos (indiretos), com os valores experimentais estimados a partir da absorção de 3,7 eV e 3,8 eV (3,8 eV e 4,0 eV), na mesma ordem. Os resultados LDA mostraram gaps de energia menores do que os valores experimentais, como esperado, e os gaps experimentais estimados a partir da absorção ótica são, em geral, menores do que os valores experimentais disponíveis na literatura (exceto, para a guanina). A ordem crescente nos valores calculados dos gaps de energia para os cristais é dada por G < A < C < T, enquanto os valores experimentais obtidos nesta tese (a partir da absorção óptica) seguem a ordem A < G < C < T em contraste com as medidas de raios-x, que indicam a sequência G < C < A < T. Para os elétrons e buracos se movendo das ligações de hidrogênio (paralelas ao plano molecular da base), as massas efetivas são geralmente elevadas, exceto para a timina. Quando os mesmos elétrons se movimentam ao do eixo de empilhamento molecular, entretanto, as massas efetivas ficam entre 4,0 e 6,3m0, sugerindo estes cristais se comportam como semicondutores de gap largo ao longo das direções de empilhamento molecular. O transporte de buracos também é favorecido ao longo da direção de empilhamento, exceto para a timina. Finalmente, a função dielétrica complexa foi calculada para cada cristal anidro das bases do ADN, sendo observada uma forte anisotropia para a incidência de luz polarizada nos casos da guanina, adenina e timina, mas não para a citosina.
16

Análise, desenvolvimento e ensaio de um dispositivo experimental para fornecer álcool etílico hidratado como segundo combustível para motores do ciclo diesel / not available

Gilberto Hirotsugu Azevedo Koike 19 September 2003 (has links)
Um grande problema atual do mundo é o efeito estufa causado pela combustão de petróleo e seus derivados. Além disso, as reservas de petróleo não são ilimitadas, nem renováveis. Uma maneira de minimizar o problema é a utilização de combustíveis renováveis, tais como o etanol, derivado da cana de açúcar. É o caso dos motores de ignição por centelha que usam o etanol há décadas no Brasil. Este trabalho descreve as tecnologias existentes para utilização de etanol em motores de ignição por compressão. Apresenta resultados energéticos e de consumo de mistura de etanol anidro com diesel em diversas proporções. Mostra como substituir parcialmente o Diesel pelo etanol hidratado em determinadas proporções, sem realizar a mistura de combustíveis. Os combustíveis entram no motor por caminhos diferentes. Finaliza realizando estudos econômicos da utilização do etanol etílico em conjunto com o óleo diesel. / A major problem in the world nowadays is the \"green-house\" effect, caused by the combustion of petrol and its derivatives. Besides, oil reserves are not lirnitless, nor renewable. One way to rninirnize this problem is by using renewable combustibles, like ethanol, derived from sugar cane. This is the case of ignition spark engines, that have been using ethanol for decades, in Brazil. This thesis describes the existing technologies for ethanol utilization in ignition compression engines. It also presents energy and consumption results for the rnixture of anhydrous ethanol and diesel, in different proportions. It shows how to partially replace the diesel by hydrated ethanol in certain proportions, without fuel\'s blend. The fuels enter into the motor by different routes. It finally describes econornic studies for the utilization of ethylic alcohol m association to diesel.
17

High Temperature Proton Conducting Materials and Fluorescent-Labeled Polymers for Sensor Applications

Martwiset, Surangkhana 01 September 2009 (has links)
The majority of this dissertation focuses on proton conducting materials that could be used at high operating temperatures. Higher operating temperatures are desirable as they will increase fuel cell efficiency, reduce cost, and simplify the heat management system. The factors governing proton conduction including segmental mobility, protogenic group identity, and charge carrier density were investigated on a variety of polymers containing 1H-1,2,3-triazole moieties. Proton conductivity measurements were made using AC impedance spectroscopy. Random copolymers and terpolymers of triazole-containing acrylates and poly(ethylene glycol)methyl ether acrylate (PEGMEA) have been synthesized. Conductivity increased with increasing degree of PEG incorporation until reaching a maximum at 30% mole PEGMEA. In comparison to benzimidazole-functionalized polyacrylate with 35% mole PEGMEA, the triazole analog showed a higher proton conductivity, and a less pronounced conductivity temperature dependence. Further increases in conductivity was achieved through the addition of trifluoroacetic acid. To study the effect of charge carrier density on proton conduction, polyacrylates containing a different number of triazole groups per repeat unit were synthesized. The result showed that introduction of more than one triazole per repeat unit did not result in an increase in conductivity as there was an accompanying increase in Tg. To improve the thermal and mechanical properties, triazole groups were tethered to a higher Tg backbone polymer, polynorbornene. Introduction of polyhedral oligomeric silsesquioxane (POSS) into triazole-functionalized polynorbornene was also investigated. In a parallel set of investigations, poly(2-(dimethylamino)ethyl methacrylate), PDMAEMA, and copolymers of DMAEMA and methyl methacrylate (PDMAEMA-co-PMMA) were synthesized via atom transfer radical polymerization (ATRP). Fluorescently-labeled PDMAEMAs were synthesized using fluorescent ATRP initiators to ensure the presence of one dye molecule on every polymer chain. PDMAEMAs and PDMAEMA-co-PMMA with different molecular weights have been deposited onto a negatively-charged silica surface via controlled flow deposition. The results show that the polymer deposition rate depends on molecular weight, and is inversely proportional to molecular weight. A preliminary adhesion study of 1-μm negatively charged silica spheres onto these functionalized surfaces indicates that by varying the molecular weight, the adhesion threshold can be changed. System modeling is being conducted to support experimental observations.
18

