Дисертації: "Ionic Liquid interaction"

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Wang, Yong-Lei. "Electrostatic Interactions in Coarse-Grained Simulations : Implementations and Applications." Doctoral thesis, Stockholms universitet, Institutionen för material- och miljökemi (MMK), 2013. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-92707.

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Electrostatic interactions between charged species play a prominent role in determining structures and states of physical system, leading to important technological and biological applications. In coarse-grained simulations, accurate description of electrostatic interactions is crucial in addressing physical phenomena at larger spatial and longer temporal scales. In this thesis, we implement ENUF method, an abbreviation for Ewald summation based on non-uniform fast Fourier transform technique, into dissipative particle dynamics (DPD) scheme. With determined suitable parameters, the computational complexity of ENUF-DPD method is approximately described as O(N logN). The ENUF-DPD method is further validated by investigating dependence of polyelectrolyte conformations on charge fraction of polyelectrolyte and counterion valency of added salts, and studying of specific binding structures of dendrimers on amphiphilic membranes. In coarse-grained simulations, electrostatic interactions are either explicitly calculated with suitable methods, or implicitly included in effective potentials. The effect of treatment fashion of electrostatic interactions on phase behavior of [BMIM][PF6] ionic liquid (IL) is systematically investigated. Our systematic analyses show that electrostatic interactions should be incorporated explicitly in development of effective potentials, as well as in coarse-grained simulations to improve reliability of simulation results. Detailed image of microscopic structures and orientations of [BMIM][PF6] at graphene and vacuum interfaces are investigated by using atomistic simulations. Imidazolium rings and alkyl side chains of [BMIM] lie preferentially flat on graphene surface. At IL-vacuum interface, ionic groups pack closely together to form polar domains, leaving alkyl side chains populated at interface and imparting hydrophobic character. With the increase of IL filmthickness, orientations of [BMIM] change gradually from dominant flat distributions along graphene surface to orientations where imidazolium rings are either parallel or perpendicular to IL-vacuum interface with tilted angles. The interfacial spatial ionic structural heterogeneity formed by ionic groups also contributes to heterogeneous dynamics in interfacial regions.

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França, João. "Solid-liquid interaction in ionanofluids. Experiments and molecular simulation." Thesis, Université Clermont Auvergne‎ (2017-2020), 2017. http://www.theses.fr/2017CLFAC077.

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L'un des principaux domaines de recherche en chimie et en ingénierie chimique implique l'utilisation de liquides ioniques et de nanomatériaux comme alternatives à de nombreux produits chimiques et processus chimiques, comme ce dernier étant actuellement considérés comme non respectueux de l'environnement. Leur utilisation potentiel comme nouveaux fluides de transfert de chaleur et matériaux de stockage de chaleur, qui peuvent obéir à la plupart des principes de la chimie verte, nécessite l'étude expérimentale et théorique des mécanismes de transfert de chaleur dans les fluides complexes comme les ionanofluides. Le but de cette thèse était d'étudier les ionanofluides, qui consistent en la dispersion de nanomatériaux dans un liquide ionique.Le premier objectif de ce travail était de mesurer les propriétés thermophysiques des liquides ioniques et ionanofluides, à savoir la conductivité thermique, la viscosité, la densité et la capacité thermique dans une gamme de température comprise entre -10 et 150 ºC et à pression atmosphérique. Dans ce sens, les propriétés thermophysiques d'un ensemble considérable de liquides ioniques et d'ionanofluides ont été mesurées, avec un accent particulier sur la conductivité thermique des fluides. Les liquides ioniques étudiés étaient [C2mim][EtSO4], [C4mim][(CF3SO2)2N], [C2mim][N(CN)2], [C4mim][N(CN)2], [C4mpyr][N(CN)2], [C2mim][SCN], [C4mim][SCN], [C2mim][C(CN)3], [C4mim][C(CN)3], [P66614][N(CN)2], [P66614][Br] et leurs suspensions avec 0.5% et 1% w/w de nanotubes de carbone multi-parois (MWCNTs - de l'anglais multi-walled carbon nanotubes). Les résultats obtenus montrent qu'il y a une augmentation substantielle de la conductivité thermique du fluide de base due à la suspension du nanomatériau, en considérant les deux fractions massiques. Cependant, l'amélioration varie de manière significative lorsqu'on considère différents liquides ioniques de base, avec une gamme comprise entre 2 et 30%, avec une température croissante. Ce fait rend plus difficile l'unification des informations obtenues afin d'obtenir un modèle permettant de prédire l'amélioration de la conductivité thermique. Les modèles actuellement utilisé pour calculer la conductivité thermique des nanofluides présentent des valeurs considérablement sous-estimées par rapport aux valeurs expérimentales, en partie à cause des considérations sur le rôle de l'interface solide-liquide sur le transport de la chaleur.En ce qui concerne la densité, l'impact de l'ajout de MWCNTs sur la densité du fluide de base est très faible, variant entre 0.25% et 0.5% pour 0.5% w/w et 1% w/w MWCNTs, respectivement. Cela était assez attendu et est dû à la différence considérable de densité entre les deux types de matériaux. Cependant, la viscosité était la propriété pour laquelle les valeurs les plus élevées d' augmentation ont été vérifiées, allant de 28 à 245% pour les deux fractions massiques de MWCNT. La capacité calorifique était la seule des quatre propriétés mentionnées ci-dessus à ne pas être étudiée dans ce travail en raison de problèmes techniques avec le calorimètre à utiliser. Néanmoins, la quantité de données recueillies sur les propriétés thermophysiques restantes était extensif. On pense que ce dernier contribue de manière significative à une base de données croissante des propriétés des liquides ioniques et des ionanofluides, tandis que en fournissant un aperçu de la variation des propriétés obtenues à partir de la suspension de MWCNTs dans des liquides ioniques.(...)
One of the main areas of research in chemistry and chemical engineering involves the use of ionic liquids and nanomaterials as alternatives to many chemical products and chemical processes, as the latter are currently considered to be environmentally non-friendly. Their possible use as new heat transfer fluids and heat storage materials, which can obey to most principles of green chemistry or green processing, requires the experimental and theoretical study of the heat transfer mechanisms in complex fluids, like the ionanofluids. It was the purpose of this dissertation to study ionanofluids, which consist on the dispersion of nanomaterials in an ionic liquid.The first objective of this work was to measure thermophysical properties of ionic liquids and ionanofluids, namely thermal conductivity, viscosity, density and heat capacity in a temperature range between -10 e 150 ºC and at atmospherical pressure. In this sense, the thermophysical properties of a considerable set of ionic liquids and ionanofluids were measured, with particular emphasis on the thermal conductivity of the fluids. The ionic liquids studied were [C2mim][EtSO4], [C4mim][(CF3SO2)2N], [C2mim][N(CN)2], [C4mim][N(CN)2], [C4mpyr][N(CN)2], [C2mim][SCN], [C4mim][SCN], [C2mim][C(CN)3], [C4mim][C(CN)3], [P66614][N(CN)2], [P66614][Br] and their suspensions with 0.5% and 1% w/w of multi-walled carbon nanotubes (MWCNTs). The results obtained show that there is a substantial enhancement of the thermal conductivity of the base fluid due to the suspension of the nanomaterial, considering both mass fractions. However, the enhancement varies significantly when considering different base ionic liquids, with a range between 2 to 30%, with increasing temperature. This fact makes it more difficult to unify the obtained information in order to obtain a model that allows predicting the enhancement of the thermal conductivity. Current models used to calculate the thermal conductivity of nanofluids present values that are considerably underestimated when compared to the experimental ones, somewhat due to the considerations on the role of the solid-liquid interface on heat transport.Considering density, the impact from the addition of MWCNTs on the base fluid’s density is very low, ranging between 0.25% and 0.5% for 0.5% w/w and 1% w/w MWCNTs, respectively. This was fairly expected and is due to the considerable difference in density between both types of materials. However, viscosity was the property for which the highest values of enhancement were verified, ranging between 28 and 245% in both mass fractions of MWCNTs. The heat capacity was the only of the four properties mentioned above not to be studied in this work due to technical issues with the calorimeter to be used. Nevertheless, the amount of data collected on the remainder thermophysical properties was extensive. It is believed that the latter contributes meaningfully to a growing database of ionic liquids and ionanofluids’ properties, while providing insight on the variation of said properties obtained from the suspension of MWCNTs in ionic liquids.The second objective of this work consisted on the development of molecular interaction models between ionic liquids and highly conductive nanomaterials, such as carbon nanotubes and graphene sheets. These models were constructed based on quantum calculations of the interaction energy between the ions and a cluster, providing interaction potentials. Once these models were obtained, a second stage on this computational approach entailed to simulate, by Molecular Dynamics methods, the interface nanomaterial/ionic liquid, in order to understand the specific interparticle/molecular interactions and their contribution to the heat transfer. This would allow to study both structural properties, such as the ordering of the ionic fluid at the interface, and dynamic ones, such as residence times and diffusion. (...)

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Cremer, Till [Verfasser], and Hans-Peter [Akademischer Betreuer] Steinrück. "Ionic Liquid Bulk and Interface Properties : Electronic Interaction, Molecular Orientation and Growth Characteristics = Ionische Flüssigkeiten und deren Volumen- und Grenzflächeneigenschaften / Till Cremer. Betreuer: Hans-Peter Steinrück." Erlangen : Universitätsbibliothek der Universität Erlangen-Nürnberg, 2012. http://d-nb.info/1021259578/34.

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Cho, Chul-Woong [Verfasser], Jorg Akademischer Betreuer] Thöming, and Ingo [Akademischer Betreuer] [Krossing. "The contribution of molecular interaction potentials to properties and activities of ionic liquid ions in solution / Chul-Woong Cho. Gutachter: Jorg Thöming ; Ingo Krossing. Betreuer: Jorg Thöming." Bremen : Staats- und Universitätsbibliothek Bremen, 2012. http://d-nb.info/1071993739/34.

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Ashworth, Claire. "A computational investigation of local interactions within ionic liquids and ionic liquid analogues." Thesis, Imperial College London, 2015. http://hdl.handle.net/10044/1/58256.

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The potential applications of ionic liquids and related analogues are diverse. However, for large-scale industrial applications low cost ionic liquids are required. Moreover, for the full potential of ionic liquids to be realised, a fundamental link between molecular level interactions, structuring and the bulk phase properties must be established. Deep eutectic solvents (DESs) and protic ionic liquids have been identified as candidates for the potential application of chalcopyrite leaching. The choline chloride – urea DES and 1- butylimidazolium hydrogensulphate protic ionic liquid were selected as systems of primary interest. Local structuring within the selected systems has been investigated, with an emphasis on the hydrogen bonding interactions. The choline chloride – urea mixture is a prototypical example of a DES. Using DFT, the pairwise interactions between the constituent components, and within clusters composed of n.urea.choline-chloride (n = 1-3), have been evaluated. Many different types of hydrogen bond have been identified, exhibiting flexibility in both strength and number. The formation of the commonly proposed [2urea⋅Cl]– complexed anion has been scrutinised and found to be energetically competitive with other interactions. Moreover, contrary to existing proposals, the negative charge is found to remain localised on chloride. The cation-anion and anion-anion interactions within [C4Him][HSO4] and related systems have been compared and contrasted;; ion pairs were evaluated using DFT and the bulk systems modelled using classical MD. Local structuring within [C4Him][HSO4] exhibits features of both the aprotic analogue and alkylammonium protic ionic liquids. [HSO4]–⋅⋅⋅[HSO4]– interactions have been considered and found to be a notable feature of the [HSO4]– ionic liquids studied. It is anticipated that the formation of [HSO4]– aggregates influences the properties of the bulk systems. A QM/MM method for the study of ionic liquids is introduced. Preliminary analysis suggests that this is a viable approach for the investigation of local structuring within ionic liquids.

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Mamusa, Marianna. "Colloidal interactions in ionic liquids." Phd thesis, Université Pierre et Marie Curie - Paris VI, 2014. http://tel.archives-ouvertes.fr/tel-01058482.

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Ionic liquids (ILs) are a novel class of ionic solvents, which are being used more and more often in chemical systems based on nanoparticles (NP) for several industrial and technological applications. However, at present we are unable to master the state of dispersion or aggregation of NP in these solvents, and the classic theories applied to colloidal stability, such as the DLVO, cannot be applied. In particular, the difficulty is found in the description of the electrostatic interactions in these ionic media. In this work, we try to better understand colloidal interactions in ILs through two systems that have been thoroughly characterized separately: magnetic maghemite nanoparticles, whose surface is well controlled in water, and the ionic liquid ethylammonium nitrate (EAN), known for its resemblance to water. These two systems are finally mixed together and studied at both the macroscopic and microscopic levels. We perform characterizations through several techniques: flame atomic absorption spectroscopy, optical microscopy under magnetic field, scattering methods (neutrons, X-rays and light), magneto-optic birefringence. We discover the importance of having a charged NP surface in order to obtain stable maghemite dispersions in EAN. In particular, the best colloidal stability is reached by adsorbing citrate molecules on the NP surface. We further investigate the effect of the NP's size and concentration, of the cationic counterion used to compensate the charge of citrate, of water content. Finally, we transfer our acquired knowledge to the realization of dispersions in biocompatible ILs.

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Hessey, Stephen. "Surface interactions of ionic liquids." Thesis, University of Nottingham, 2012. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.664318.

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This thesis presents an investigation into the interactions between IL surfaces and gases through studying the kinetics of absorption, adsorption and desorption. A model for absorption is presented in which a gaseous molecule that impacts the surface first enters a physisorbed state, from which it can either desorb or be absorbed into the bulk IL.

