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Engineering, Synthesis and Characterization of New - π Conjugated (Macro)molecular Architectures for Organic Optoelectronics : application toward ambipolar materials / Ingénierie, synthèse et charactérisation d'architectures nouvelles π-conjuguées (macro)moléculaires pour des optoélectroniques organiques : application vers des matériaux ambipolairesXiao, Yiming 23 October 2014 (has links)
Dans le domaine de l’électronique organique comprenant les cellules photovoltaïques (OPV), les diodes électroluminescentes (OLED) et les transistors à effet de champ (OFET), l’intérêt pour des matériaux ambipolaires a fortement augmenté au cours de ces dernières années.Dans ce contexte, nous nous sommes intéressés au cours de cette thèse au design et à la préparation de différentes architectures semi-conductrices auto-organisées avec lesquelles il serait possible d’injecter et de transporter à la fois les trous et les électrons. Notre approche est basée sur des matériaux cristaux liquide (LC) incorporant différents types de systèmes électron-donneurs (p-type) ou électron-accepteurs (n-type) dans une architecture moléculaire ou macromoléculaire unique. Ainsi, nous avons synthétisé et caractérisé différentes séries de semi-conducteurs organiques tels que des diades discotiques LC donneur-σ-accepteur, des diades calamitiques LC donneur-σ-accepteur, et des polymères en peigne LC donneur-σ-accepteur portant des groupements latéraux discotiques. Leurs comportement thermiques, leurs propriétés optiques et électroniques, leurs propriétés d’auto-organisation en volume et en film mince, ainsi que leurs propriétés de transport de charge sont présentées et discutés.Ces études ont montré que tous ces matériaux présentent des propriétés liquide-cristallines en s’auto-organisant selon différentes structures telles que des organisations colonnaires, lamellaires et lamello-colonnaires. Plus particulièrement, ces matériaux montrent une nano-ségrégation spontanée en volume des fragments de type p et de type n, formant des chemins bien distincts pour chaque type de porteurs de charge, ces résultats étant bien mis en évidence par les premières mesures de transport de charge ambipolaire observées par temps de vol et en configuration transistor à effet de champs. / In the general field of organic electronics, including Organic Photovoltaic (OPV), Organic Light-Emitting Diode (OLED) and Organic Field-Effect Transistor (OFET), the interest for the ambipolar organic materials have increased remarkably during the recent years.In this context, we were interested, in this present work, in designing and preparing different new self-organized semiconducting architectures in which it could be possible to inject and transport both holes and electrons. Our approach is based on liquid crystalline (LC) materials incorporating different kinds of electron-donor (p-type) and electron acceptor (n-type) π-conjugated systems in a unique molecular or macromolecular architecture. Thus, we synthesized and characterized different series of organic semiconductors such as donor-σ-acceptor discotic LC dyads and triads, donor-σ-acceptor calamitic LC dyads, and donor-σ-acceptor side-chain LC polymers bearing discotic side-groups. Their thermal behaviors, optical and electronic properties, self-organization properties both in bulk and in thin films, and finally charge transport properties are presented and discussed.Based on different characterization techniques, we demonstrated that all these series of materials present liquid crystalline properties in self-organizing in different structure such as columnar, lamellar, and lamella-columnar organizations. More particularly, these materials exhibit spontaneous nanosegregation of p-type and n-type entities in bulk, leading to well defined distinct conductive channels for each type of charge carriers as evidenced by the preliminary ambipolar charge transport properties observed by Time-of-flight and Field effect transistor measurements.