Functional Polymers for Anhydrous Proton Transport

Chikkannagari, Nagamani 01 February 2012 (has links)
Anhydrous proton conducting polymers are highly sought after for applications in high temperature polymer electrolyte membrane fuel cells (PEMFCs). N-heterocycles (eg. imidazole, triazole, and benzimidazole), owing to their amphoteric nature, have been widely studied to develop efficient anhydrous proton transporting polymers. The proton conductivity of N-heterocyclic polymers is influenced by several factors and the design and development of polymers with a delicate balance among various synergistic and competing factors to provide appreciable proton conductivities has been a challenging task. In this thesis, the proton transport (PT) characteristics of polymers functionalized with two diverse classes of functional groups - N-heterocycles and phenols have been investigated and efforts have been made to develop the molecular design criteria for the design and development of efficient proton transporting functional groups and polymers. The proton conduction pathway in 1H-1,2,3-triazole polymers is probed by employing structurally analogous N-heterocyclic (triazole, imidazole, and pyrazole) and benz-N-heterocyclic (benzotriazole, benzimidazole, and benzopyrazole) polymers. Imidazole-like pathway was found to dominate the proton conductivity of triazole and pyrazole-like pathway makes only a negligible contribution, if any. Polymers containing benz-N-heterocycles exhibited higher proton conductivity than those with the corresponding N-heterocycles. Pyrazole-like functional groups, i.e. the molecules with two nitrogen atoms adjacent to each other, were found not to be good candidates for PT applications. A new class of proton transporting functional groups, phenols, has been introduced for anhydrous PT. One of the highlighting features of phenols over N-heterocycles is that the hydrogen bond donor/acceptor reorientation can happen on a single -OH site, allowing for facile reorientational dynamics in Grotthuss PT and enhanced proton conductivities in phenolic polymers. Unlike the case of N-heterocycles, comparable conductivities were achieved between poly (3,4,5-trihydroxy) styrene and the corresponding small molecule, pyrogallol. This observation suggests that reorientation should be considered as a crucial design parameter for PT functional groups. The PT characteristics of phenol-based biaryl polymers are studied and compared with the analogous phenol-based linear styrenic polymers. The two-dimensional disposition of -OH moieties in biaryl polymers, although resulted in lower apparent activation energies (Ea), did not improve the net proton conductivity due to the accompanying increase in glass transition temperature (Tg). Thus, the ease of synthesis and lower Tg values of phenol-based styrene polymers make the styrenic polymer architecture preferable over the biaryl architecture. Finally, the synthesis of a series of poly(3,4-dihydroxy styrene)-b-polystyrene block copolymers has been demonstrated via anionic polymerization. These block copolymers will provide an opportunity to systematically investigate the effect of nanoscale morphology on proton transport.
19

Colligative Measurements in Anhydrous Hydrogen Fluoride.

Humphreys, David Alan 09 1900 (has links)
<p> Techniques have been developed for making cryoscopic and vapour pressure measurements in anhydrous hydrogen fluoride. The cryoscopic constant for the solvent has been determined. </p> <p> The techniques developed have been used to determine the mode and extent of the ionization of some acids and bases of the HF system. The formation and stability of polymeric ions in the solvent has been investigated and the formation of the previously unknown anion As₂F₁₁⁻ has been shown. Cryoscopy has been used to detect a new polymeric 1:1 adduct of XeF₂ and SbF₅. Solutions of cyanides in HF have been investigated and the formation of a new polymeric cation Hg₂CN₃⁺, formed when mercury cyanide dissolves in HF, has been suggested. The results of some experiments on solvolysis reactions are also reported. </p> / Thesis / Doctor of Philosophy (PhD)
20

Observation of highly decoupled conductivity in protic ionic conductors

Wojnarowska, Z., Wang, Y., Paluch, Krzysztof J., Sokolov, A.P., Paluch, M. 27 March 2014 (has links)
Yes / Ionic liquids (ILs) are key materials for the development of a wide range of emerging technologies. Protic ionic liquids, an important class of ILs, have long been envisioned as promising anhydrous electrolytes for fuel cells. It is well known that in comparison to all other cations, protons exhibit abnormally high conductivity in water. Such superprotonic dynamics was expected in protic ionic conductors as well. However, many years of extensive studies led to the disappointing conclusion that this is not the case and most protic ionic liquids display subionic behavior. Therefore, the relatively low conductivity seems to be the main obstacle for the application of protic ionic liquids in fuel cells. Using dielectric spectroscopy, herein we report the observation of highly decoupled conductivity in a newly synthesized protic ionic conductor. We show that its proton transport is strongly decoupled from the structural relaxation, in terms of both temperature dependence and characteristic rates. This finding offers a fresh look on the charge transport mechanism in PILs and also provides new ideas for design of anhydrous materials with exceptionally high proton conductivity. / National Science Centre within the framework of the Opus project (Grant No. DEC 2011/03/B/ST3/02072). Financial assistance from FNP START. The LDRD Program of ORNL, managed by UT-Battelle, LLC, for the U.S. DOE. Support from the NSF under grant CHE-1213444.

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