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Choudhury, Subhankar. "Physicochemical study of diverse interactions of ionic liquids and biologically active solutes prevailing in liquid environments." Thesis, University of North Bengal, 2016. http://ir.nbu.ac.in/handle/123456789/2763.

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Turner, Adam Henry. "Investigations of ionic liquid-solute interactions towards applications." Thesis, Queen's University Belfast, 2016. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.713456.

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He, Yunfei. "Study on the interfacial properties of surfactants and their interactions with DNA." Thesis, Paris 11, 2013. http://www.theses.fr/2013PA112112/document.

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Ayant une partie hydrophile et une partie hydrophobe, les tensioactifs peuvent s'adsorber sur des interfaces et d'abaisser la tension interfaciale (γ), ce qui améliore les propriétés interfaciales. Tensioactifs chargés sont également utilisés dans des applications biologiques, par exemple dans la livraison de gènes. Dans cette thèse, nous avons étudié les propriétés d'adsorption des tensioactifs, à la fois aux interfaces air/eau et sur l'ADN pour former des complexes.La première partie de la thèse se concentre sur les études d'interface de tensioactifs. Pour comprendre comment ils fonctionnent dans ces applications, il est important de connaître les échelles de temps de l'adsorption et la désorption de surfactant. Ainsi, il est nécessaire d'étudier l'adsorption et la cinétique de désorption, qui sont déjà largement étudié. Cependant, les études traditionnelles ont tendance à faire de nombreuses hypothèses, par exemple, l'extension de l'applicabilité des relations d'équilibre à des cas de non-équilibre. Dans cette mémoire, l'adsorption des deux systèmes tensioactifs différents a été étudiée, C12E6 de tensioactif non ionique et d'agent tensio-actif ionique CTAB avec suffisamment de sel. Une mesure de la compression de la bulle unique combiné avec une tension superficielle d'équilibre connue (γeq) de valeur permet de déterminer γ(Γ), ce qui est plus précis que les résultats des méthodes traditionnelles. Les concentrations de surface en fonction du temps sont mesurés, ce qui montre que l'adsorption est contrôlée par la diffusion à temps courts.Après avoir montré que l'adsorption est contrôlée par diffusion, nous rapportons la désorption des tensioactifs à partir de l'interface air/eau pour différents systèmes. Les processus de désorption sont confirmées pas être purement limitée par diffusion, indiquant la présence d'une barrière d'énergie. La barrière d'énergie est influencée par la longueur de la chaîne alkyle, et non le type de contre-ion.Dans la deuxième partie de la thèse, nous nous concentrons sur les systèmes d'ADN/tensioactif. Bien que l'interaction entre les tensioactifs cationiques et anioniques polyélectrolyte a été largement étudiée, il reste nécessaire de mieux comprendre le système complexe, en particulier pour rationaliser le choix des tensioactifs pour atteindre une capacité de liaison de l'ADN contrôlable et une faible toxicité pour l'organisme. Dans cette thèse, nous avons lancé l'enquête systématique sur les interactions des deux tensioactifs cationiques avec l'ADN.Le premier tensioactif utilisé est un gemini tensioactifs cationiques 12-2-12∙2Br. Avant de l'utiliser avec l'ADN d'une caractérisation approfondie a été effectuée. L'équilibrage du 12-2-12∙2Br sur une interface air/eau en l'absence d'électrolyte est très lent. Ajout de NaBr affecte peu la cinétique d'adsorption à des temps courts, pendant lesquels l'adsorption de diffusion. Cependant, l'adsorption s'équilibre beaucoup plus rapide. La formation de micelles de tensioactif cationique gemini 12-3-12∙2Br a été étudiée. La concentration micellaire critique (CMC) augmente légèrement avec la température et diminue avec la force ionique. 12-3-12∙2Br interagit fortement avec l'ADN, en raison de l'attraction électrostatique entre les deux et les interactions hydrophobes entre les chaînes alkyles. Sel écrans l'attraction électrostatique, tout en augmentant la longueur d'écartement des Gémeaux tensioactif affaiblit son interaction avec l'ADN.Un autre agent a également été étudié pour sa capacité de liaison à l'ADN et nous présentons une étude systématique sur les interactions entre tensioactif cationique liquide ionique [C12mim]Br et de l'ADN par des techniques expérimentales et de dynamique moléculaire (MD) de simulation. En ajoutant [C12mim]Br, les chaînes d'ADN sont soumis à compactage, des changements conformationnels, avec le changement de charge nette portée par le complexe ADN/tensioactif. simulation de MD confirme les résultats expérimentaux
Bearing a hydrophilic part and a hydrophobic part, surfactants can adsorb onto interfaces and lower the interfacial tension (γ), thereby enhancing the interfacial properties and leading to the applications in cleaning, surface functionalization, foaming and emulsification. Charged surfactants are also used in biological applications, in particular to extract and purify DNA, or for gene delivery. In this thesis we have studied the adsorption properties of surfactants, both to air/water interfaces and onto DNA to form complexes. The first part of the thesis concentrates on interfacial studies of surfactants. To understand how they work in these applications it is important to know the time-scales of the surfactant adsorption and desorption. Thus it is necessary to investigate the adsorption and desorption kinetics, which are already widely studied. However, traditional studies tend to make many assumptions, for example, extending the applicability of equilibrium relations to non-equilibrium cases. In this dissertation, the adsorption of two different surfactant systems has been investigated, non-ionic surfactant C12E6 and ionic surfactant CTAB with sufficient salt. A single bubble compression measurement combined with a known equilibrium surface tension (γeq) value allows the determination of γ(Γ), which is more accurate than results from traditional methods. The time-dependent surface concentrations are measured, showing that the adsorption is diffusion controlled at short times.Having shown that adsorption is diffusion controlled, we report desorption of surfactants from the air/water interface for different systems. The desorption processes are confirmed not to be purely diffusion-limited, showing the presence of an energy barrier. The energy barrier is influenced by the alkyl chain length, but not the counterion type.In the second part of the thesis we concentrate on DNA/surfactant systems. Although the interaction between cationic surfactant and anionic polyelectrolyte has been extensively studied, there still remains need to further understand the complex system, especially to rationalize the choice of surfactants to reach controllable DNA binding ability and low toxicity to the organism. In this dissertation, we introduced the systematic investigation on the interactions of two cationic surfactants with DNA.The first surfactant used is a cationic gemini surfactant 12-2-12∙2Br. Before using it with DNA a thorough characterization has been carried out. The equilibration of 12-2-12∙2Br onto an air/water interfaces in the absence of electrolyte is very slow. Addition of NaBr hardly affects the adsorption kinetics at short times, during which the adsorption is diffusive. However, the adsorption equilibrates much faster. The micellization of cationic gemini surfactant 12-3-12·2Br has been investigated. The critical micelle concentration (CMC) increases slightly with temperature and decreases with ionic strength. 12-3-12·2Br interacts strongly with DNA, due to the electrostatic attraction between the two and the hydrophobic interactions between alkyl chains. Salt screens the electrostatic attraction, while increasing spacer length of gemini surfactant weakens its interaction with DNA.Another surfactant has also been studied for its DNA binding ability and we present a systematic study on interactions between cationic ionic liquid surfactant [C12mim]Br and DNA by experimental techniques and Molecular Dynamics (MD) simulation. By adding [C12mim]Br, DNA chains undergo compaction, conformational changes, with the change of net charges carried by the DNA/surfactant complex. MD simulation confirms the experimental results

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Jain, P. "Ionic liquids: hydrophobicity, enthalpic effects accompanying ionic interactions and their transport properties." Thesis(Ph.D.), CSIR-National Chemical Laboratory, Pune, 2017. http://dspace.ncl.res.in:8080/xmlui/handle/20.500.12252/4353.

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Mendonça, Carlos Miguel Nóbrega. "Interactions between ionic liquids and cell membrane models." Master's thesis, Universidade de Aveiro, 2014. http://hdl.handle.net/10773/13836.

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Mestrado em Biotecnologia Molecular
This work proposes the study of the interactions, at a molecular level, between diverse ionic liquids (ILs) and the membrane cells, by applying membrane cell models, namely Langmuir-Blodgett technique. We intend to establish a better understanding about the role of the interactions of ILs with membrane cells, in specific, the imidazolium and choliniumcholinium families. Hence, we propose the evaluation of the effect of the concentration as well as of the alkyl chain lengths of imidazolium ILs, on the lipid monolayers organization and stability and compare it with the behaviour of choliniumcholinium ILs. Summing up, this work is expected to provide an insight into the molecular mechanism contributing to the IL toxic activity that should help in the design of less toxic ILs.
Este trabalho propõe o estudo das interações, ao nível molecular, entre diversos líquidos iónicos (ILs) e membranas celulares mediante a aplicação de modelos de membrana celular segundo a técnica de Langmuir Blodgett. Pretendemos estabelecer uma melhor compreensão sobre o papel fundamental das interações de ILs com as membranas celulares, em particular os ILs da família imidazólio e colina. Assim, propõe-se a avaliação do efeito da concentração, bem como dos comprimentos da cadeia alquílica de ILs da família imidazólio, na organização e estabilidade de monocamadas lipídicas e a comparação com o comportamento de líquidos iónicos da família das Colinas. Em suma, este trabalho pretende fornecer uma visão sobre os factores moleculares que contribuem para a toxicidade dos ILs, que possam ajudar no desenvolvimento de ILs menos tóxicos.

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Sinxi, Monde. "The nature of interactions in Alkylimidazolium based ionic liquids." Master's thesis, University of Cape Town, 2015. http://hdl.handle.net/11427/16197.

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Ionic liquids are materials that have the ability to be designed for specific tasks. Their properties can be adjusted by changing the molecular constituents of the liquid or the intermolecular interactions between composite ions through functionalisation. Therefore, understanding the nature of the interactions between ions is important. In the thesis, we use density functional theory calculations to obtain conformers of 1-ethyl-3-methylimidazolium ([emim]+)paired with the anions [Cl]-, [Br]-, [MeCO2]-, [CF3CO2]-, [MeSO3]-, [CF3SO3]-, [BF4]- and [PF6]-. We analyse the structures of the pairs and then explore the nature of the electrostatic, dispersion and hydrogen bonding interactions. Electrostatic interactions were the most dominant interactions. The dispersion interaction energies were found to be of the same order as the estimated energy of the hydrogen bond. The non-covalent index (NCI) analysis was used to visualise the non-covalent interactions in real space as enclosed surfaces. The properties of the surfaces were used to characterise interaction types, namely van der Waals interactions and hydrogen bonds. Furthermore, we find that the density enclosed within the hydrogen bonding surfaces can be used to estimate the potential of the hydrogen bond. To our knowledge, a potential for hydrogen bonding from NCI has not been explored for ionic liquids. Finally, the average strength of the hydrogen bond was calculated from structures extracted from molecular dynamics simulations. They reveal that the hydrogen bond strength for [emim][MeCO2] is approximately two-thirds weaker in the condensed phase than in the gas phase. The effect of the polarising environment is also found to weaken the hydrogen bond slightly.

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Martin, Pierre. "Studies of interactions between ions in ionics liquids electrolytes by nuclear magnetic resonance." Thesis, Orléans, 2018. http://www.theses.fr/2018ORLE2044/document.

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Ce travail de thèse porte sur l’étude d’électrolytes pour utilisation dans des systèmes de stockage énergétiques tels que les batteries lithium-ions. Les matériaux spécifiques à cette étude sont des liquides ioniques à base de pyrrolidinium avec le fluorosulfonylimide (FSI) en tant que contre-ion, le tout dopé au lithium.La méthode de caractérisation principale est la spectroscopie par Résonance Magnétique Nucléaire (RMN) qui peut être utilisée pour résoudre la structure, la dynamique ou encore l’arrangement spatial entre les anions et les cations. Des mesures de diffusion et des expériences de relaxation réseau-spin, utilisant 1H pour les cations, 19F pour les anions et 7Li, sont effectuées pour étudier le transport ionique dans le liquide ainsi que la rotation moléculaire respective des différents ions.Toutefois, dans le but de mieux comprendre le mécanisme de transport des ions à un niveau moléculaire dans ces liquides ioniques, l’expérience Heteronuclear Overhauser Effect SpectroscopY (HOESY) a été employée. Cette technique est basée sur le transfert d’aimantation entre deux isotopes nucléaires dans l’espace. Puisque le transfert est généralement dû à des interactions de courtes portées, des informations concernant les différentes proximités des espèces dans le liquide sont obtenues.Une grande partie de cette étude est concentrée sur le développement de la technique HOESY elle-même, avec l’amélioration de la séquence d’impulsion RMN mais aussi de l’analyse du signal, dans l’optique d’une étude quantitative et du développement d’une procédure automatique et systématique d’ajustement des données théoriques aux données expérimentales. Des simulations par Dynamique Moléculaire (DM) et des mesures de relaxation RMN sont utilisées pour permettre l’analyse des expériences OESY, permettant alors d’accéder à la corrélation des distances entre les noyaux et des paramètres de relaxation tels que les temps de corrélation, pouvant permettre une meilleure compréhension du transport ionique. En plus du développement de cette technique, de nouveaux liquides ioniques incluant des chaînes alkyles plus longues, des cycles plus longs ou encore un groupe ethero-alkyle sur la chaine alkyle sont étudiés par HOESY dans le ut d’observer l’impact de la structure du cation sur les interactions ioniques. Une autre technique complémentaire, la polarisation dynamique nucléaire, est aussi adoptée afin d’étudier les liquides ioniques dans un état vitreux imitant leur structure à l’état liquide
This work is focused on the study of electrolytes for energy storage devices such as lithium ion batteries. The specific materials are pyrrolidinium-based ionic liquid electrolytes with bis-fluorosulfonylimide (FSI) as the counter anion, and also containing lithium.The main experimental method of characterization is Nuclear Magnetic Resonance (NMR) spectroscopy, which can be used to probe structure, dynamics and spatial arrangements between anions and cations. NMR-based diffusion measurements or spin lattice relaxation experiments, using 1H for cations, 19F for anions and 7Li, are used to study the ionic transport in the liquid and the molecular tumbling of the different ions respectively.However, in order to attempt to better understand the ion transport mechanism at the molecular level in these ionic liquids, the HOESY (Heteronuclear Overhauser Effect SpectroscopY) experiment is used. This technique is based on a transfer of magnetization through space between two different nuclear isotopes. As this transfer is generally mediated by short-range interactions, it provides information on which species are close together in the liquid.A large part of this work is based on the development of the HOESY technique itself, both improving the implementation of the NMR pulse sequence to reduce the experimental time, but also improving ways to analyze the resulting data in a quantitative way and developing an automatic and systematic data fitting procedure. Molecular Dynamics (MD) simulations and NMR relaxation measurements are also used to assist the HOESY analysis, allowing correlations with distances between nuclei and motional parameters such as correlation times to be established, which will lead to a better understanding of the ion interactions. In addition to this technique development, others ionic liquids including longer alkyl, longer cycle or even an ether-o-alkyl group on the alkyl chain, are studied by HOESY in order to observe the impact of the cation structure on the ionic interactions. Another complementary technique, dynamic nuclear polarization, is also used in order to study the ionic liquid in the glassy state structure which mimics the liquid state

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17

Roy, Milan Chandra. "Investigation of assorted interactions of vital compounds aqueous ionic liquid and vitamin solutions and solvent arrangements." Thesis, University of North Bengal, 2016. http://ir.nbu.ac.in/handle/123456789/2756.