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The effect of global climate change on the release of terrestrial organic carbon in the Arctic RegionDogrul Selver, Ayca January 2014 (has links)
The Arctic Region is currently experiencing an amplified warming if compared to the rest of the world. The soils in this region store approximately half of the global soil organic carbon (OC), mainly locked in the permanently-frozen ground (permafrost). This carbon sink is sensitive to global warming meaning that the predicted warming will likely increase the thaw-release of this ‘old’ carbon. However, what happens to this remobilized OC once it is transported to the Arctic Ocean, including the potential conversion to greenhouse gasses causing a positive feedback to climate warming, remains unclear. In this work, we further investigate the fate of terrestrial derived OC (terrOC) in the Eurasian Arctic Region. The key findings of this work are: • Glycerol dialkyl glycerol tetraethers (GDGTs) and bacteriohopanepolyols (BHPs) are present in marine sediments of the Eurasian Arctic Region and the associated Branched and Isoprenoidal tetraether (BIT) and Rsoil indices can be used to trace terrOC in marine realm. However, a slight modification in the Rsoil index is suggested (R’soil). • Analyses indicate that the behaviour of BIT is largely controlled by a marine GDGT contribution while the R’soil index is mainly controlled by the removal of soil marker BHPs. Although both indices suggest a non-conservative behavior for the terrOC, this leads to differences in the estimations for the percentage terrOC present. A multi-proxy approach is essential since the use of a single-proxy approach can lead to over/under estimation.• Comparison of BIT and 13Csoc indices across the East Siberian Shelf indicates that the BIT index is possibly reflecting a predominantly fluvial input while 13Csoc represents a mixed fluvial and coastal erosion input.• The macromolecular terrOC composition varies along a west-east Eurasian Arctic climosequence and is mainly controlled by the river runoff of surface derived terrOC and wetland coverage (sphagnum vs. higher plants) but is not affected by the presence/absence of continuous permafrost. • The phenols/(phenols+pyridines) ratio was suggested as a proxy to trace terrOC at the macromolecular level along the Kolyma River-East Siberian Sea transect. The results indicate a non-conservative behavior of the macromolecular terrOC comparable to the bulk of the terrOC.All molecular analyses/based proxies used showed that the remobilized terrOC in the Eurasian Arctic region behaves non-conservatively potentially causing a positive feedback to global climate change.
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Mechanism and Function of Actin Pedestal Formation by Enterohemorrhagic <em>Escherichia coli</em> O157:H7: A DissertationBrady, Michael John 14 June 2007 (has links)
Enterohemorrhagic Escherichia coli O157:H7 (EHEC) and enteropathogenic E. coli O127:H7 (EPEC) induce characteristic F-actin rich pedestals on infected mammalian cells. Each pathogen delivers its own translocated intimin receptor (Tir) to the host cell to act as a receptor for the bacterial outer membrane adhesin, intimin. Interaction of translocated Tir with intimin is essential for mammalian cell binding and host colonization, as well as to induce actin pedestal formation in vitro. In spite of these parallels, EHEC and EPEC Tir appear to generate actin pedestals by distinct mechanisms. Further, while the ability to form actin pedestals is a striking phenotype, the function of pedestals during infection remains unclear. To address these issues, a systematic and quantitative analysis of Tir-mediated actin assembly was conducted. We identified a three-residue Tir sequence involved in actin pedestal formation for both EHEC and EPEC, and developed evidence that the two pathogens trigger a common pathway for actin assembly. Further, the ability of these bacteria to promote actin assembly appears to promote both intimin-mediated bacterial binding in vitro and optimal colonization during experimental animal infection.
