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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.
61

Understanding the mechanism of permeation through graphene-based membranes using molecular dynamics simulations

Dix, James January 2017 (has links)
The UN predicts that by 2050 there will water shortages throughout the globe. Current sources for safe, clean drinking water are being over mined and exhausted. Seawater provides an alternative water source, but a high salt content makes it unsuitable for the majority of applications. However, reverse osmosis lowers the salt content producing water that is safe for human consumption. Reverse osmosis uses a semi-permeable membrane to prevent the transport of salt but allows for the transport of water. Currently these membranes are susceptible to fouling and contamination, which reduces their efficiency. Graphene-oxide membranes offer a new material for reserves osmosis membranes. Sheets of graphene-oxide are stacked in a layered structure. The separation between the sheets can be controlled using physical confinement, resulting in limited ion permeation of abundant cations in seawater, like Na+ and K+. This is believed to be due to the separation of 0.76 nm between the graphene sheets, forcing the ions to lose its surrounding water molecules, making it unfavourable for the ion to travel through the membrane. Molecular dynamics simulations can give an atomic level insight into the molecular processes within GO membranes. Recent simulations have shown that charged species are attracted to graphene surfaces due to polarisation of the pi-electron system. This work has managed to incorporate these ion-pi interactions into molecular dynamics simulations. Including ion-pi interactions caused some ions, like Na+ and K+, to prefer to lose water molecules and reside at a graphene surface. This work observed the same phenomena when ions were confined to graphene channel ranging from 1.3 nm - 0.7 nm. This observation could have a large impact on whether dehydration is limiting the permeation of these two ions, or if there are additional processes that limit their molecular transport.
62

Signaling mechanism underlying the stimulatory effects of Bak Foong pills and its active components on gastrointestinal epithelia. / CUHK electronic theses & dissertations collection

January 2004 (has links)
Zhu Jinxia. / "July 2004." / Thesis (Ph.D.)--Chinese University of Hong Kong, 2004. / Includes bibliographical references (p. 142-170). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.
63

Olivin-Typ Lithiumeisenphosphat (Li1-xFePO4) - Synthese, Li-Ionentransport und Thermodynamik

Loos, Stefan 23 February 2015 (has links) (PDF)
Die vorliegende Dissertation beschäftigt sich mit der Synthese, den Li+-Transporteigenschaften und der Thermodynamik von Olivin-Typ LiFePO4. Es werden verschiedene Solvothermalsynthesen untersucht. Neben der Einstellung von Partikelgröße und Partikelmorphologie steht die Analyse der Hydrothermalsynthese aus Li3PO4 und Vivianit durch in situ Messung der elektrolytischen Leitfähigkeit im Vordergrund. Die Untersuchung des Li+-Transportes geschieht auf Basis von Redoxreaktionen. Die formalkinetische Auswertung von Lithiierungs- und Delithiierungsreaktionen und eine Nukleationsanalyse wird durch ein Modell zur Auswirkung von antisite-Defekten auf die Kapazität des Elektrodenmaterials ergänzt. Die Ramanspektroskopie wird in Verbindung mit Lösungsenthalpien zur Identifizierung reaktiver Spezies herangezogen. Schwerpunkt der thermodynamischen Charakterisierung ist die experimentelle Ermittlung der Wärmekapazität. Diese wurde unter Berücksichtigung einer magnetischen Phasenumwandlung im Bereich von 2 K bis 773 K ermittelt. Die Daten erlauben die Berechnung wichtiger thermodynamischer Funktionen.
64