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18

Ferguson, J. L. "Interactions of Ionic Liquids with Micro-organisms, Enzymes, and Polymers." Thesis, Queen's University Belfast, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.527694.

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19

Buckley, Matthew. "Ionic liquids interacting with small molecules and a gold (110) surface." Thesis, University of Nottingham, 2016. http://eprints.nottingham.ac.uk/33771/.

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This thesis presents investigations into the interactions of ionic liquids (ILs). An investigation on the interaction of the ionic liquid 1-octyl-3-methylimidazolium tetrafluoroborate ([C8C1Im][BF4]) with three small molecules will focus on how the desorption kinetics are perturbed by interaction with the IL. A monolayer of 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C2C1Im][NTf2]) interacting with a Au(110) crystal facet is investigated using normal incidence x-ray standing wave (NIXSW) to resolve positional information. Acetone, sulfur dioxide and water interacting with [C8C1Im][BF4] are investigated. The desorption of pure species has been characterised. Acetone multilayers desorb with an activation energy of Ea = 38(2) kJ mol^-1 and a pre-exponential of A = 4.3x10^14(1) s^-1. Sulfur dioxide desorbs with an activation energy of Ea = 32(2) kJ mol^-1 and a pre-exponential of A = 6x10^14(1) s^-1. Water is observed to have an amorphous to crystalline phase change over the desorption region. Amorphous water is calculated to have a desorption activation energy of Ea = 49(5) kJ mol^-1 compared to Ea = 43(2) kJ mol^-1 for crystalline water. The pre-exponential is calculated to be A = 10^17(2) s^-1 and A = 10^15(1) s^-1 for the amorphous and crystalline water respectively. [C8C1Im][BF4] is found to stabilise both acetone and sulfur dioxide to a fixed capacity. A mole fraction of 1.2 of acetone to [C8C1Im][BF4] was stabilised over a range of Ea = 45 – 61 kJ mol^-1. A mole fraction of 6 of sulfur dioxide to [C8C1Im][BF4] was stabilised over a range of Ea = 40 – 52 kJ mol^-1. No fixed capacity was found for water despite being in great excess of the [C8C1Im][BF4]. The full coverage of water was influenced by the presence of [C8C1Im][BF4] with an activation energy of Ea = 42 kJ mol^-1 at full water coverage which increased to Ea = 49 kJ mol^-1 as the water coverage tended to zero. Several possible positions of [C2C1Im][NTf2] on Au(110) are presented. Near edge absorption fine structure (NEXAFS) spectroscopy informed that the imidazolium ring is flat on the surface. The position of the cation and the anion on the surface is found through simulation of each ion separately. The NIXSW is used to propose two real space position which the cation could occupy. The position of the anion is reduced to five possible configurations on the surface through the use of NIXSW.

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20

Captain, Janine Elizabeth. "Non-thermal Interactions on Low Temperature Ice and Aqueous Interfaces." Diss., Georgia Institute of Technology, 2005. http://hdl.handle.net/1853/6995.

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Electron-impact ionization of low-temperature water ice leads to H+, H2+, and H+(H2O)n=1-8 desorption. The threshold energy for ESD of H2+ from CI and H3O+ from PASW and ASW is 22 ± 3 eV. There is also a H2+ yield increase at 40 ± 3 eV and a 70 ± 3 eV threshold for ESD of H+(H2O)n=2-8 from PASW and ASW. H2+ production and desorption involves direct molecular elimination and reactive scattering of an energetic proton. Both of these channels likely involve localized two-hole one-electron and/or two-hole final states containing 4a1, 3a1 and/or 2a1 character. The 70 eV cluster ion threshold implicates either an initial (2a1-2) state localized on a monomer or the presence of at least two neighboring water molecules each containing a single hole. The resulting correlated two-hole or two-hole, one-electron configurations are localized within a complex and result in an intermolecular Coulomb repulsion and cluster ion ejection. The changes in the yields with phase and temperature are associated with structural and physical changes in the adsorbed water and longer lifetimes of excited state configurations containing a1 character. The dependence of the ESD cation yields on the local potential has been utilized to examine the details of HCl interactions on low temperature ice surfaces. The addition of HCl increases cluster ion yields from pure ice while decreasing H+ and H2+ yields. These changes reflect the changes in the local electronic potential due to the changing bond lengths at the surface of the ice as HCl ionizes and the surrounding water molecules reorient to solvate the ions. This work has been extended to ionic solutions at higher temperatures using a liquid jet and ultraviolet photoionization to interrogate the surface of aqueous ionic interfaces. Desorption of protonated water clusters and solvated sodium ion clusters were measured over a range of concentrations from NaCl, NaBr, and NaI solutions. The flux dependence indicated a multiple photon process and the proposed mechanism involves a Coulomb explosion resulting from the repulsion of nearby ions. The surface is investigated with regard to its importance in heterogeneous atmospheric chemistry.

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21

Fields, Patrice R. "Methods for the Characterization of Electrostatic Interactions on Surface-Confined Ionic Liquid Stationary Phases for High Pressure Liquid Chromatography." University of Cincinnati / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1307044073.

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22

Dutta, Ashutosh. "Exploration of diversified interactions of some significant compounds prevalent in several environments by physicochemical contrivance." Thesis, University of North Bengal, 2018. http://ir.nbu.ac.in/handle/123456789/2787.

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23

Nyberg, Erik. "Lubrication mechanism of hydrocarbon-mimicking ionic liquids." Licentiate thesis, Luleå tekniska universitet, Maskinelement, 2017. http://urn.kb.se/resolve?urn=urn:nbn:se:ltu:diva-65505.

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Lubrication is critical in order to achieve high efficiency and reliability of machine elements such as gears, bearings, and other moving mechanical assemblies (MMA). In space applications, tribological properties of lubricants are quickly growing more important. Traditional space systems such as satellites imply MMA such as gyroscopes, antenna pointing mechanisms, and solar array drives. These MMA operate in high vacuum (<10-5 Pa) under lightly loaded conditions. Modern space missions on the other hand, such as remotely operated vehicles used for in-situ Mars exploration relies on different types of MMA. In these robotic systems, electromechanical actuators are being used extensively to provide controlled motion. Gears and bearings in these actuators operate in an atmosphere mainly consisting of CO2 at ~10+3 Pa under heavily loaded contact conditions. In these conditions, the tribosystem is likely to operate in the boundary lubricated regime, with consequent risk of high friction and wear. High molecular weight fluids have significant heritage in space because of their low vapor pressure. They are currently employed as lubricants in a wide range of space applications, as they meet high demands on resistance to vacuum outgassing. Unfortunately, the large molecules are susceptible to degradation under heavy load. Ionic liquids (ILs) on the other hand, are synthetic fluids that consist entirely of ion pairs with opposing charge. The resulting ion bonds enable inherently low vapor pressure of the fluid without the need for a high molecular weight. For this reason ILs have been advocated as potential lubricants for space applications, but so far compatibility issues have hampered their use as lubricants. Countless IL variations are possible, and solutions are thus likely to exist. Constituent ions can be designed individually and combined in various configurations. However, the fundamental understanding of the lubricating mechanism of ionic liquids is still incomplete, and consequently the optimum molecular structure for IL lubricants remain unknown. In this thesis, a stepwise approach to molecular design of IL lubricants is described, and the resulting hydrocarbon-mimicking ionic liquids are evaluated in tribological experiments. In this thesis, the experiments focus on tribological performance, using steel-steel tribopairs in air environment under boundary lubrication (Paper I). Boundary film formation under a range of contact pressures and temperatures, is analyzed after tribotesting by optical profilometry, scanning electron microscopy (SEM), and energy dispersive X- iii ray spectroscopy (EDS) in Paper II. The analysis reveal formation of a highly effective boundary film based on silicate, that can be further enhanced by amine additives. This thesis demonstrates the feasibility of improving tribological performance of ionic liquids by molecular design.
Projekt: Rymdforskarskolan 2015

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24

Gibson, Joshua Simon. "Probing the interaction of 1-octyl-3-methylimidazolium containing ionic liquids with small molecules." Thesis, University of Nottingham, 2017. http://eprints.nottingham.ac.uk/48171/.

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Ionic Liquids (ILs) have drawn a great deal of attention as carbon capture agents, and in order to understand them studies must be performed probing the CO2–IL interaction. Many studies have focused upon measuring the solubility of CO2 within ILs, with fewer studies directly probing the CO2 adsorption environments within the IL. Understanding of the adsorption environments is of fundamental for the use of ILs industrially, if they are to be successfully applied within carbon capture and storage devices. Temperature programmed desorption (TPD) has been used to study the CO2–IL interaction within two ionic liquids; 1-octyl-3-methylimidazolium tetrafluoroborate ([C8C1Im][BF4]) and 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C8C1Im][Tf2N]). Experiments were performed utilising low temperature line of sight mass spectrometry (LTLOS MS), ensuring that only species desorbing from the surface are observed. Surfaces were formed through a coadsorption method, where IL was deposited by chemical vapour deposition at a rate of ≈ 1 layer per minute while CO2 was simultaneously leaked into the chamber at pressures between 2×10−8 and 2×10−6 mbar. This study finds that CO2 does not form a monolayer on a gold surface at ≈ 90 K, with no CO2 TPD peak seen for those experiments, showing Edes,CO2 (the activation energy of desorption of CO2) < 24.5 kJ mol−1. When IL and CO2 are coadsorbed the IL is seen to stabilise the CO2, such that a TPD peak for CO2 is seen, with the amount of stabilisation depending upon the IL used. Comparison of experimental TPD curves with calculated TPD profiles, using CO2 states with a range of binding energies, shows that there are multiple CO2 environments within the ILs. The use of TPD allowed the relative populations of these CO2 adsorption environments to be measured, which is not possible using solubility measurements and Henry’s constants, providing insights into the IL–CO2 interaction. CO2 was observed to desorb from sites within the bulk IL, which have activation energies of desorption in the range 24.5 to 43 kJ mol−1. The CO2 was seen to be stabilised most within the [C8C1Im][BF4], giving a stabilisation in Edes of up to 18.5 kJ mol−1. The [C8C1Im][Tf2N] was typically seen to stabilise twice as much CO2 as [C8C1Im][BF4], which is consistent with the experimental Henry’s constants. Further to this a new experimental technique for determining surface structure, utilising high energy X-rays in the total reflection regime, to generate an X-ray standing wave (XSW) and detect the resulting photoelectrons from layered surfaces has been demonstrated. The variable period X-ray standing wave (VPXSW) technique relies on the fact that at low incident angles (typically < 2°) total external reflection of X-rays is observed. The incident and reflected X-rays interact to generate an XSW along the surface normal, with nodes and antinodes at different heights, z, above a reflector for different angles of incidence. By scanning the incident angle of the X-ray from 0° upwards the periodicity of the XSW decreases, resulting in the nodes and antinodes sweeping towards the surface. As this sweeping occurs the nodes and antinodes pass through material adsorbed on the surface of the reflector, and the photoelectron signal fluctuates. Comparing the fluctuations in the measured photoelectron signal to a theoretical model allows surface layering to be detected at larger depths and with a higher information content than with other surface science techniques. This allows distance information, relative to the interfaces between different materials, to be obtained for different chemical species. Data is presented from a surface consisting of the ionic liquid [C8C1Im][BF4] on a Si(001) reflector, held at ≈ 90 K, with a thick IL layer adsorbed on the reflector and a CHCl3 marker layer on top of the IL. Results from the frozen surface indicate a 12 Å layer of CHCl3 and background water had been dosed on top of a 211 Å IL layer. These values agree well with what was expected for this model IL system with a thin marker layer, designed to test the technique. It is therefore shown that VPXSW with photoelectron emission can be used to successfully characterise thin films with thicknesses between 15 Å and ≈ 300 Å with chemical shift specificity, something not possible with current experimental techniques.