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Výstavy pořádané v prostorách Československé akademie věd a Akademie věd České republiky / Exhibitions held in the spaces of the Czechoslovak Academy of Sciences and the Academy of Sciences of the Czech Republic.Šandová, Nela January 2017 (has links)
The diploma thesis will focus on the exhibition activities of institutes of the Czechoslovakian Academy of Sciences (ČSAV) from the 1970s until nowadays exhibition activities of the Academy of Sciences of the Czech Republic (AV ČR). The institutes of the ČSAV were among a few places where unofficial and often also politically undesirable artists could exhibit their work. One of the main chapters in my thesis will deal with the Institute of Macromolecular Chemistry, in particular, where exhibitions in the entrance hall are still held until nowadays. Furthermore I will focus on architect of The Macromolecular institute and the artists whose work has been presented here, eg. V. Boštík, A. Šimotová, O. Zoubek etc., as well as the particular places serving as alternative galleries. The aim of my thesis will be also showing the function of those places in these days and investigating the overall public interest in the cultural activities of the AV ČR. Keywords Czechoslovakian Academy of Sciences (ČSAV), Academy of Sciences of the Czech Republic (AV ČR), Institute of Macromolecular Chemistry, Karel Prager, Makráč, Gallery 4P, Philosophical club, Alternative exhibition places, Prohibited art
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High Temperature Semiconducting Polymers and Polymer BlendsAristide Gumyusenge (8086511) 05 December 2019
Organic semiconductors have witnessed a prolific boom for their potential in the manufacturing of lightweight, flexible, and even biocompatible electronics. One of the fields of research that has yet to benefit from organic semiconductors is high temperature electronics. The lightweight nature and robust processability is attractive for applications such as aerospace engineering, which require high temperature stability, but little has been reported on taking such a leap because charge transport is temperature dependent and commonly unstable at elevated temperatures in organics. Historically, mechanistic studies have been bound to low temperature regimes where structural disorders are minimal in most materials. Discussed here is a blending approach to render semiconducting polymer thin films thermally stable in unprecedented operation temperature ranges for organic materials. We found that by utilizing highly rigid host materials, semiconducting polymer domains could be confined, thus improving their molecular and microstructural ordering, and a thermally stable charge transport could be realized up to 220°C. With this blending approach, all-plastic high temperature electronics that are extremely stable could also be demonstrated. In efforts to establish a universal route towards forming thermally stable semiconducting blends, we found that the molecular weight of conjugated polymer plays a crucial role on the miscibility of the blends. Finally, we found that the choice of the host matrix ought to consider the charge trapping nature of the insulator.<br>
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Structure of the Plant-Conserved Region of Cellulose Synthase and Its Interactions with the Catalytic CorePhillip S Rushton (9143657) 29 July 2020 (has links)
<p><a>The processive plant cellulose synthase (CESA) synthesizes
(1→4)-β-D-glucans. CESAs assemble into a six-fold symmetrical cellulose
synthase complex (CSC), with an unknown symmetry and number of CESA isomers.
The CSC synthesizes a cellulose microfibril as the fundamental scaffolding unit
of the plant cell wall. CESAs are approximately 110 kDa glycosyltransferases
with an N-terminal RING-type zinc finger domain (ZnF), seven transmembrane
α-helices (TMHs) and a cytoplasmic catalytic domain (CatD). In the CatD, the uridine
diphosphate glucose (UDP-Glc) substrate is synthesized into</a>
(1→4)-β-D-glucans. The ZnF is likely to facilitate
dimers in the CSC. Recombinant class-specific region (CSR), a plant specific
insertion to the C-terminal end of the CatD is also known to form dimers<i> in
vitro</i>. The CSR sequence is the primary source of distinction between CESA
isoforms and class structure. Also within the CESA CatD is a 125-amino acid
insertion known as the plant-conserved region (P-CR), whose molecular structure
was unknown. The function of the P-CR is still unclear, especially in the
context of complete CESA and CSC structures. Thus, one major knowledge gap is
understanding how multimeric CSCs synthesize multiple chains of (1→4)-β-D-glucans
that coalesce to form microfibrils. The specific number of CESAs in a CSC and
how interactions of individual CESA isoforms contribute to the CSC are not
known. Elucidating the structure-function relationships of the P-CR domain, and
with the consideration of the ability of CSR and ZnF domains to dimerize, it is
possible to more completely model the structure of the CSC.</p>
<p>Recombinantly expressed rice (<i>Oryza
sativa</i>) secondary cell wall OsCESA8 P-CR domain purifies as a monomer and
shows distinct α-helical secondary structure by circular dichroism analysis. A
molecular envelope of the P-CR was derived by small angle X-ray scattering
(SAXS). The P-CR was crystallized and structure solved to 2.4 Å resolution
revealing an anti-parallel coiled-coiled domain. Connecting the coiled-coil
α-helices is an ordered loop that bends back towards the coiled-coils. The P-CR
crystal structure fits the molecular envelope derived by SAXS, which in turn
fits into the CatD molecular envelope. The best fit places the P-CR between the
membrane and substrate entry portal. In depth analysis of structural similarity
to other proteins, and 3D-surface structure of the P-CR, leads to hypotheses
that it could function in protein-protein interactions as a dimer, trimer or
tetramer in the CSC, that it could form protein-protein interactions with CESA-interacting
proteins, and/or modulate substrate entry through its N- and/or C-terminus.