Towards voltage-gated ion channels synthesized by solid-phase organic synthesis

Luong, Horace 24 April 2008 (has links)
The goal of this thesis was to develop a method for efficiently synthesizing a large suite of asymmetric oligoester ion channel-forming compounds. A solid-phase organic synthesis (SPOS) approach on Wang resin was used to generate the ion channel candidates. A follow-on goal is to survey the compounds produced to uncover structure-related controls on ion transport activity. Two classes of building blocks were used to generate the oligoesters – head groups and cores. The core building blocks were three omega-hydroxy acid derivatives six, eight and twelve carbons in length and the alcohol protected as a tetrahydropyranyl ether. The head group building blocks were either a glutaric acid monoester derivative of varying lipophilicity (12 to 16 carbon long alkyl tail) or a beta-hydroxy acid derivative; these building blocks used a tert-butyldimethylsilyl ether for alcohol protection. Optimized conditions for building block coupling, deprotection, and product cleavage were first established by the generation of dimeric and trimeric products. The building blocks were coupled using diisopropylcarbodiimide/ dimethylaminopyridine conditions. The deprotection of the tetrahydropyranyl ether group from the alcohol used a dilute acid solution in methanol and dichloromethane. A fluoride solution (from tetrabutylammonium fluoride) in tetrahydrofuran was used to deprotect the tert-butyldimethylsilyl ether group. Cleavage of the product synthesized on Wang resin was achieved by treatment with a trifluoroacetic acid/dichloromethane or ethereal hydrogen chloride solution. The products were then isolated by gel filtration. Mass spectrometry was used to identify the minor impurities which were quantified by proton nuclear magnetic resonance integrations. With the nine building blocks, many tetrameric and pentameric structures can be made, but a directed-library approach was used to address structure-activity related questions. Three pentameric oligoester products were the largest products synthesized to determine the scope and limitations of the SPOS methodology. The oligoester ion channel candidates were tested for ion transport activity using a 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt fluorescence vesicle assay. For each compound a pseudo-first order rate constant was derived at a particular concentration. A more useful normalized rate constant was calculated for an interpolated transporter concentration which allowed for transport activity comparison between compounds. The results from the fluorescence assay showed that some compounds and some isomers were substantially more active than others. There appeared to be an optimal core length and lipophilicity for relatively high activity. The aggregation of the compounds in buffer solution was probed using a pyrene fluorescence experiment. The solid-phase methodology was extended to include coupling of amino acids. A tryptophan derivative was made from one of the most active SPOS oligoester ion channel-forming compounds. The integrity of the molecules synthesized by SPOS which contain the tryptophan group could then be determined by high performance liquid chromatography. The fluorescence of the indole is quenched by acrylamide. By first equilibrating the vesicles with the tryptophan-containing oligoesters and then adding a fluorescence quencher, the resulting indole fluorescence was monitored as a function of quencher concentration. A Stern-Volmer plot was derived based on the quenching data which reported the possible orientations of the tryptophan-containing oligoester within the vesicle.
65

Stimulation de cellules épithéliales bronchiques humaines par la GnRH : effet sur le transport ionique médié par le CFTR / No title