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25

Chen, Mingtao. "Bridging Mesoscale Phenomena and Macroscopic Properties in Block Copolymers Containing Ionic Interactions and Hydrogen Bonding." Diss., Virginia Tech, 2018. http://hdl.handle.net/10919/84525.

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Anionic polymerization and controlled radical polymerization enabled the synthesis of novel block copolymers with non-covalent interactions (electrostatic interaction and/or hydrogen bonding) to examine the relationships between mesoscale phenomenon and macroscopic physical properties. Non-covalent interactions offer extra intra- and inter-molecular interactions to achieve stimuli-responsive materials in various applications, such as artificial muscles, thermoplastic elastomers, and reversible biomacromolecule binding. The relationship between non-covalent interaction promoted mesoscale phenomenon (such as morphology) and consequent macroscopic physical properties is the key to optimize material design and improve end-use performance for emerging applications. Pendant hydrogen bonding in ABA block copolymers promoted microphase separation and delayed the order-disorder transition, resulting in tunable morphologies (through composition changes) and extended rubbery plateaus. Reversible addition-fragmentation chain transfer (RAFT) polymerization afforded a facile synthesis of ABA triblock copolymers with hydrogen bonding (urea sites) and electrostatic interactions (pyridinium groups). Pyridine groups facilitated hydrogen bonding through a preorganization effect, leading to highly ordered, long-range lamellar morphology and a significant increase of flow temperature (Tf) 80 °C above the hard block Tg. After quaternization of pyridine groups, electrostatic interaction, as a second physical crosslinking mechanism, disrupted ordered lamellar morphology and decreased Tf. Yet, extra physical crosslinking from electrostatic interactions pertained ordered hydrogen bonding at high temperature and exhibited improved stress-relaxation properties. Both conventional free radical polymerization and RAFT polymerization generated a library of poly(ionic liquid) (PIL) homopolymers with imidazolium groups as bond charge moieties. A long chain alkyl spacer between imidazolium groups and the polymer backbones ensured a low glass transition temperature (Tg), which is beneficial to ion conductivity. Four different counter anions enabled readily tunable Tgs all below room temperature and showed promising ion conductivities as high as 2.45 × 10⁻⁵ S/cm at 30 °C. For the first time, the influence of counter anions on radical polymerization kinetics was observed and investigated thoroughly using in situ FTIR, NMR diffusometry, and simulation. Monomer diffusion and aggregation barely contributed to the kinetic differences, and the Marcus theory was applied to explain the polymerization kinetic differences which showed promising simulation results. RAFT polymerization readily prepared AB diblock, ABA triblock and (AB)3 3-arm diblock copolymers using the ionic liquid (IL) monomers discussed above and deuterated/hydrogenated styrene. We demonstrated the first example of in situ morphology studies during an actuation process, and counter anions with varied electrostatic interactions showed different mesoscale mechanisms, which accounted for macroscopic actuation. The long chain alkyl spacer between imidazolium groups and polymer backbones decoupled ion dynamics and structural relaxation. For the first time, composition changes of block copolymers achieved tunable viscoelastic properties without altering ion conductivity, which provided an ideal example for actuation materials, solid electrolytes, and ion exchange membranes.
Ph. D.

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26

Kim, Hannah. "The synthesis and purification of Chiral Amino Acid Ionic Liquids and Investigation of Quantitative Solvent-Solute Interactions." Thesis, Imperial College London, 2007. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.486364.

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This project divides into two halves: the synthesis, purification and characterisation of numerous ionic liquids including amino acid based chiral ionic liquids and polarity studies, which have been undertaken to further the understanding and quantification ofthe solvent-solute interactions by use of Kalmet-Taft measurements. In the early 1980s, the introduction of cleaner technologies to eliminate or significantly reduce hazardous waste generation became a major concern. In particular, a high priority to find alternatives to volatile organic compounds (VOC's), which were found to be very damaging solvents, was realised. Ionic liquids (IL's) remained a curiosity until recently, when the chemists discovered that it was possible to replace the VOC's with IL's and in some cases, the reactions were much improved. Since then, the field of IL's has exploded, which led to a vast increase in the number of publications and in the number of groups throughout the world who have started to work in the field. This project has reviewed some of the synthesis, purification and characterisation of chiral amino acid ILs and improved upon these procedures. The second halfofthe project involved investigating the overall solvating ability some of these purified IL's to obtain a better understanding ofhow these solvents may affect a reaction. This ability is not dependant on one particular physical measurement of the solvent, but is rather a sum ofall the specific and non-specific interactions that might occur between a solvent and solute. A large number of interactions are involved; these could include columbic, directional, inductive, dispersion, hydrogen-bonding, and electron pair donor/acceptor forces. The polarity ofthe IL's and mixtures of ILs with water or dichloromethane were investigated using UV dyes.

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27

Galluzzi, M. "INTERFACIAL PROPERTIES OF IONIC LIQUIDS:ELECTRIC PROPERTIES OF THIN FILMS AND INTERACTION WITH MODEL MEMBRANES AND LIVING CELLS." Doctoral thesis, Università degli Studi di Milano, 2014. http://hdl.handle.net/2434/229734.

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Room-Temperature Ionic Liquids (ILs) have attracted considerable interest in recent years. This interest is motivated by the physico-chemical properties of these systems, tunable modifying the chemical structure of ions. Generally, ILs show chemical and thermal stability, i.e. they do not easily decompose or react. Furthermore, these compounds remain liquid over an extended range of temperatures, in which they show also a remarkably low volatility. The low vapor pressure of ILs, promote them as good solvents for the growing field of the ”Green Chemistry”, in substitution of the volatile organic compounds. The fact that ILs are composed solely by ions, and can have a quite wide electrochemical window, make them very interesting as electrolytes. For these purposes, this PhD thesis is devoted to the investigation of ILs in contact with solid interfaces, primary targets of interaction. To deepen the analysis of electric properties at the solid interface, thin layers of ILs deposited on conductive substrates were investigated by means of AFM. The ”Green” character of these compounds was investigated studying their interaction with biomembrane models and external membranes of living cells, by means of AFM and electrochemical methods. Because of their ionic nature, ILs can be used as electrolytes in several devices aimed at conversion and storage of energy, such as electrochemical supercapacitors, Graetzel solar cells and batteries. In these devices a key role is played by the interface between the surface of the electrodes and the electrolyte; in particular, structural-morphological and electrical properties of the first few nanometers of IL interacting with the solid electrode surface are expected to have the strongest impact on device performance. AFM morphological analysis of small quantity of [C 4 MIM] [NTf 2 ] IL, deposited on various insulating surfaces revealed a population of nanodroplets and new structures. Remarkably, the solid surfaces induce the organization of the ionic liquid into regular, lamellar solid-like nanostructures presenting a high degree of vertical structural order and high mechanical resistance to normal compressive stresses. Nanomechanical investigation reveals that the structures resist to normal compressive loads up to 1.5 MPa; beyond that limit, indentation, in discrete steps, occurs. Furthermore, lamellar [C 4 MIM] [NTf 2 ] islands are not affected when scanned by a biased AFM tip under the influence of an electric field as intense as 10 8 V/m, while the liquid nano-and micro-droplets are easily swept away. These results confirm the solid-like character of the ordered lamellar nanostructures observed when thin films of [C 4 MIM] [NTf 2 ] are deposited on solid surfaces, and suggest that these films may possess an insulating, dielectric behavior, at odd with the case of the bulk ionic liquids. Nanoscale impedance measurements (capacitance vs. distance) and electrostatic force spectroscopy (electric force vs. distance) between a conductive AFM tip and the IL structures confirmed that values of the dielectric constant (ε r = 3-5) are significantly smaller than those measured in the bulk liquid (ε r = 9-15). These results support the picture of solid-like ordered domains where the ion mobility is significantly inhibited with respect to the bulk liquid phase. These findings also highlight the potentialities of scanning probe techniques for the quantitative investigation of the interfacial electrical properties of thin ionic liquid films, suggesting that ILs at electrified solid surfaces may possess unexpected electrical and structural properties, thus influencing the behavior of photo-electrochemical devices. The ”green” character of ionic liquids (ILs) is dependent on their negligible vapor pressure but in contrast to their environmental behavior their intrinsic toxicity is not at present completely understood. Accordingly, although ILs will not evaporate which alleviates air pollution problems, a potential hazard of Ils to living organisms via aqueous media cannot be ruled out. A rigorous investigation on the interaction of ILs with biomaterials is required to provide information about their intrinsic toxicity. In order to test the biocompatible character of ILs, as a first objective, the interaction of various ILs with biological membrane (biomembrane) models was studied using electrochemical methods. A series of imidazolium based ILs were investigated whose interactions highlighted the role of anion and lateral side chain of cation during the interaction with dioleoyl phosphatidylcholine (DOPC) monolayer. It was shown that the hydrophobic and lipophilic character of the IL cations is a primary factor responsible for this interaction. The modifications of the Hg supported monolayer caused by ILs were simultaneously monitored electrochemically in a well controlled manner using rapid cyclic voltammetry (RCV), alternating current voltammetry (ACV), and electrochemical impedance spectroscopy (EIS). Hg supported monolayers provide an accurate analysis of the behavior of ILs at the interface of a biomembrane leading to a comprehensive understanding of the interaction mechanisms involved. At the same time, these experiments show that the Hg-phospholipid model is an effective toxicity sensing technique as shown by the correlation between literature in vivo toxicity data and the data from this study. Cell membrane is the main target of ILs interaction, depending on the lipophilicity of hydrophobic lateral chain of cation. In order to test the biocompatible character of ILs, the interaction of various imidazolium-based ILs with supported DOPC phospholipid bilayers (as models of the cell membrane) and living MDA-MB-231 cells (@37 ◦C) was investigated. Atomic Force Microscopy (AFM) was used to carry on a combined topographic and mechanical analysis of supported DOPC bilayers as well as of living cells. During the analysis of DOPC bilayers we have observed modifications in breakthrough force and membrane elasticity related to the ingress of lateral chains of cations in the bilayer, demonstrating agreement with electrochemical results. The parallel nanomechanical analysis performed on living cells interacting with ILs at various concentrations showed modifications of elasticity (effective Young’s modulus) and morphology of cells after exposure to ILs dispersed in their culture medium. The measurements confirmed the primary action of ILs on membrane and actin cytoskeleton, highlighting a subtoxic/toxic effect dependent on ILs concentration and chemical nature of cation. Our results may be helpful for filling existing gaps of knowledge about ionic liquids toxicity and their impact on living organisms. From these evidences, interaction of ILs with micro-organisms and single cells is an important step to assess the environmental sustainability of this novel and promising class of solvents and to attribute a ”green” label to it. Studying the interaction of ionic liquids, it has been recognized that the interface is a vital component. When the bulk symmetry of IL is broken by surfaces, the electrical properties are greatly affected, leading from a ion conductor to an insulator behavior. Also the interaction with biological entity is driven, in first instance, by surface interaction. Biomembrane models and cell membranes are affected by ILs that accumulate/penetrate the surface interface, leading to structural reorganization/damage of external membrane.

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28

Bordes, Emilie. "Graphène dans des liquides ioniques : interactions aux interfaces, exfoliation, stabilisation." Thesis, Université Clermont Auvergne‎ (2017-2020), 2017. http://www.theses.fr/2017CLFAC052.