From modeling, hypothetically important residues within the P-CR or related to
the P-CR through potential protein contacts were mutated in <i>Arabidopsis
thaliana</i> <i>AtCESA1</i> constructs. These constructs were expressed in the
temperature-sensitive <i>radial swelling</i> (<i>rsw</i>)<i> rsw1-1</i> mutant
of <i>AtCESA1 </i>to test for complementation of growth phenotypes at
restrictive temperatures. Preliminary experiments indicate that some mutated
CESA1 sequences fail to complement the <i>rsw1-1</i> phenotype, suggesting that
specific functions of individual amino can be tested using this system.</p>
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Study of the Function and Dynamics of Myosin II and Actin in Cytokinesis: A DissertationZhou, Mian 26 May 2009 (has links)
Myosin II and actin are two major components of the ingressing cortex during cytokinesis. However, their structural dynamics and functions during cytokinesis are still poorly understood. To study the role of myosin II in cortical actin turnover, dividing normal rat kidney (NRK) cells were treated with blebbistatin, a potent inhibitor of the non-muscle myosin II ATPase. Blebbistatin caused a strong inhibition of actin filament turnover and cytokinesis. Local release of blebbistatin at the equator caused inhibition of cytokinesis, while treatment in the polar region also caused a high frequency of abnormal cytokinesis, suggesting that myosin II may play a global role. These observations indicate that myosin II ATPase is essential for actin turnover and remodeling during cytokinesis.
To further study the mechanism of myosin II and actin recruitment to the cytokinetic furrow, equatorial cortex were observed with total internal reflection fluorescence microscope (TIRF-M) coupled with spatial temporal image correlation spectroscopy (STICS) and a new approach termed temporal differential microscopy (TDM). The results indicated at least partially independent mechanisms for the early equatorial recruitment of myosin II and actin filaments. Cortical myosin II showed no detectable directional flow toward the equator. In addition to de novo equatorial assembly, localized inhibition of disassembly appeared to contribute to the formation of the equatorial myosin II band. In contrast, actin filaments underwent a striking, myosin II dependent flux toward the equator. However, myosin II was not required for equatorial actin concentration, suggesting that there was a flux-independent, de novo mechanism.
The study was then extended to retraction fibers found typically on mitotic adherent cells, to address the hypothesis that they may facilitate post-mitotic spreading. Cells with retraction fibers showed increased spreading speed in post-mitotic spreading compared to cells without retraction fibers. In addition, micromanipulation study suggested that retraction fibers may guide the direction of post-mitotic spreading. Focal adhesion proteins were present at the tips of retraction fibers, and may act as small nucleators for focal adhesions reassembly that help cell quickly respread and regrow focal adhesions. These findings may suggest a general mechanism utilized by adherent cells to facilitate post-mitotic spreading and reoccupy their previous territory.