Benz, Nathalie 13 December 2013 (has links)
Introduction : La mucoviscidose est une maladie génétique autosomale récessive causée par des mutations dans le gène CFTR (cystic fibrosis transmembrane conductance regulator). Ce dernier code un canal chlorure AMPc-dépendant localisé dans la membrane apicale des cellules épithéliales, dont l’activité est régulée par de nombreuses interactions protéine-protéine. Dans le cadre de la recherche de nouveaux partenaires du CFTR, une interaction directe entre le canal (sauvage et muté F508del) etl’annexine A5 (AnxA5) a été mise en évidence dans notre laboratoire. Des stratégies de sur et de sousexpression nous ont également permis d’établir un lien fonctionnel entre les deux protéines. En effet, nos travaux montrent que les sécrétions ioniques dépendantes du CFTR sont corrélées au niveau d’expression intracellulaire de l’AnxA5. Par ailleurs, une élévation des courants médiés par le CFTR ainsi qu’une augmentation de la quantité de canaux dans la membrane plasmique sont observées suite à la surexpression de l’AnxA5 dans des cellules exprimant le CFTR muté F508del.But de l’étude : Au vu de ces observations, l’AnxA5 apparaît comme une cible potentielle pour la correction de certains défauts engendrés par la mutation F508del. Une piste thérapeutique pourrait être l’identification de composés capables d’augmenter son expression dans des cellules épithéliales exprimant le mutant F508del de la protéine CFTR. Considérant les informations fournies par la littérature, notre choix s’est porté sur la GnRH (gonadotropin-releasing hormone), molécule utilisée en thérapeutique humaine depuis plus de 25 ans. Ainsi, nous avons évalué l’effet de la GnRH sur la modulation de l’expression de l’AnxA5 et sur le transport ionique dépendant du CFTR dans nos différents modèles d’étude Résultats : Outre la présence du récepteur de la GnRH dans nos modèles cellulaires, nous montrons également que l’expression de l’AnxA5 y est augmentée dès 60 minutes de traitement avec l’hormone (1 nM). De plus, comparativement à des cellules non stimulées, des cellules prétraitées avec la GnRH présentent une hausse significative des sorties actives d’iodure, corrélant avec une augmentation de la quantité de CFTR à la surface cellulaire. Ces observations ont été faites dans les modèles exprimant le CFTR muté F508del ainsi que dans ceux exprimant le CFTR sauvage. Conclusion : Dans nos modèles et selon nos conditions de stimulation, un traitement avec la GnRH augmente l’expression intracellulaire de l’AnxA5 et conduit à une élévation des sécrétions ioniques médiées par le canal CFTR. Néanmoins, au vu de la multitude de voies de signalisation susceptibles d’être activées et de gènes pouvant être régulés suite à la liaison de la GnRH sur son récepteur, l’effet observé sur l’AnxA5 ne représente probablement pas le seul évènement cellulaire à l’origine de l’impact positif enregistré sur l’activité du canal CFTR. / Background: Cystic fibrosis (CF) is an autosomal recessive disorder caused by mutations in the cystic fibrosis transmembrane conductance regulator (CFTR) gene, which encodes a cAMP-stimulated chloride channel. CFTR is primarily located at the apical surface of epithelial cells, where its activity is regulated by some protein-protein interactions. As part of new CFTR’s partners research, we previously showed that annexin A5 (AnxA5) binds directly to both normal and F508del-CFTR. Moreover, under and overexpression strategies led us to establish a functionnal link between these two proteins. In fact, CFTR-dependent ion secretions are correlated to the intracellular level of AnxA5. Otherwise, in transfected epithelial cells, AnxA5 overexpression increases CFTR’s level in plasma membranes and raises CFTR-mediated currents in F508del-CFTR expressing cells. Aim of the study: In the light of these findings, AnxA5 appears as a potential target in order to correct some defects caused by the F508del mutation. A therapeutic approach would be to find some compounds capable of increasing AnxA5 expression in F508del-CFTR expressing epithelial cells. Reviewing the literature, our choice fell on GnRH (gonadotropin-releasing hormone), a commonly used molecule for diverse clinical applications for 25 years. So, the effects of GnRH on the modulation of AnxA5 expression and on CFTR-dependent ion transport were assessed in our different cellular models. Results: Beside the GnRH receptor expression, we show that AnxA5 expression is augmented in all cell lines after one hour incubation with the hormone (1 nM). Moreover, compared to untreated cells, a significant iodide efflux peak is measured in GnRH pretreated, which is correlated with an increased cell surface expression of CFTR. It is of interest to note that these observations have been made in CF and non-CF cells. Conclusion: In our models and according to our stimulation conditions, GnRH treatment enhances AnxA5 intracellular expression and leads to a rise of CFTR-dependent ion secretions. Nevertheless, given the multitude of activated signaling pathways and regulated genes in response to GnRH binding to its receptor, the positive impact on CFTR activity is probably not solely explained by the effect on AnxA5 expression.
66

Comparative analyses of plant responses to drought and salt stress in related taxa: A useful approach to study stress tolerance mechanisms