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L'exfoliation en phase liquide du graphite est l'une des méthodes les plus prometteuses pour augmenter la production et la disponibilité commerciale du graphène. Le processus d'exfoliation peut être décrit, de manière conceptuelle, en quatre étapes: le contact du graphite avec le liquide, l'intercalation du solvant entre les feuillets de graphène, la dispersion du matériau à deux dimension et sa stabilisation en phase liquide. Comme les liquides ioniques peuvent être facilement obtenus avec différentes structures moléculaires et donc des propriétés physicochimiques modulables, ils ont été utilisés dans cette thèse comme milieux liquides pour l'exfoliation du graphite. Notre objectif est d'optimiser l'exfoliation du graphite à travers la compréhension des mécanismes moléculaires et des interactions impliquées dans chaque étape du processus. Les énergies interfaciale graphite-liquide ont été calculées à partir de tensions de surface et d'angles de contact mesurées entre des liquides ioniques et du graphite pour déterminer l'affinité de différents liquides à la surface du graphite. Afin d'étudier cette interface liquide - solide, des simulations en dynamique moléculaire ont été menées pour analyser l'organisation des liquides ioniques à la surface du graphite. De même, l'énergie libre nécessaire pour créer des cavités au sein du liquide ionique a été calculée.Des simulations moléculaires ont également été réalisées pour modéliser l'exfoliation d'un feuillet de graphène à partir de graphite en apportant une vue microscopique de l'intercalation des molécules de solvant. L'énergie nécessaire à l'exfoliation a pu être calculée en présence de différents liquides. Des composés polyaromatiques ont été considérés comme des modèles pour le graphène car ils peuvent être facilement obtenus purs, sans variabilité de structure, défauts ou groupes fonctionnels non contrôlés. Les enthalpies de dissolution du naphtalène, anthracène et pyrène dans différents liquides ioniques ont été mesurées par calorimétrie en solution et liées à leur solubilité. L'organisation des ions autour de ces composés modèles a été étudiée par simulation moléculaire et spectroscopie Infra-Rouge.Après l'exfoliation, les échantillons de graphène en suspension dans différents liquides ioniques ont été caractérisés expérimentalement en termes de taille de feuillets (microscopie électronique à transmission et microscopie à force atomique), nombre de couches de graphène (microscopie à force atomique, spectroscopie Raman), concentration totale (spectroscopie UV-visible) et pureté du matériau exfolié (spectroscopie de photoélectrons~X). Vingt liquides ioniques différents à base de cations imidazolium, pyrrolidinium et ammonium et d'anions bis (trifluorométhylsulfonyl)imide, triflate, dicyanamide, tricyanométhanide et méthylsulfate ont été testés. Les interactions moléculaires permettant d'établir de règles de conception pour les liquides ioniques capables d'exfolier les matériaux carbonés ont été identifiées. Le cation pyrrolidinium a montré des résultats prometteurs dans toutes les étapes du processus d'exfoliation, par rapport au cation imidazolium ou ammonium. La sélection d'un grand anion flexible a réduit l'énergie interfaciale avec le graphite, dispersé les nanocarbones en augmentant l'entropie du système et stabilisé le graphite exfolié en plus grande quantité. Un petit anion tel que le triflate semble être favorable à l'obtention de graphène, même si la taille des couches et leur quantité sont réduites. Un liquide ionique ayant une partie apolaire importante facilitera l'insertion et la dispersion du nanomatériau de carbone. Pour la stabilisation du graphite, les interactions alkyle-π et π- π sont décisives
The liquid-phase exfoliation of graphite is one of the most promising methods to increase production and commercial availability of graphene. The exfoliation process can be conceptually described in four steps: the contact of the graphite with liquid, the intercalation of the solvent between layers, the dispersion of the two dimensional material, and its stabilization in the liquid-phase. Because ionic liquids can be easily obtained with chosen molecular structures and tunable physicochemical properties, they were used in this study as liquid media for the exfoliation of graphite. Our aim is to optimize the exfoliation of graphite through the understanding of the molecular mechanisms and of the interactions involved in each step of the process.The liquid-graphite interfacial energies from measured surface tensions and contact angles, between ionic liquids and pristine graphite surface, were used to determine the affinity of different liquids at the surface of graphite. In order to investigate this interface, molecular dynamics simulations were conducted to analyse the ordering of ionic liquids at the surface of graphite. The free energies necessary to create cavities inside the bulk ionic liquid have also been studied.Molecular simulations were also used to study the exfoliation of one graphene layer from a stack of graphite and hence provide a microscopic view of the intercalation of solvent molecules. The energies involved in the process have been calculated.Polyaromatic compounds were regarded as models for graphene as they can be easily obtained pure, without structure variability, defects or uncontrolled functional groups. Enthalpies of dissolution of polyaromatic hydrocarbons (naphthalene, anthracene and pyrene) in different ionic liquids were measured by solution calorimetry and related with their solubility. The ordering of the ions around this model compounds were studied by molecular simulation and spectroscopy Infra-Red.After exfoliation, samples of suspended graphene in different ionic liquids have been characterized experimentally in terms of flake size (using transmission electron microscopy and atomic force microscopy), number of layers (atomic force microscopy, spectroscopy Raman), total concentration (UV-visible spectroscopy) and purity of the exfoliated material (X-ray photoelectron spectrometry).Twenty different ionic liquids based on imidazolium, pyrrolidinium and ammonium cations and on bis(trifluoromethylsulfonyl)imide, triflate, dicyanamide, tricyanomethanide, and methyl sulfate have been tested. The molecular interactions have been identified thus allowing the establishment of design rules for ionic liquids capable of exfoliating carbon materials. The pyrrolidinium cation has shown promising results in all the steps of exfoliation process, compared to the imidazolium or ammonium cation. Selecting a large and flexible anion reduced the interfacial energy with graphite, dispersed the nanocarbons by increasing the entropy of the system and stabilized the exfoliated graphite in larger quantity. A small anion such as triflate appears to be favorable for obtaining graphene, whereas the size of the layers and their quantity is reduced. An ionic liquid having an important apolar portion will facilitate the insertion and dispersion of graphene layers. For the stabilization of graphite, the alkyl-π et π -π interactions are decisive

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29

Schmeißer, Matthias [Verfasser], and Rudi van [Akademischer Betreuer] Eldik. "Kinetic, Mechanistic and Structural Studies on Metal-Ligand-Interactions in Ionic Liquids / Matthias Schmeißer. Betreuer: Rudi van Eldik." Erlangen : Universitätsbibliothek der Universität Erlangen-Nürnberg, 2011. http://d-nb.info/1015781993/34.

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Möller, Johannes [Verfasser], Metin [Akademischer Betreuer] Tolan, and Roland [Akademischer Betreuer] Winter. "Liquid-liquid phase separation and intermolecular interactions in dense protein solutions : High pressure SAXS studies on lysozyme solutions of high ionic strength / Johannes Möller. Betreuer: Metin Tolan. Gutachter: Roland Winter." Dortmund : Universitätsbibliothek Dortmund, 2014. http://d-nb.info/1096224976/34.

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31

Möller, Johannes Verfasser], Metin [Akademischer Betreuer] [Tolan, and Roland [Akademischer Betreuer] Winter. "Liquid-liquid phase separation and intermolecular interactions in dense protein solutions : High pressure SAXS studies on lysozyme solutions of high ionic strength / Johannes Möller. Betreuer: Metin Tolan. Gutachter: Roland Winter." Dortmund : Universitätsbibliothek Dortmund, 2014. http://nbn-resolving.de/urn:nbn:de:101:1-201604121768.

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Anderson, Emily Baird. "Synthesis and Non-Covalent Interactions of Novel Phosphonium-Containing Polymers." Diss., Virginia Tech, 2010. http://hdl.handle.net/10919/28849.

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Phosphonium ions readily compare to ammonium ions in regards to their aggregate characteristics, thermal stability, and antibacterial activity. Ionic aggregation in phosphonium-based polymers provides thermoreversible crosslinks, ideal for reversible self-assembly, self-healing, and smart response. In polymers, these ionic functionalities aggregate, providing improved moduli, and altering the size and structure of ionic aggregates regulates polymer melt processability. This dissertation highlights phosphonium-based chemistry for the synthesis of novel step-growth ionomers and structure-property relationships in ionic polymers. The synthesis of phosphonium endcapping reagents for melt polyester reactions afforded a thermally stable ionic functionality that controlled molecular weight. Weak association was present with phosphonium ions at low ion concentrations below 7.7 mole %. The use of novel ionic bisacetoacetate monomers in the formation of networks from Michael addition reactions led to the synthesis of ionic networks with increased and broadened glass transitions and improved tensile stresses at break and strains at break compared to those in the non-ionic networks. The first electrospun fibers from Michael addition crosslinking reactions are reported, and equilibrium ionic liquid uptake experimental results indicated that ionic functional networks absorb close to three times the amount of ionic liquid as non-ionic, poly(ethylene glycol)-based films. Chain-extending polyurethanes with a phosphonium diol and subsequently varying the hard segment content led to changes in ionic aggregation, crystallinity, and thermal transitions in the polymers. Additionally, novel phosphonium-based methacrylate monomers incorporated into diblock copolymers with styrene exhibited microphase separation. Overall, the inclusion of phosphonium ions pendant to or in the main chain of various types of polymers led to changes in morphology, improved tensile properties, enhanced moduli, broadened transitions, changes in crystalline melting points, changes in solubility, and appearance of ionic aggregation.
Ph. D.

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Crohare, Adeline. "Mélanges de polymères thermoplastiques, compatibilisés par des liquides ioniques, pour le développement de multifilaments." Thesis, Lyon, 2017. http://www.theses.fr/2017LYSEI029.

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Cette étude décrit l’élaboration de nouveaux multifilaments textiles offrant un compromis ténacité/élasticité inédit. Ces multifilaments sont composés de mélanges de polymères immiscibles, soit PA66/élastomère soit PET/élastomère, compatibilisés tous les deux par des liquides ioniques. L’incorporation de 1%m de liquide ionique dans ces mélanges a permis de diminuer la tension interfaciale entre les polymères, permettant ainsi d’affiner les morphologies des mélanges binaires et d’améliorer les propriétés mécaniques. Cette compatibilisation a été réalisée sans augmentation de la viscosité des mélanges, critère indispensable pour conserver la filabilité des formulations. L’utilisation de liquide ionique a également permis de façonner la morphologie des mélanges en choisissant judicieusement le couple « cation/anion ». La nature du cation (phosphonium vs imidazolium) et de l’anion a été étudiée. Ainsi, des morphologies nodulaires, fibrillaires ou intermédiaires ont pu être obtenues avec des propriétés mécaniques différentes. De nombreuses formulations ont pu être filées, étirées, puis prototypées sous forme de tissus et cordages de tennis afin de tester l’apport élastique des élastomères. Les liquides ioniques capables de réagir chimiquement avec le thermoplastique ouvrent des perspectives intéressantes
This work highlights the role of ionic liquids (ILs) as compatibilizers in immiscible polymer blends to increase the springback of polyamide or polyester multiyarns due to the presence of elastomeric nodules. The influence of ionic liquid nature on the morphology of PA66/rubber and PET/rubber blends and on thermal, rheological and mechanical properties has been investigated. The incorporation of only 1 wt% of ionic liquids leads to a decrease of interfacial tension between the polymers. The morphology of blends can be tuned by the chemical nature of ionic liquids to reduce largely the nodule size of the dispersed phase and/or to generate fibrillar shape morphology. The reduction of particles size leads to an improvement of mechanical properties with an increase of elongation at break and the same stiffness. Moreover the incorporation of IL has no effect on the viscosity of blends. Several formulations could be spun and prototypes of fabric and tennis racket strings could be made with multiyarns

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Mouawad, Charbel. "Transfert de matière dans un système solide/liquide "ions/eau/pectine" : interactions, partage ionique et simulation par dynamique moléculaire." Thesis, Vandoeuvre-les-Nancy, INPL, 2007. http://www.theses.fr/2007INPL072N/document.

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Mass transfer intervening during the process of immersion influences the final composition of the product. These transfers primarily depend on the size of the immersed products, as well as temperature, the concentration and the nature of the solution of immersion. The main objective of this work is to study the mass transfer phenomena (water loss and solid gain) in solid/liquid system constituted of vegetable product (eggplant) immerged in salt solution. We determined the kinetic studies of eggplant in different salts solutions with two concentrations (saturation and 20%) at 3°C. The physicochemical properties of solution and salt such as molar concentration, molecular weight and ionic type affected the mechanism of water loss and solid gain. Knowledge about interaction ions/vegetable pectin is important for new product formulation. Determination of partition coefficient of ion in equilibrium system showed that the main physicochemical properties of ions and solution are ionic radius, electronegativity, ionic force and molar concentration. Mathematical predictive model was developed to predict the partition coefficient of ions in food/ solution system. Molecular dynamics simulations using a dynamic force field have been carried out to investigate the absorption of ions (K+, Na+, Ca2+, Mg2+, Cl-) in pectin/water/ion/aqueous solution system. Four systems were used. The results showed that the ionic type (cation and anion) influence the type and number of interactions between pectin-ion and water-ion and then offered an explicit description transfer phenomena and distribution of ions in the system solid/liquid
Les transferts de matière intervenant au cours du procédé d’immersion dépendent essentiellement de la taille des produits immergés, la température, la concentration et la nature de la solution d'immersion. L’objectif principal de ce travail porte sur l’étude des transferts dans un système solide/liquide constitué d’un produit végétal (aubergine) et d’une solution saline. Afin de parvenir à une bonne maîtrise de ces paramètres, les études cinétiques ont été conduites à 3°C sur des aubergines immergées dans des solutions salines avec deux concentrations. Les propriétés des solutions et des sels telles que la concentration molaire, la masse molaire et surtout la nature ionique influencent le mécanisme de perte et de gain. Les connaissances sur les interactions ions/pectines végétaux sont importants pour la formulation de nouveaux produits La détermination du coefficient de partage des ions à l’équilibre dans le système aubergine/solution ont montré que les principales propriétés des ions et des solutions influençant le coefficient de partage sont le rayon ionique, l’électronégativité, la force ionique et la concentration molaire. Un modèle mathématique a permis de prédire le coefficient de partage des ions dans ce système. Dans le but d’expliquer l’absorption des ions par la phase solide, une simulation par dynamique moléculaire a été menée sur un système pectine-eau-sels. Quatre systèmes ont été utilisés. Les résultats obtenus ont montré que la nature ionique influencent la nature et le nombre d’interaction entre pectine-ion et eau-ion et donc offrent une description explicite des phénomènes de transferts et distribution des ions dans le système solide/liquide

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Rodrigues, Fabio. "Espectroscopia Raman de líquidos iônicos imidazólicos: interações interiônicas, organização estrutural e efeitos de micro-ambiente." Universidade de São Paulo, 2010. http://www.teses.usp.br/teses/disponiveis/46/46132/tde-10112010-103107/.