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Mechanical Activation of Valvular Interstitial Cell Phenotype: A DissertationThrom Quinlan, Angela M. 01 August 2012 (has links)
During heart valve remodeling, and in many disease states, valvular interstitial cells (VICs) shift to an activated myofibroblast phenotype which is characterized by enhanced synthetic and contractile activity. Pronounced alpha smooth muscle actin (αSMA)-containing stress fibers, the hallmark of activated myofibroblasts, are also observed when VICs are placed under tension due to altered mechanical loading in vivo or during in vitro culture on stiff substrates or under high mechanical loads and in the presence of transforming growth factor-beta1 (TGF-β1). The work presented herein describes three distinct model systems for application of controlled mechanical environment to VICs cultured in vitro. The first system uses polyacrylamide (PA) gels of defined stiffness to evaluate the response of VICs over a large range of stiffness levels and TGF-β1 concentration. The second system controls the boundary stiffness of cell-populated gels using springs of defined stiffness. The third system cyclically stretches soft or stiff two-dimensional (2D) gels while cells are cultured on the gel surface as it is deformed. Through the use of these model systems, we have found that the level of 2D stiffness required to maintain the quiescent VIC phenotype is potentially too low for a material to both act as matrix to support cell growth in the non-activated state and also to withstand the mechanical loading that occurs during the cardiac cycle. Further, we found that increasing the boundary stiffness on a three-dimensional (3D) cell populated collagen gel resulted in increased cellular contractile forces, αSMA expression, and collagen gel (material) stiffness. Finally, VIC morphology is significantly altered in response to stiffness and stretch. On soft 2D substrates, VICs cultured statically exhibit a small rounded morphology, significantly smaller than on stiff substrates. Following equibiaxial cyclic stretch, VICs spread to the extent of cells cultured on stiff substrates, but did not reorient in response to uniaxial stretch to the extent of cells stretched on stiff substrates. These studies provide critical information for characterizing how VICs respond to mechanical stimuli. Characterization of these responses is important for the development of tissue engineered heart valves and contributes to the understanding of the role of mechanical cues on valve pathology and disease onset and progression. While this work is focused on valvular interstitial cells, the culture conditions and methods for applying mechanical stimulation could be applied to numerous other adherent cell types providing information on the response to mechanical stimuli relevant for optimizing cell culture, engineered tissues or fundamental research of disease states.
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Biomimetic Synthetic Tissue Scaffolds for Bone Regeneration: A DissertationFilion Potts, Tera M. 21 July 2011 (has links)
Injury to bone is one of the most prevalent and costly medical conditions. Clinical treatment of volumetric bone loss or hard-to-heal bony lesions often requires the use of proper bone grafting materials, with or without adjuvant anabolic therapeutics. Despite significant problems associated with autografting (donor site morbidity, limited supplies) and allografting (disease transmissions, high graft failure rates) procedures, synthetic bone grafts remain the least utilized clinically. Existing synthetic orthopaedic biomaterials rarely possess a combination of bone-like structural and biochemical properties required for robust osteointegration, scalable and user-friendly characteristics indispensable for successful clinical translations. This thesis tests the hypothesis that by recapitulating key structural elements and biochemical components of bone in 3- and 2-dimensional biomaterials, scalable synthetic bone grafts can be designed to enable expedited healing of hard-to-heal volumetric bone loss. Specifically, FlexBone, a 3-dimensional hydrogel scaffold encapsulating 50 wt% of structurally well integrated nanocrylstalline hydroxyapatite, the main inorganic component of bone, was developed. The large surface area of nanocrystalline hydroxyapatite combined with its intrinsic affinity to proteins and its excellent structural integration with the hydrogel matrix enabled FlexBone to both sequester endogenous protein signals upon press-fitting into an area of skeletal defect and to deliver exogenous protein therapeutics in a localized and sustained manner. We demonstrated that FlexBone enabled the functional healing of critical-size long bone defects in rats in 8 – 12 weeks with the addition of a very low dose of osteogenic growth factor BMP-2/7. This promising synthetic bone graft is now being explored for the delivery of multiple growth factors to expedite the healing of diabetic bony lesions. In addition, a 2-dimensional electrospun cellulose fibrous mesh was chemically modified with sulfate residues to mimic sulfated polysaccharide ECM components of skeletal tissues to enabled progenitor cell attachment and differentiation as well as controlled retention and localized/sustained delivery of protein therapeutics. This sulfated fibrous mesh is currently explored as synthetic periosteum to augment the osteointegration of devitalized structural allografts. Finally, a rat subcutaneous implantation model developed to examine the biocompatibility of newly developed biodegradable shape memory polymer bone substitutes is also presented.