AL HASSAN, MOHAMAD 19 January 2018 (has links)
[EN] Abstract Introduction Salinity and drought are the most important environmental stress conditions reducing crop yields worldwide and limiting the distribution of wild plants in nature. Soil salinity, especially secondary salinity caused by anthropogenic practices, such as prolonged irrigation, lead to substantial agricultural yield losses, especially in arid and semiarid regions. Drought, caused by reduced water content in the soil, occurs due to disorders in nature's water cycle, chiefly when evapotranspiration exceeds precipitation in a certain area, to the point where soil water reserves can no longer support plant growth. Drought and salt stress trigger the activation of a series of basic stress mechanisms that includes among others, the control of ion transport, exclusion and compartmentalization, as well as the accumulation of compatible solutes ('osmolytes'), and the activation of antioxidant systems. These mechanisms are conserved in all plants, stress tolerant and sensitive alike, and don't necessarily confer tolerance. To decipher those mechanisms and have a better understanding on the contribution of different stress responses to the stress tolerance of a given species, we have carried out comparative studies on the responses to drought and salinity in a number of genetically related taxa with different tolerance potentials. Methodology The experimental approach was mostly based on i) establishing the relative tolerance to water and salt stress in the studied species from their distribution in nature (in the case of wild species) and through the relative inhibition of growth in the presence of stress, and ii) correlating changes in the levels of biochemical 'stress markers' associated to specific response pathways (ion transport, osmolyte accumulation¿) upon stress treatments, with the already established relative tolerance to stress. This strategy proved to be appropriate to distinguish mere general responses to stress from those mechanisms relevant for stress tolerance of the investigated species and cultivars. The work also sheds light on other aspects affected by salt stress, specifically regarding germination and reproductive success or anatomical changes in salt-stressed plants. The expression patterns of the gene NHX1, encoding a vacuolar Na+/H+ antiporter were also studied in the Plantago taxa, as a first step in the full characterisation of this ion transporter, that appears to play an important role in the mechanisms of salt tolerance in this genus. Conclusion The results obtained in this work contribute to a better understanding of general stress tolerance mechanisms in plants, and provides clear insights into the mechanisms conferring tolerance, specifically, to drought and salt stress in some wild species and crops. This work also shed more light on the highly efficient responses to stress in halophytes, plants that could be viewed as nature's answer to the aforementioned adverse environmental conditions via evolution and adaptation. Halophytes can therefore be considered as a suitable source - underutilized at present, in our opinion - of knowledge, genetic resources and biotechnological tools for the needed improvement of stress tolerance in crops. / [ES] Resumen Introducción La salinidad y la sequía son las condiciones de estrés ambiental más importantes, que reducen los rendimientos de los cultivos en todo el mundo y que limitan la distribución de las plantas silvestres en la naturaleza. La salinidad del suelo, especialmente la salinización secundaria causada por prácticas antropogénicas, como la irrigación prolongada, conducen a pérdidas importantes de rendimiento agrícola, especialmente en las regiones áridas y semiáridas. La sequía, provocada por la reducción de contenido de agua en el suelo, se produce debido a alteraciones en el ciclo del agua en la naturaleza, principalmente cuando la evapotranspiración excede la precipitación en un área determinada, hasta el punto que las reservas de agua del suelo ya no pueden soportar el crecimiento de la planta. La sequía y el estrés salino desencadenan la activación de una serie de mecanismos básicos de respuesta, que incluyen entre otros el control del transporte, la exclusión y la compartimentación de iones, así como la acumulación de solutos compatibles ('osmolitos'), y la activación de sistemas antioxidantes. Estos mecanismos están conservados en todas las plantas, tolerantes y sensibles a estrés por igual, y no confieren necesariamente tolerancia. Para descifrar estos mecanismos y conseguir una mejor comprensión de la contribución de diferentes respuestas a estrés a la tolerancia al estrés en una especie dada, hemos llevado a cabo estudios comparativos sobre las respuestas a la sequía y la salinidad, en un número de taxones relacionados genéticamente con diferentes potenciales de tolerancia. Metodología El enfoque experimental se basó principalmente en i) establecer la tolerancia relativa al estrés hídrico y al estrés salino en las especies estudiadas, a partir de su distribución en la naturaleza (en el caso de especies silvestres) y atendiendo a la inhibición relativa de su crecimiento en presencia de estrés, y ii) correlacionar cambios en los niveles de 'marcadores bioquímicos de estrés' asociados a vías específicas de respuesta (transporte de iones, acumulación de osmolitos ...) inducidos por los tratamientos de estrés, con la tolerancia relativa a estrés de las plantas, previamente establecido. Esta