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O presente trabalho tem como objetivo principal um estudo sistemático de líquidos iônicos imidazólicos, ou seja, sais líquidos a temperaturas relativamente baixas derivados do anel imidazol, tendo como técnica principal a espectroscopia Raman. Foram estudados os cátions 1-alquil-3- metilimidazólio e 1-alquil-2,3-dimetilimidazólio, sendo o grupo alquil composto por 2, 4, 6, 8 ou 10 átomos de carbono, com os ânions brometo, hexafluorofosfato ou bis(trifluorometanosulfonil)imida (TFSI-), totalizando 30 sistemas distintos. O estudo foi dividido em três partes. Na primeira, foram estudados compostos derivados de imidazol, neutros e catiônicos, para entender as diferenças entre os cátions formadores (o ânion foi desconsiderado) de ILs e seus precursores. A espectroscopia Raman forneceu informações sobre as alterações nos modos vibracionais com as substituições, sendo possível constatar que os modos do anel se tornaram menos intensos com as substituições e a contribuição de grupos -CH se tornou mais importante. Cálculos de cargas de Mulliken foram realizados para estas espécies e os resultados obtidos reforçam as interpretações dos espectros vibracionais. A segunda etapa consistiu no estudo de ILs puros, analisando tanto cátion quanto ânion. A cadeia carbônica tem grande influência no espectro Raman, sendo observadas bandas atribuídas a confôrmeros diferentes, que aparecem em maior número e menor intensidade à medida que a cadeia se torna menor. Os ânions foram estudados nos ILs e em sais inorgânicos, sendo observados espectros muito semelhantes destes nos diversos ILs, porém diferentes nos sais inorgânicos. Os mesmos resultados foram encontrados nas medidas de XANES (espectroscopia de raio-X próxima à borda de absorção), que permitiu sondar a estrutura eletrônica ao redor de diversos átomos, utilizada como técnica auxiliar. Após analisado cátions e ânions, foi possível caracterizar o par iônico formado por estes íons, enfocando as bandas Raman das cadeias carbônicas, já que, como a interação de Coulomb é baixa, estes se ligam principalmente via ligação de hidrogênio. Para os ILs com -H no carbono 2, o ânion Br- forma um par iônico mais forte com os diversos cátions, enquanto PF6- e TFSI-The present work aims to be a systematic study, by Raman spectroscopy, of imidazolic ionic liquids, which means low temperature molten salts derived from imidazole ring. The study involved the cations 1-alkil-3-methylimidazolium and 1-alkyl-2,3-dimethylimidazolim, being alkyl chain composed of 2, 4, 6, 8 or 10 carbon atoms and with the anions bromide, hexafluorophosphate and bis(trifluoromethanesulfonyl)imide (TFSI-), in a grand total of 30 species with distinct properties. The study has been separated in three steps. The first one aimed to study both neutral and cationic molecules derived from imidazolic ring to understand the difference between cations that can form ILs and their precursors. Raman spectroscopy gave information about the changes in the vibrational modes with the substitutions. The results show that the intensity of modes from the ring decreases with the substitutions, while the contribution of -CH modes increases. In accordance with this are the results obtained from theoretical calculation of Mulliken charge, used as an auxiliary technique. The second step consisted in the study of pure ILs, analyzing both cation and anion effects. The carbonic chain plays a major role in Raman spectra, exhibiting bands attributed to different conformers. These bands become more abundant and less intense when the chain length increases. The anions have been studied in both ILs and inorganic salts, being observed very similar spectra for all the ILs but different ones for the inorganic salts. These results have been confirmed by XANES (X-ray absorption near edge structure) spectroscopy, which makes possible to probe the electronic structure of different atoms. After the analysis of both cation and anion, it was possible to better understand the ion pair formation in ILs, focusing in hydrogen bonds in the carbonic chain, since the Coulombic interaction is too weak. For ILs with hydrogen in carbon 2, it could be observed that bromide anion forms a stronger ion pair when compared to PF6- and TFSI-, less coordinating anions. The addition of methyl group in carbon 2 modifies this behavior, and even bromide does not form the strong ion pair. At last, the third step focused in the better understanding of binary systems containing ILs and a molecular solvent, dimethylformamide (DMFA), used also as probe since the shift of the band attributed to C=O group was used in this study. In a first stage it has been studied equimolar solutions of ILs and DMFA, in which it has been observed the organization of ILs in the mixture, and the contribution of both cation and anion. The second stage was dedicated to the understanding of these mixtures with different molar fraction of ILs and DMFA, for which some ILs have been selected. For low concentration of ILs, their behavior was similar to molecular solvents, but when the concentration of IL was increased, an anomalous behavior in the shift of C=O band has been observed, which can be attributed to the ionic character of these systems.

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Nicolau, Bruno Giuliano. "Estudos espectroscópicos de misturas líquido iônico/sal de lítio." Universidade de São Paulo, 2011. http://www.teses.usp.br/teses/disponiveis/46/46132/tde-31082011-150312/.

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A adição de sais de lítio à líquidos iônicos gera mudanças em propriedades físicas relevantes, que comprometem sua possível aplicação em baterias de lítio, como aumento de viscosidade e redução da condutividade iônica. Possíveis causas para tais efeitos foram estudadas através da utilização de Espectroscopia Raman e Espectroscopia de Efeito Óptico Kerr. Foram estudadas as misturas dos liquídos iônicos: 1-butil-3metilimidazólio, N-(3- etóxietil)-N-metilmorfolínio e cátion 1-(3-etóxietil)-2,3-dimetilimidazólio possuindo em comum o contra-íon bis(trifluorometanosulfonil)imideto com diferentes concentrações de bis(trifluorometanosulfonil)imideto de lítio. O trabalho se dividiu em duas etapas principais, na primeira utilizou-se a espectroscopia Raman e observou-se o desdobramento da banda referente ao ânion em aproximadamente 740 cm-1, em dois diferentes picos, após a adição de lítio ao sistema. Esta observação forneceu indícios da ocorrência de mudanças estruturais possivelmente relacionadas a formação de agregados entre os ânions e o Li+. A partir destes resultados a obtenção de um valor aproximado para o número de coordenação médio dos cátions Li+ foi possível através da comparação da intensidade relativa dos dois picos para diferentes concentrações de sal. Foi ainda estudado o efeito da adição de água no sistema, causando o desaparecimento do pico Raman formado após a adição do sal de lítio, o que evidencia a capacidade da mesma de reduzir o efeito de agregação dos ânions ao redor do Li+. Na segunda etapa do trabalho, a técnica de espectroscopia de efeito óptico Kerr via detecção heterodina foi utilizada para a observação do perfil de relaxação orientacional nos sistemas descritos acima, a fim de examinar mudanças nos processos dinâmicos presentes após a adição sal inorgânico ao sistema. Os resultados foram analisados no contexto da teoria de acoplamento de modos, de maneira que utilizou-se um modelo fenomenológico desenvolvido através da observação de diferentes sistemas e da aplicação das equações propostas no modelo esquemático de Sjögren para a descrição da função de correlação polarizabilidade-polarizabilidade obtida pelo experimento. Os parâmetros encontrados demonstraram um alto grau de concordância com as observações estruturais observadas na primeira etapa, fornecendo evidências de que o lítio é capaz de afetar as estruturas locais presentes no líquido iônico puro de uma maneira similar ao efeito Chemla. O trabalho demonstrou que os mesmos princípios necessários para a síntese de líquidos iônicos a temperatura ambiente, primando a redução das interações atrativas entre os cátion e ânions para a estabilização da fase líquida, possui como efeito colateral o fato de que diversas moléculas apresentam interações mais fortes com seus íons alterando suas propriedades, neste caso prejudicando a utilização de líquidos iônicos como solventes alternativos em baterias de lítio.
The introduction of lithium salts to room temperature ionic liquids causes unwanted changes to the electrochemically relevant properties of these compounds, such as increase in viscosity and the reduction of ionic conductivity. Possible causes for these effects were studied with spectroscopic techniques such as Raman spectroscopy and Optical Kerr Effect spectroscopy. Mixtures of three different ionic liquids containing the cations: 1-butyl-3- methylimidazolium, N-(3-etoxyethyl)-N-methylmorfolinium and cátion 1-(3-etoxyethyl)-2,3- dimethylimidazolium and possessing the common counter ion bis(trifluoromethane sulfonyl)imide with lithium bis(trifluoromethane sulfonyl)imide. This work was divided in two parts, the first consisting of the use of Raman spectroscopy and the observation of the changes in the 740 cm-1 peak, pertaining to anion vibration after the introduction of lithium to the system, shown as the appearance of a new peak at higher frequencies. The approximate average lithium coordination number was determined by comparison of the relative intensities for different salt concentrations. The effect of water absorption in this system was also observed, showing that water molecules tend to hinder the formation of aggregates between the anion and Li+. The second step was carried out with the use of optically heterodyne detected optical Kerr effect spectroscopy to the analysis of the orientational relaxation profile for the systems described above. Results were analyzed through the application of Mode Coupling Theory models, both a phenomenological model obtained by the observation of different classes of liquids and the Mode Coupling Schematic model proposed by Sjögren were used to describe the polarizability-polarizabilty correlation function obtained from the experiments. The parameters obtained showed a high degree of correlation with the results obtained in the first part indicating that the introduction of a highly polarizing cation to the pure ionic liquid causes an effect similar to the Chemla effect observed in inorganic salt mixtures. The work showed evidences that the same principles used for the synthesis of room temperature ionic liquids, i.e. the reduction of attractive interactions between cation and anion or the addition of alkyl chains to reduce symmetry, result in various different compounds showing stronger interactions with the different ions resulting in changing properties, in this case hindering the use of ionic liquids as alternative green solvents for lithium ion batteries.

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Böes, Elvis Sidnei. "Estudo computacional de líquidos iônicos do tipo imidazólio com substituintes insaturados." reponame:Biblioteca Digital de Teses e Dissertações da UFRGS, 2012. http://hdl.handle.net/10183/55483.

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Os métodos computacionais da química quântica foram empregados para estudar as estruturas moleculares e as energias de interação de cátions e ânions que são componentes de alguns líquidos iônicos funcionalizados, derivados do imidazólio. O estudo teve como objetivo comparar e relacionar os efeitos da presença de funcionalização nos substituintes das posições 1 e 3 do cátion imidazólio, nas propriedades desses líquidos iônicos. Essa funcionalização pode ocorrer pela presença de insaturações, grupos aromáticos, éteres, álcoois, tióis, aminas, nitrilas entre outros grupos nas cadeias dos substituintes. Nesta tese são reportados os estudos dos complexos formados por ânions tetrafluorborato e cátions imidazólio substituídos por grupos metila, etila, propila, butila, isobutila, vinila, propargila, alila, crotila e metalila, observando assim o efeito da presença de substituintes contendo cadeias insaturadas em comparação com os de cadeias saturadas nas estruturas, distribuições de carga, energias de interação e propriedades físico-químicas desses sistemas. Nesses sistemas foram observados intensos efeitos de polarização e transferência de carga ânion-cátion. Foram encontradas diversas relações entre volumes iônicos, energias de interação dos íons e as propriedades de transporte dos respectivos líquidos iônicos.
The methods of computational quantum chemistry have been used to study the molecular structures and the interaction energies of cations and anions which are components of some functionalized ionic liquids derived from imidazolium. The objective of this study is comparing and relating the effects of the presence of functionalization of the side chains of the imidazolium with the properties of these ionic liquids. This functionalization can occur by the presence of unsaturated side chains, aromatic groups, ether, alcohols, thiols, amines, nitriles among other groups in the side chains. In this thesis are reported the studies of the complexes formed of tetrafluorborate anions and imidazolium cations with side chains methyl, ethyl, propyl, butyl, isobutyl, vinyl, propargyl, allyl, crotyl and methallyl, thus observing the effects of the presence of unsaturated side chains compared to saturated ones on the structures, charge distributions, interaction energies and physicochemical properties of these systems. It was observed in these systems strong effects of polarization and anion-cation charge transfer. It was found several relations between ionic volumes, interation energies of the ions and the transport properties of the respective ionic liquids.

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Raw, Juliana. "Estudo da interação de líquidos iônicos com proteínas modelo." Universidade de São Paulo, 2016. http://www.teses.usp.br/teses/disponiveis/43/43134/tde-22112016-153329/.