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Electrolytes polymères monofonctionnels à conduction monocationique : synthèse et propriétés de transport d'ions lithium / Mono-EndCapped Single-Ion Polymer Electrolytes : Synthesis & Lithium-Ion Transport PropertiesOverton, Philip 27 March 2019 (has links)
Cette thèse décrit des électrolytes polymères à conduction mono-ionique (EC-SIPEs). Ces macromolécules sont constituées de n* unités répétition d’oxyde d’éthylène (OE) et d’un groupe fonctionnel ionique à une des extrémités de leur architecture macromoléculaire asymétrique. La bibliothèque des EC-SIPEs synthétisée est basée sur des poly(oxyde d’éthylène) mono méthyl éther (mPOEn-OH) ayant 8, 10, 20 et 55 unités EO. Les anions sont liés de manière covalente au squelette polymère via une des extrémités. Leur mobilité est donc limitée par celles de ces macromolécules fonctionnelles. Les EC-SIPES constituent des conducteurs mono-ioniques; la majorité des charges étant transférées par les cations Li+ comme démontré par chronoampérométrie.Les extrémités de chaînes sont sélectionnées pour développer des interactions ioniques facilitant la conduction de cation Li+ ainsi que des interactions non-covalentes de types dipôles-dipôles, Van der Waals, et d’empilements π-π. Des hydrocarbures aromatiques polycycliques de type naphtalène (naph) et pyrène (pyr) sont étudiés comme extrémités de chaines. Les groupes terminaux fonctionnels sont lithiés : sulfonates (-SO3Li, -PhSO3Li), N-naphtyl sulfonamide (-SO2N(Li)Naph) et N-arylamines (-N(Li)Naph, -N(Li)Pyr). Deux types d'extrémités ciblent des propriétés spécifiques : i) "double-sel" possédant deux fonctions ioniques et ii) zwittérionique conduisant le cation Li+ et l’anion TFSI-. Le doublement du nombre de Li+ par groupe terminal n’autorise pas l’amélioration attendue de la conductivité ionique (σ). Ceci implique que σ est limitée par la physicochimie des chaînes polymères et non par la concentration en Li+. L'EC-SIPE zwittérionique a un nombre de transport de lithium élevé (t+Li= 0,8) qui implique une mobilité réduite de l’anion TFIS- par rapport au cation Li+. La meilleure performance est obtenue avec le mPOEn-N(Li)Pyr (OEn= 10, 20, 55) : σ > 1,0*10-4 S/cm à T > 40 °C et 1*10-3 S/cm à 100 °C. Cet EC-SIPE à une résistivité constante en cyclage galvanostatique (j= 10 μA/cm^2 ; 10 périodes de 4h ; pile Li|Li ; 40 °C) et une stabilité électrochimique dans la plage de potentiel 0 V-3,7 V vs. Li/Li+ (pile Li|Stainless steel ; vitesse de balayage en potentiel 1,0 mV/s ; 40 °C).Le contexte de cette thèse vis à vis de l’état de l’art des électrolytes polymères pour les batteries Li-Ion est présenté dans le chapitre I. Deux sous-classes d’électrolytes sont discutées: i) les polymères dans lesquels un sel est solvaté (SiP) et ii) les polymères à conduction mono-ionique. La conception d'électrolytes polymères efficaces à conductivité ionique améliorée est ciblée. Une attention toute particulière est accordée aux concepts d'auto-organisation hiérarchique visant à la création de chemins percolant assurant le transport d’ions sur les distances microniques séparant les électrodes d’une batterie. Enfin, la stratégie de synthèse mise en œuvre dans cette thèse est décrite.Les principaux résultats de cette thèse sont présentés et discutés au chapitre II. Une bibliothèque d'EC-SIPEs est caractérisée vis-à-vis de leurs performances électrochimiques, thermiques et de leurs propriétés de transport ionique spécifique. Des caractéristiques résistives apparaissent à haute température et sont supposées résulter de l'agrégation des groupes ioniques terminaux. Les valeurs de conductivité des EC-SIPEs (55 Unités OE) s'améliorent d'un demi-ordre de grandeur lors du cyclage en température au-delà de la température de fusion des domaines cristallins de POE. La discussion se termine par la proposition d'un modèle de percolation des domaines ioniques dans les EC-SIPEs où les groupes ioniques sont localisés aux interfaces des domaines POE. La percolation des domaines ioniques devrait être améliorée dans des conditions