estrategia ha resultado ser apropiada para distinguir meras respuestas generales a estrés de los mecanismos relevantes para la tolerancia a estrés de las especies y cultivares investigados. El trabajo también arroja luz sobre otros aspectos afectados por el estrés salino, específicamente en relación con la germinación y el éxito reproductivo, o cambios anatómicos en las plantas tratadas con sal. También se estudiaron los patrones de expresión del gen NHX1, que codifica un antiportador vacuolar Na+/H+, en las especies de Plantago, como un primer paso en la caracterización completa de este transportador de iones, que parece desempeñar un papel importante en los mecanismos de tolerancia a sal en este género. Conclusión Los resultados obtenidos en este trabajo contribuyen a una mejor comprensión de los mecanismos generales de tolerancia al estrés en plantas, y proporcionan ideas claras sobre los mecanismos que confieren tolerancia, en concreto, a la sequía y al estrés salino, en algunas especies silvestres y cultivadas. Este trabajo también arroja más luz sobre las respuestas a estrés altamente eficientes en halófitas, plantas que podrían ser vistas como la respuesta de la naturaleza a las condiciones ambientales adversas antes mencionadas, a través de la evolución y la adaptación. Por lo tanto, las halófitas pueden ser consideradas como una fuente adecuada - infrautilizada en la actualidad, en nuestra opinión - de conocimiento, recursos genéticos y herramientas biotecnológicas para la necesaria mejora de la tolerancia al estrés en plantas cultivadas. / [CA] Resum Introducció La salinitat i la sequera són les condicions d'estrès ambiental més importants, que redueixen els rendiments dels cultius a tot el món i que limiten la distribució de les plantes silvestres en la naturalesa. La salinitat del sòl, especialment la salinització secundària causada per pràctiques antropogèniques, com la irrigació perllongada, condueixen a pèrdues importants de rendiment agrícola, especialment en les regions àrides i semiàrides. La sequera, provocada per la reducció de contingut d'aigua en el sòl, es produeix a causa d'alteracions en el cicle de l'aigua en la naturalesa, principalment quan la evapotranspiració excedeix la precipitació en un àrea determinada, fins al punt que les reserves d'aigua del sòl ja no poden suportar el creixement de la planta. La sequera i l'estrès salí desencadenen l'activació d'una sèrie de mecanismes bàsics de resposta, que inclouen entre uns altres el control del transport, l'exclusió i la compartimentació d'ions, així com l'acumulació de soluts compatibles ('osmolits'), i l'activació de sistemes antioxidants. Aquests mecanismes estan conservats en totes les plantes, tolerants i sensibles a estrès per igual, i no confereixen necessàriament tolerància. Per a desxifrar aquests mecanismes i aconseguir una millor comprensió de la contribució de diferents respostes a estrès a la tolerància a l'estrès en una espècie donada, hem dut a terme estudis comparatius sobre les respostes a la sequera i la salinitat, en un nombre de taxons relacionats genèticament amb diferents potencials de tolerància. Metodologia L'enfocament experimental es va basar principalment en i) establir la tolerància relativa a l'estrès hídric i a l'estrès salí en les espècies estudiades, a partir de la seua distribució en la naturalesa (en el cas d'espècies silvestres) i atenent a la inhibició relativa de el seu creixement en presència d'estrès, i ii) correlacionar canvis en els nivells de 'marcadors bioquímics d'estrès' associats a vies específiques de resposta (transport d'ions, acumulació d'osmolits ...) induïts pels tractaments d'estrès, amb la tolerància relativa a estrès de les plantes, prèviament establert. Aquesta estratègia ha resultat ser apropiada per a distingir meres respostes generals a estrès dels mecanismes rellevants per a la tolerància a estrès de les espècies i conreus investigats. El treball també llança llum sobre altres aspectes afectats per l'estrès salí, específicament en relació amb la germinació i l'èxit reproductiu, o canvis anatòmics en les plantes tractades amb sal. També es van estudiar els patrons d'expressió del gen NHX1, que codifica un anti-portador vacuolar Na+/H+, en les espècies de Plantago, com un primer pas en la caracterització completa d'aquest transportador d'ions, que sembla exercir un paper important en els mecanismes de tolerància a sal en aquest gènere. Conclusió Els resultats obtinguts en aquest treball contribueixen a una millor comprensió dels mecanismes generals de tolerància a l'estrès en plantes, i proporcionen idees clares sobre els mecanismes que confereixen tolerància, en concret, a la sequera i a l'estrès salí, en algunes espècies silvestres i conreades. Aquest treball també llança més llum sobre les respostes a estrès altament eficients en halòfites, plantes que podrien ser vistes com la resposta de la naturalesa a les condicions ambientals adverses abans esmentades, a través de l'evolució i l'adaptació. Per tant, les halòfites poden ser considerades com una font adequada - infrautilitzada en l'actualitat, en la nostra opinió - de coneixement, recursos genètics i eines biotecnològiques per a la necessària millora de la tolerància a l'estrès en plantes conreades. / Al Hassan, M. (2016). Comparative analyses of plant responses to drought and salt stress in related taxa: A useful approach to study stress tolerance mechanisms [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/61985 / TESIS
67