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Líquidos iônicos (LIs) são sais que se encontram no estado líquido em temperaturas menores que 100ºC e que vêm ganhando protagonismo na área chamada química verde, prometendo: substituir solventes nocivos ao meio ambiente, aprimorar componentes eletrônicos, favorecer biocatálises dentre outros. Sua alta estabilidade e baixa toxicidade são frequentemente afirmadas, porém, devem ainda ser melhor investigadas. Com o objetivo de implementar o entendimento da interação dos líquidos iônicos com sistemas de relevância biológica, realizamos um estudo sistemático acerca da interação de 3 diferentes líquidos iônicos anfifílicos de mesma cabeça polar e diferentes caudas carbônicas ([C10mim][Cl], [C12mim][Cl] e [C14mim][Cl]) com 3 diferentes proteínas modelo, através das técnicas de absorção óptica, fluorescência, dicroísmo circular (CD) e espalhamento de raios-X a baixos ângulos (SAXS). Para Tanto, utilizamos as proteínas BSA e HSA (Albuminas de Soro Bovino e Humano, respectivamente) além da lisozima. Observamos a supressão da fluorescência das proteínas em todos os casos analisados, onde a diminuição da intensidade correspondeu a, para as proteínas BSA, HSA e lisozima, respectivamente, (55±3)%, (16.1±0.8)% e (4.1±0.2)%, em presença de 0.6mM de [C14mim][Cl], (38±2)%, (13.2±0.7)% e (0.6±0.1)% em presença de 0.6mM de [C12mim][Cl] e (11.0±0.5)%, (9.2±0.5)% e (0.0±0.1)% em presença de 0.6mM de [C10mim][Cl]. Os espectros de absorbância e fluorescência de todos os sistemas nos indicam uma interação de contato entre as proteínas e os líquidos iônicos. Constatamos também o deslocamento do pico de fluorescência, das proteínas BSA e HSA, para menores comprimentos de onda (blue-shift), na medida em que a concentração de LI era aumentada. O máximo deslocamento () alcançado correspondeu a (21±1)nm para ambas albuminas, enquanto que a lisozima não apresentou deslocamento significativo. O blue-shift pode ser explicado pela aproximação das cadeias carbônicas e formações de pontes de hidrogênio nas proximidades dos triptofanos. De acordo com a técnica de SAXS, evidenciamos o aumento do raio de giro das proteínas, na medida em que adicionamos LIs. O raio de giro da BSA, da HSA e lisozima em ausência de LI são (29±1)Å, (30±1)Å e (15±1)Å, respectivamente, e passam para (46±1)Å, (44±1)Å e (20±1)Å respectivamente, em presença de 0.6mM de [C14mim][Cl]. As curvas de SAXS também apresentaram o indício da formação de estruturas micelares a partir de uma dada concentração. Além da alteração em sua estrutura terciária, os dados de CD indicam uma leve perda de estrutura secundária de ambas as albuminas (BSA e HSA), passando de 80 para 65% de -hélice em ausência e presença de 0.6mM de [C14mim][Cl], respectivamente. Sugerimos que as interações das proteínas com os líquidos iônicos, embora inicialmente movidas por forças eletroestática, possuem como principal fator o efeito hidrofóbico, portanto quanto maior a cadeia carbônica do LI maior é sua interação com a proteína. Tal interação causa o desenovelamento das proteínas e formação de um complexo e estruturas micelares a altas concentrações de LI. Acreditamos que este trabalho traz novas informações acerca da interação dos LIs com proteínas modelo, indicando sua capacidade de alterar a conformação das mesmas.
Ionic liquids (ILs) are salts that are liquid at temperatures smaller than 100 ° C and are gaining prominence in the so-called green chemistry, promising: replace harmful solvents to the environment, improve electronic components, and favor biocatalysis, among others. Its high stability and low toxicity are often asserted; nevertheless, they are ascribed to ILs due to its small volatility. With the aim of improving the understanding of the interaction of ILs with biological relevant systems, we conducted a systematic study of the interaction of three different ionic liquids of the same polar head and different paraffinic tails ([C10mim][Cl], [C12mim][Cl] and [C14mim][Cl]) with three different model proteins, through the techniques of optical absorption, fluorescence, circular dicrhoism (CD) and small angle X-ray scattering (SAXS). To do so, we use BSA and HSA proteins (Bovine Serum Albumin and the Human Serum Albumin, respectively) and lysozyme. We observed fluorescence quenching, of all studied proteins, where the decrease in the fluorescence was (for BSA, HAS and lysozyme, respectively): (55 ± 3)%, (16.1 ± 0.8)% to (4.1 ± 0.2 )% in the presence of 0.6mm [C14mim][Cl], (38 ± 2)%, (13.2 ± 0.7)% to (0.6 ± 0.1)% in the presence of 0.6mm [C12mim][Cl] and ( 11.0 ± 0.5)% (9.2 ± 0.5)% and (0.0 ± 0.1)% in the presence of 0.6mm [C10mim][Cl]. UV-vis absorbance spectra and fluorescence indicate all systems in a contact interaction between proteins and ionic liquids. We also note the shift of the fluorescent peak of BSA and HSA proteins for shorter wavelengths (blue-shift), as the IL content was increased. The maximum shift () achieved corresponded to (21 ± 1) nm for both albumins, whereas no significant displacement was observed for lysozyme. The blue-shift can be explained by the approach of carbon chains and formation of hydrogen bonds in the vicinity of tryptophan. SAXS data indicate an increasing in the proteins radius of gyration value as ILs was added in the solution. The turning radius of BSA, HSA and lysozyme in the absence of IL are (29 ± 1) Å, (30 ± 1) Å and (15 ± 1) Å, respectively, and go to (46 ± 1) Å, ( 44 ± 1) Å and (20 ± 1) Å, respectively, in the presence of 0.6mm [C14mim][Cl]. The SAXS curves also show evidence of the formation of micellar structures from a given concentration. Besides the change in its tertiary structure, the CD data indicates a slight loss of secondary structure of both albumins (BSA and HSA), from 80 to 65% of -helix in the absence and presence of 0.6mm [C14mim][Cl], respectively. We suggest that the interactions of the protein with the ionic liquid, although initially driven by electrostatic forces, have a major factor hydrophobic effect and thus the higher the carbon chain of greater IL is its interaction with the protein. This interaction causes unfolding of the protein and formation of a micellar structures at high concentrations of IL. We believe this work provides new information about the interaction of ILs with model proteins, indicating its ability to alter the conformation of the same.

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39

Bär, Jaciara. "Absorção de SO2 por líquidos iônicos: efeito do ânion." Universidade de São Paulo, 2016. http://www.teses.usp.br/teses/disponiveis/46/46136/tde-18082016-085659/.

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O dióxido de enxofre (SO2) é um dos principais poluentes atmosféricos e a busca por sistemas capazes de absorver, detectar e/ou quantificar este gás tem sido de grande interesse. Neste contexto, os líquidos iônicos (LI) têm demonstrado potencial aplicação em metodologias de captura e armazenamento de gases. Neste estudo, nosso maior interesse consiste em entender os principais fatores que governam as interações entre o SO2 e diferentes íons formadores de líquidos iônicos. Em particular, foi explorada a interação específica de transferência de carga entre ânions (base de Lewis) e o SO2 (ácido de Lewis). A abordagem deste trabalho foi baseada em uma investigação sistemática de LI formados pelo cátion 1-butil,3-metilimidazólio (BMI) e diferentes ânions, utilizando da espectroscopia vibracional (Raman e IR), sobretudo a espectroscopia Raman ressonante, aliada a cálculos teóricos baseados na teoria do funcional da densidade (DFT). Os resultados de espectroscopia vibracional Raman e IR, mostraram mudanças na posição e formato da banda referente ao modo de estiramento simétrico vs(SO2) dependendo do ânion e da concentração de SO2 em LI. Verificou-se deslocamentos significativos para menor número de onda em relação ao SO2 líquido puro (1145 cm-1) em menores concentrações de SO2 em LI. Na série dos haletos, Cl-, Br- e I-, quanto maior o ânion, maior o deslocamento (1138, 1133 e 1123 cm-1, respectivamente para a fração molar 0,5). No caso do tiocianato, considerado como um pseudo-haleto, a banda do modo vs(SO2) aparece em cerca de 1130 cm-1 na mesma fração molar, ou seja, em um valor intermediário entre o Br- e o I-. Esses deslocamentos observados podem ser interpretados de acordo com a interação específica de transferência de carga do ânion para o SO2. Um resultado observado que merece destaque consiste na dependência da banda Raman do modo vs(SO2) com a energia da radiação excitante, o que é denominado de dispersão Raman. Tal fenômeno pôde ser explicado utilizando o modelo de \"excitação seletiva do estado de solvatação\" em que foi possível caracterizar os diferentes estados de solvatação do SO2 em líquidos iônicos.
Sulfur dioxide (SO2) is one of the main atmospheric pollutants and the search for systems capable of absorbing detect and/or quantify such gas has been of great interest. In this context, ionic liquids (IL) have shown potential application in capture methodologies and gas storage. In this study, our interest consists in the understanding of the main factors that govern the interactions between SO2 and diferents ions of ionic liquids. In particular, the charge transfer specific interaction was explored between anions (Lewis base) and SO2 (Lewis acid). The approach of this study was based on a systematic investigation of LI formed by 1-butyl cation, 3-methylimidazolium (BMI) and different anions, using vibrational spectroscopy (Raman and IR), especially resonance Raman spectroscopy, allied with theoretical calculations based on density functional theory (DFT). The vibrational spectroscopic results (Raman and IR) showed changes in the position and shape of the band assigned to the symmetric stretching mode vs(SO2) depending on the anion and SO2 concentration in LI. There were significant shifts to lower wavenumbers with respect to pure liquid SO2 (1145 cm-1) at lower SO2 concentrations in IL. In the series of halides, Cl-, Br- and I-, the bigger the anion, the larger the displacement (1138, 1133 and 1123 cm-1, respectively at 0.5 mole fraction). In the case of thiocyanate, regarded as a pseudo-halide, the band vs(SO2) appears at about 1130 cm-1 at the same molar fraction, i.e. at an intermediate value between the Br- and I-. The observed displacement can be interpreted accordingly to the specific interaction of charge transfer from the anion to SO2. A result that is worth mentioning is the dependence of the wavenumber of the Raman band vs(SO2) with the energy of the exciting radiation, which is called Raman scattering. This phenomenon could be explained using the model of \"solvation state selective excitation\" in which was possible to characterize the diferente solvation states of the SO2 in ionic liquids

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40

Cheng, Shijing. "Synthesis and Characterization of Cation-Containing and Hydrogen Bonding Supramolecular Polymers." Diss., Virginia Tech, 2011. http://hdl.handle.net/10919/77185.

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Non-covalent interactions including nucleobase hydrogen bonding and phosphonium/ammonium ionic aggregation were studied in block and random polymers synthesized using controlled radical polymerization techniques such as nitroxide mediated polymerization (NMP) and reversible addition-fragmentation chain transfer polymerization (RAFT). Non-covalent interactions were expected to increase the effective molecular weight of the polymeric precursors through intermolecular associations and to induce microphase separation. The influence of non-covalent association on the structure/property relationships of these materials were studied in terms of physical properties (tensile, DMA, rheology) as well as morphological studies (AFM, SAXS). Ionic interactions, which possess stronger interaction energies than hydrogen bonds (~150 kJ/mol) were studied in the context of phosphonium-containing acrylate triblock (ABA) copolymers and random copolymers. Phosphonium-containing ionic liquid monomers with different alkyl substituent lengths and counterions enabled an investigation of the effects of ionic aggregation of phosphonium cations on the polymer physical properties. The polymerization of styrenic phosphonium-containing ionic liquid monomers using a difunctional alkoxyamine initiator, DEPN2, afforded an ABA triblock copolymer with an n-butyl acrylate soft center block and symmetric phosphonium-containing external reinforcing blocks. Small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) of triblock copolymers revealed pronounced microphase separation at the nanoscale. Phosphonium aggregation governed block copolymer flow activation energies. In random copolymers, the phosphonium cations only weakly aggregated, which strongly depended on the length of alkyl substituents and the type of counterions. Acrylate random copolymers consisting of quaternary ammonium functionalities were synthesized using reversible addition-fragmentation chain transfer polymerization (RAFT). The obtained copolymers possessed controlled compositions and narrow molecular weight distributions with molecular weights ranging from Mn =50,000 to 170,000 g/mol. DMA evidenced the weak aggregation of ammonium cations in the solid state. Additionally, this ionomer was salt-responsive in NaCl aqueous solutions. Hydrogen bonding, a dynamic interaction with intermediate enthalpies (10-40 kJ/mol) was introduced through complementary heterocyclic DNA nucleobases such as adenine, thymine and uracil. Our investigations in this field have focused on the use of DNA nucleobase pair interactions to control polymer self-assembly and rheological behavior. Novel acrylic adenine- and thymine-containing monomers were synthesized from aza-Michael addition reaction. The long alkyl spacers between nucleobase and polymer backbone afforded structural flexibility in self-assembly process. Adenine-containing polyacrylates exhibited unique morphologies due to adenine-adenine π-π interactions. The complementary hydrogen bonding of adenine and thymine resulted in disruption of adenine-adenine π-π interactions, leading to lower plateau modulus and lower softening temperatures. Moreover, hydrogen bonding interactions enabled the compatibilization of complementary hydrogen bonding guest molecules such as uracil phosphonium chloride.
Ph. D.

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Fernandes, Mendonça Ana Catarina. "Simulations moléculaires d'une nouvelle classe de liquides ioniques basés sur la fonction ammonium pour l'utilisation potentielle en tant qu'huiles lubrifiantes respectueuses de l'environnement." Phd thesis, Université Blaise Pascal - Clermont-Ferrand II, 2013. http://tel.archives-ouvertes.fr/tel-00857336.

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L'objectif de ce travail est de comprendre la structure et les interactions des liquides ioniques au contact de surfaces métalliques à l'échelle moléculaire en ayant recours aux méthodes de dynamique moléculaire. Il s'agit également d'étudier l'impact de ces caractéristiques microscopiques sur les propriétés tribologiques du système. Les liquides ioniques choisis en tant qu'huiles lubrifiantes potentielles présentent des propriétés biodégradables et des caractéristiques tribologiques appropriées. Ils reposent sur des cations alkylammonium combinés avec des anions alkylsulfonate et bistriflamide. Notre étude est structurée en quatre parties. Elle commence par l'analyse des liquides ioniques purs puis, des liquides ioniques confinés entre deux surfaces de fer à l'équilibre et sous cisaillement, et enfin, en présence d'eau. Les propriétés structurales et dynamiques des liquides ioniques sont étudiées à travers la fonction de distribution radiale et les coefficients d'auto-diffusion. L'organisation des charges ainsi que la formation de micro-domaines en solution sont étudiées conjointement au comportement diffusif des espèces ioniques. Un champ de forces atomique, basé sur des méthodes quantiques, a été développé pour modéliser les interactions entre les liquides ioniques et la surface métallique. Des calculs DFT ont été réalisés sur des fragments de liquides ioniques en interaction avec un cluster de fer en fonction de la distance et de leur orientation. Une fonction modélisant des interactions site-site a été ajustée aux valeurs d'énergies fragment-cluster calculées par DFT afin d'obtenir les paramètres du champ de forces. Finalement, la polarisation du métal par les ions a été prise en compte en utilisant un modèle de dipôles induits afin de reproduire l'énergie d'interaction entre les charges et la surface conductrice. Avec ce modèle d'interaction, les simulations de dynamique moléculaire ont permis d'étudier la structure de l'interface entre une surface de fer plane et différents liquides ioniques. Cette analyse s'est concentrée sur l'étude du positionnement des différentes espèces au niveau de la surface, sur l'orientation des chaines alkyles et sur les profils de densité de charge. Des simulations de dynamique moléculaire hors-équilibre de liquides ioniques en interaction avec des surfaces de fer ont été réalisées en utilisant le champ de forces développé précédemment. Un protocole de simulation, basé sur une définition locale de la pression, a été développé pour prédire de manière quantitative le coefficient de friction en fonction de la valeur de la charge et du taux de cisaillement. La dépendance de la friction avec la charge, la vitesse de cisaillement, la topologie de la surface et la taille de la chaine alkyle du liquide ionique a été étudiée. La variation des forces de friction s'explique par l'arrangement spécifique des ions et l'orientation des groupements du liquide ionique à proximité de la surface. Finalement, l'effet de la présence d'eau en petite quantité dans une solution de liquide ionique a aussi été étudié à l'équilibre et hors-équilibre. Un potentiel a été construit pour décrire les interactions entre l'eau et une surface de fer en utilisant la même approche que celle décrite précédemment. Des résultats préliminaires concernant la structure de l'interface liquide-métal et la valeur du coefficient de friction ont été présentés et comparés avec ceux obtenus pour les liquides ioniques purs.