appropriées de température et de force électromagnétique. Les méthodes de synthèse mises en œuvre dans cette thèse et les caractérisations des EC-SIPEs sont décrites au chapitre III. / This thesis presents "End-Capped Single-Ion Polymer Electrolytes" (EC-SIPEs) that are ionically conductive polymers having n repeating ethylene oxide (EO) units and an ionic functional group at one chain terminal. The library of EC-SIPEs presented are based on poly(ethylene oxide) mono methyl ether (mPEOn-OH) having EOn = 8, 10, 20 and 55. The anions of the electrolyte salt pair are covalently bound to the polymer as part of the end-group design. The mobility of the anion is thus limited by the low mobility of the polymer, relative to Li+. These are "Single-Ion" conductors because the majority of ionic charge transferred by Li+ cations, as demonstrated by chronoamperometry.The end-group designs target not only ionic interactions that facilitate "single-ion" conduction of Li+, but also other specific non-covalent interactions such as dipole-dipole, Van der Waals, and π-π stacking. End-groups having naphthalene (naph) and pyrene (pyr) polycyclic aromatic hydrocarbon (PAH) moieties are investigated. The functional end-groups are lithiated sulfonates (-SO3Li, -PhSO3Li), a N-naphyl sulfonamide (-SO2N(Li)Naph), and secondary N-aryl amines (-N(Li)Naph, -N(Li)Pyr). Two end-groups target specific properties: i) a "double salt" end-group has two ionic functions at one chain end, and ii) a zwitterionic EC-SIPE that conducts Li+ cations and TFSI- anions. The doubling of the number of Li+ per end-group does not correlate to an expected improvement in ionic conductivity (σ). This implies that σ is limited by the physicochemical properties of the EC-SIPE and not the Li+ concentration. The zwitterionic EC-SIPE has a high lithium transference number (t+Li= 0.8) that implies decreased mobility of the TFIS- counter-anion relative to Li+. The best overall performance is achieved by mPEOn-N(Li)Pyr (EOn= 10, 20, 55), that has σ > 1.0*10-4 S/cm at T > 40 °C, and reaches 1*10-3 S/cm at 100 °C. It exhibits constant resistivity under galvanostatic cycling (j= 10 μA.cm-2, 10*4h periods, Li|Li cell, 40 °C) and is electrochemically stable in the 0 V-3.7 V vs. Li/Li+ potential range (Li|stainless steel cell, 1.0 mV/s sweep rate, 40 °C).In Chapter I the context of the thesis is discussed through review of state-of-the-art polymer electrolytes for Li-ion batteries. These are divided into two sub-classes: i) Salt-in-Polymer (SiP) and ii) "Single-Ion" polymer electrolytes. The design of polymer electrolytes towards efficient and effective ionic conductivity is emphasized. Special attention is given to concepts for the organisation of bulk morphology for the creation of ion transport pathways that efficiently percolate through the micron length scale separating electrodes of a battery. Finally, the synthetic strategy implemented in this thesis is described.The principle results of the thesis are presented and discussed in Chapter II. A library of EC-SIPEs are characterised in terms of their electrochemical, thermal and specific ion-transport performances. Resistive features appear at high temperature and are expected to result from the aggregation of ionic end-groups. Surprisingly, the σ of EC-SIPEs having EOn= 55 improves by as much as half an order of magnitude with repeated cycling of temperature to above Tm of crystalline PEO (in the +40 °C to +100 °C range). The analysis of EC-SIPEs having different end-groups and PEO chains having EOn= 8, 10, 20, and 55 lead to the proposition of a tentative model for the percolation of ionic pathways through the EC-SIPE bulk. It is hypothesized that the ionic end-groups are localised at the grain boundaries of PEO domains. Percolation of these boundaries are proposed to be improved under appropriate, mild conditions of temperature and electromagnetic force. Finally, the synthesis methods implemented in this thesis and characterizations of EC-SIPEs are described in Chapter III.
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