Modeling of Ion Transport for Micro/Nano Size Particles in Coulter Counter Application

Qin, Zhenpeng 09 June 2009 (has links)
No description available.
68

The Effects of Amino Acids and Mitogen Activated Protein Kinase (MAPK) Inhibitors on Fluid Secretion and Ion Transport by Isolated Malpighian Tubules of Rhodnius Prolixus and Drosophila Melanogaster

Hazel, Matthew 09 1900 (has links)
Insect haemolynph typically contains very high levels of free amino acids 50 1 00 times that which is normal for mammalian plasma. This study examines the modulatory effects of amino acids on fluid secretion and ion transport by isolated MTs of Rhodnius prolixus and Drosophila melanogaster. The results show that the secretion rates of isolated Malpighian tubules of both Rhodnius and Drosophila are modulated by the presence of specific amino acids in the bathing saline. Some amino acids are stimulatory, some are inhibitory and others have little or no effect. Glutamine appears to be particularly important as a stimulant of fluid secretion. As well, secreted fluid pH and Na +concentration increase and K+ concentration decreases in response to glutamine. Amino acids do not appear to be important as metabolite. in Rhodnius tubules, nor do they act to draw significant amounts of water into the lumen by osmosis. Significant stimulation of fluid secretion can be achieved by physiological levels of particular amino acids, whereas those amino acids that inhibit fluid secretion only do so at concentrations much above those at which they occur naturally in the haemolymph. Amino acids are known to be compatible osmolytes and may be acting to maintain cell homeostasis and thus to sustain fluid secretion. The passive movement of amino acids may result in cell volume changes, and some form of osmosensor is may be coupled to activation of specific kinases to produce the observed increases in fluid secretion. The effects of several kinase inhibitors were therefore examined. The glutamine dependent increase in MT fluid secretion is blocked by two inhibitors of the stress activated protein kinase (SAPK) pathway, SP600125 and dicumoral. Inhibitors of other kinases (PKA, PKC, PKG, PI-3, p38, ERK and MEK), did not block glutamine's effects on fluid secretion rate. Alterations in cytoskeletal structure appear not to be required because cytoskeletal disrupting agents did not block the glutamine dependent inc~ease in fluid secretion, nor was the increase dependent upon protein synthesis. Results of this study are the first to suggest a role for the SAPK pathway in the control of fluid secretion rates by insect Malpighian tubules. / Thesis / Master of Science (MS)
69

Development and Characterization of Advanced Polymer Electrolyte for Energy Storage and Conversion Devices

Wang, Ying 09 January 2017 (has links)
Among the myraid energy storage technologies, polymer electrolytes have been widely employed in diverse applications such as fuel cell membranes, battery separators, mechanical actuators, reverse-osmosis membranes and solar cells. The polymer electrolytes used for these applications usually require a combination of properties, including anisotropic orientation, tunable modulus, high ionic conductivity, light weight, high thermal stability and low cost. These critical properties have motivated researchers to find next-generation polymer electrolytes, for example ion gels. This dissertation aims to develop and characterize a new class of ion gel electrolytes based on ionic liquids and a rigid-rod polyelectrolyte. The rigid-rod polyelectrolyte poly (2,2'-disulfonyl-4,4'-benzidine terephthalamide) (PBDT) is a water-miscible system and forms a liquid crystal phase above a critical concentration. The diverse properties and broad applications of this rigid-rod polyelectrolyte may originate from the double helical conformation of PBDT molecular chains. We primarily develop an ionic liquid-based polymer gel electrolyte that possesses the following exceptional combination of properties: transport anisotropy up to 3.5×, high ionic conductivity (up to 8 mS cm⁻¹), widely tunable modulus (0.03 – 3 GPa) and high thermal stability (up to 300°C). This unique platform that combines ionic liquid and polyelectrolyte is essential to develop more advanced materials for broader applications. After we obtain the ion gels, we then mainly focus on modifying and then applying them in Li-metal batteries. As a next generation of Li batteries, the Li-metal battery offers higher energy capacity compared to the current Li-ion battery, thus satisfying our requirements in developing longer-lasting batteries for portable devices and even electric vehicles. However, Li dendrite growth on the Li metal anode has limited the pratical application of Li-metal batteries. This unexpected Li dendrite growth can be suppressed by developing polymer separators with high modulus (~ Gpa), while maintaining enough ionic conductivity (~ 1 mS/cm). Here, we describe an advanced solid-state electrolyte based on a sulfonated aramid rigid-rod polymer, an ionic liquid (IL), and a lithium salt, showing promise to make a breakthrough. This unique fabrication platform can be a milestone in discovering next-generation electrolyte materials. / Ph. D.
70

Development, Characterization, and Fundamental Studies on Molecular Ionic Composites and PBDT Hydrogels

Zanelotti, Curt Joseph 28 January 2022 (has links)
This dissertation aims to develop, characterize, and fundamentally understand a new class of materials termed "molecular ionic composites" (MICs). MICs show promise as next-generation solid electrolytes for batteries. MICs form when mixing a rigid polyanion with purely ionic fluids, and they behave mechanically as a solid but contain a high density of ions that move nearly as in a neat liquid. Specifically, prototypical MICs are based on solutions of the rigid-rod polyelectrolyte poly(2,2'-disulfonyl-4,4'-benzideneterephthalamide) (PBDT), which forms a double helix, combined with imidazolium-based ionic liquids (ILs). The IL comprises 75-97 wt% of the final solid, even though the Young's modulus can reach ~ 2 GPa at 80 wt% IL. We propose that these properties are driven by a biphasic internal structure in MICs corresponding to IL-rich "puddles" (an interconnected liquid phase) and PBDT-IL associated "bundles" where IL ions form the collective electrostatic associations that cause the MICs to be a solid. Through this dissertation I will discuss a wide variety of MICs that have been created through the use of two different formation processes, the "ingot" method and the "solvent casting" method, which allow for the use of many different ionic fluid sources to further tune MIC properties. The following chapters build to the fundamental knowledge and our current understanding of the wide variety of materials that can be created from PBDT and IL. / Doctor of Philosophy / Battery electrolytes, biosensors, and hydrogels all depend on new materials for next-generation applications. For these new materials to be used characterization on the interactions, morphological restrictions, and/or what unique internal structures used to generate their properties must be performed. Through This analysis using common polymeric characterization techniques these materials can be further optimized. This dissertation highlights a new class of materials termed "molecular ionic composites" (MICs) which are formed from a rigid double helical polymer, poly(2,2'-disulfonyl-4,4'-benzideneterephthalamide) (PBDT), and fluids composed entirely of ions, including ionic liquids (ILs). These composite systems feature a unique combination of properties including high thermal stability, mechanical stability, and excellent ionic conductivity, all of which are highly tunable through the amount of PBDT incorporated or the fluid ion types. Chapters 3, 4, 5, and 6 present fundamental investigations of MICs to determine how tunable they are, the processes by which they form, and the various ways we can fabricate them. Chapter 7 describes the creation of another impressive material formed from PBDT-low-polymer-content hydrogels. These studies are intended to provide deeper understanding of the behaviors of these unique materials and how they may be used in the future.

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