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Creazzo, Fabrizio. "Oxygen evolution reaction at cobalt oxides/water interfaces : heterogeneous electrocatalysis by DFT-MD simulations & metadynamics Ab initio molecular dynamics study of an aqueous NaCl solution under an electric field Ionic diffusion and proton transfer in aqueous solutions of alkali metal salts Ionic Diffusion and Proton Transfer in Aqueous Solutions under an Electric Field: State-of-The-Art Ionic diffusion and proton transfer of MgCl2 and CaCl2 aqueous solutions: an ab initio study under electric field DFT-MD of the (110)-Co 3 O 4 cobalt oxide semiconductor in contact with liquid water, preliminary chemical and physical insights into the electrochemical environment Enhanced conductivity of water at the electrified air–water interface: a DFT-MD characterization Ions tune interfacial water structure and modulate hydrophobic interactions at silica surfaces." Thesis, université Paris-Saclay, 2020. http://www.theses.fr/2020UPASE012.

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Dans cette thèse, des simulations DFT-MD couplées à des techniques inno-vantes de métadynamique, sont appliquées pour acquérir une compréhensionglobale des interfaces aqueuses d'oxyde de cobalt Co3O4 et CoO(OH) dansla catalyse de la réaction d'évolution de l'oxygène (OER), et ainsi éventuellement aider à la conception de nouveaux catalyseurs basés sur des matériaux non précieux, un domaine clé de la recherche scientifique et technologique, particulièrement important pour l'économie de l'hydrogène, pour les technologies vertes dans une période de temps avec une demande toujours plus croissanteen énergie verte. Dans cette thèse, nous révélons étape par étape les mécanismes de l'OER sur les électrocatalyseurs aqueux d'oxyde de cobalt Co3O4 etCoO(OH) via de nouvelles techniques de métadynamique.Jusqu'à présent, la littérature n'a jamais pris en compte les modificationsau niveau atomique de la structure des électrodes ainsi que de l'eau interfaciale dans leur modélisation des processus OER. Ce manque de connaissances représente clairement un obstacle important au développement de catalyseurs améliorés, qui pourrait être surmonté en utilisant des méthodes capables de suivre les caractéristiques catalytiques de l'OER à l'échelle atomique. Pour la première fois, nous montrons combien il est important de prendre en considération la présence de l'environnement aqueux dans la caractérisation structurale des surfaces du catalyseur, c'est-à-dire (110)-Co3O4 et (0001)-CoO(OH) dans ce travail. Une caractérisation détaillée des propriétés chimiques et physiques des interfaces aqueuses est fournie (la structure, la dynamique, la spectroscopie, le champ électrique), pour les surfaces (110)-Co3O4 et (0001)-CoO(OH) en contact avec l'eau liquide.Une étude détaillée de l'OER est présentée non seulement du point de vue descatalyseurs, mais aussi en abordant le rôle de l'environnement de l'eau dans leprocessus catalytique, ce qui n'a pas été fait auparavant dans la littérature. En conséquence, l'OER en phase gazeuse et en phase liquide sont étudiés ici auxinterfaces aqueuses (110)-Co3O4 et (0001)-CoO(OH) en adoptant une nouvelleapproche de métadynamique d'échantillonnage amélioré, capable d'identifieret caractériser les mécanismes de réaction chimique et d'intégrer pleinement lerôle des degrés de liberté du solvant, permettant ainsi de dévoiler des réactivités chimiques d'une complexité remarquable. L'énergétique, la cinétique et la thermodynamique derrière l'OER sont donc trouvées à ces surfaces d'oxyde de cobalt à l'interface avec l'eau
In this thesis, DFT-MD simulations, coupled with state-of-the-art metadynamics techniques, are applied to gain a global understanding of Co3O4 and CoO(OH) cobalt oxide aqueous interfaces in catalyzing the oxygen evolution reaction (OER), and hence possibly help in the design of novel catalysts basedon non-precious materials, a current key field of research in science and technology, especially of importance for the hydrogen economy, for green technology in a period of time with an ever more growing demand in green-energy. In this thesis, we step-by-step reveal the OER mechanisms on spinel Co3O4 andCoO(OH) cobalt aqueous electrocatalysts carefully and rationally via novelmetadynamics techniques.Up to now, the literature has never taken into account the atomistic modifications on the electrode structure as well as on the interfacial water into their modeling of OER processes. Such lack of knowledge clearly represents a significant hurdle toward the development of improved catalysts, which couldbe overcome by employing methods able to track the catalytic features of theOER at the atomistic scale. For the first time, we show how important itis to take into consideration the presence of the liquid water environment inthe structural characterization of catalyst surfaces, i.e. for (110)-Co3O4 and(0001)-CoO(OH) in this work. A detailed characterization of chemical andphysical properties of the aqueous interfaces is provided (i.e. structure, dynamics, spectroscopy, electric field), for the (110)-Co3O4 and (0001)-CoO(OH)aqueous surfaces.A study of the OER is presented not only by looking at the catalysts, butalso by addressing the role of the water environment in the catalytic process,not done before in literature. Accordingly, both gas-phase and liquid-phaseOER are here investigated at the (110)-Co3O4 and (0001)-CoO(OH) adoptinga novel enhanced sampling metadynamics approach able to address a widerange of chemical reaction mechanisms and to fully include the role of thesolvent degrees of freedom, allowing to unveil reaction networks of remarkablecomplexity. The energetics, kinetics and thermodynamics behind the OER aretherefore found at these cobalt oxide surfaces

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Hennemann, Bruno Luís. "Energia de interação cátion-ânion de líquidos iônicos dicatiônicos em fase gasosa." Universidade Federal de Santa Maria, 2016. http://repositorio.ufsm.br/handle/1/11976.

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Electrospray ionization mass spectrometry (ESI-MS) with induced collision energy was used to carry out a comprehensive study on the interaction energies between cations and anions of dicationic ionic liquids. The influence of the anion ([Br]-, [NO3]-, [BF4]-, [SCN]- and [Cl]-) and the size of alkyl chain (n = 4,6,8 and 10) in the interaction energy of ionic liquids derived from the 1, n-bis (3-methylimidazolyl-1-yl) alkane with n = 4,6,8 and 10, in the gas phase was investigated. Three experiments were carried out to determine the cation-anion interaction energy: (i) ESI-MS of binary (1:1) mixtures of ionic liquids with different anions or cations; (Ii) ESI-MS of ionic liquid individually with variation of the applied collision energy and determination of the center of mass energy (Ecm) using the relation between the intensity of the precursor ion and the sum of the ions; (iii) the rate of variation of the intensity of the precursor ion as a function of collision energy at different concentrations of all ionic liquids was obtained. From this correlation, the cation-anion dissociation constant of the dicationic ionic liquids was obtained. The results showed the appearance of mixed species (example: [Bis-C8(MIM)22XY]- and [C8(MIM)XY]-) in the binary mixtures. The application of the induced collision energy in the mixtures allowed estimating which anion interacts more effectively with the cation. Also for this experiments, the dicationic ionic liquids with the anions [Cl]-, [Br]- and [NO3]- presented higher cation-anion interaction energy. The increasing order of interaction energy was [BF4]- <[SCN]- <[NO3]- <[Br]- <[Cl]-. The Ecm values for ionic liquids with different anions did not indicate trends in the interaction energy in relation to structural factors such as ionic radius and molecular volume. Thus, for the anions, it was found that the interaction increases in the following order: [SCN]- <[Cl]- <[NO3]- <[Br]- <[BF4]-. On the other hand, increasing the size of the spacer alkyl chain caused an increase in cation-anion interaction energy. As the concentration of the ionic liquid increased, an increase in the precursor ion intensity was observed.
A espectrometria de massa com ionização por electrospray (ESI-MS) com energia de colisão induzida foi utilizada para realizar um estudo compreensivo sobre as energias de interação entre cátions e ânions de líquidos iônicos dicatiônicos. Foi avaliada a influência do ânion ([Br]-, [NO3]-, [BF4]-, [SCN]- e [Cl]-) e o tamanho da cadeia alquílica espaçadora (n=4,6,8 e 10) na energia de interação dos líquidos iônicos dicatiônicos, derivados do 1,n-bis(3-metilimidazolil-1-íneo)alcano em fase gasosa. Três experimentos foram realizados para a determinação da energia de interação cátion-ânion: (i) ESI-MS de misturas binárias (1:1) de líquidos iônicos com diferentes ânions ou cátions; (ii) ESI-MS de cada líquido iônico individualmente com variação da energia de colisão aplicada e determinação da energia de centro de massa (Ecm) usando a relação entre intensidade do íon precursor e somatório dos íons. (iii) Por fim, foi obtida a taxa de variação da intensidade do íon precursor em função energia de colisão de todos os líquidos iônicos. A partir desta correlação, foi obtida a constante de dissociação cátion-ânion dos líquidos iônicos dicatiônicos. Os resultados mostraram o aparecimento de espécies mistas (exemplo: [Bis-C8(MIM)22XY]- e [C8(MIM)XY]-) nos experimentos das misturas. A aplicação da energia de colisão induzida nas misturas também permitiu estimar qual ânion interage mais efetivamente com o cátion. Ainda para este experimentos, os líquidos iônicos dicatiônicos com os ânions [Cl]-, [Br]- e [NO3]- apresentaram maior energia de interação cátion-ânion. A escala em ordem crescente de energia de interação foi [BF4]-< [SCN]- < [NO3]- < [Br]- < [Cl]-. Os valores de Ecm para os líquidos iônicos com diferentes ânions não indicou tendências na energia de interação em relação fatores estruturais tais como raio iônico e volume molecular. Dessa forma, para os ânions, foi encontrado que a interação aumenta na seguinte ordem: [SCN]-<[Cl]-<[NO3]-<[Br]-<[BF4]-. Por outro lado, o aumento do tamanho da cadeia alquílica espaçadora causou um aumento na energia de interação cátion-ânion. Com o aumento da concentração do líquido iônico, foi observado um aumento na intensidade do íon precursor.

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44

Lungwitz, Ralf. "Ionische Flüssigkeiten – Polarität und Wechselwirkungen mit silikatischen Oberflächen." Doctoral thesis, Universitätsbibliothek Chemnitz, 2011. http://nbn-resolving.de/urn:nbn:de:bsz:ch1-qucosa-68621.

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Gegenstand der vorliegenden Arbeit ist die UV/Vis-spektroskopische Bestimmung der Kamlet-Taft-Polaritätsparameter von strukturell unterschiedlichen Ionischen Flüssigkeiten (ILs), mit Hilfe von spezifischen solvatochromen Sondenmolekülen. Dabei wurden der Einfluss des Anions und Kations auf die Polarität, sowie die Stärke der Wechselwirkung zwischen beiden Ionen untersucht. Es konnte für Ionischen Flüssigkeiten mit dem 1-Butyl-3-methylimidazoliumkation eine 1H-NMR-spektroskopische Methode zur Ermittlung der Polaritätsparameter entwickelt werden. Diese bietet den Vorteil, dass sie auch bei farbigen, hydrolyseempfindlichen oder höher schmelzenden ILs eingesetzt werden kann, wenn die Anwendung solvatochromer Sondenmoleküle nicht möglich ist. Ein weiteres Augenmerk lag auf der Untersuchung der Wechselwirkung zwischen den ILs und silikatischen Oberflächen. Neben der Studie der anionenvermittelten starken Physisorption von 1-Methylimidazoliumchlorid an Aerosil®300 konnte auch eine neuartige Methode zur gezielten Chemisorption von Imidazolium- und Phosphoniumkationen an Siliziumdioxidoberflächen entwickelt werden. Dabei wurden verschieden Carbene und Ylide als basische IL-typische Kationenprecursoren eingesetzt. Die Analyse der erhaltenen Materialien erfolgte mit Hilfe verschiedener Methoden der Festkörper-NMR-Spektroskopie.

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45

Harner, John M. "Interaction of ionic liquid-dissolved polymers." 2010. https://scholarworks.umass.edu/dissertations/AAI3409586.

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Ionic liquids (ILs), neoteric salts with Tm < 100°C, have garnered vast interest due to a number of unique properties including vanishingly low volatility, non-toxicity and property tunability. Many polymers were found to dissolve in ILs, and polymer solution properties were measured using the room temperature IL 1-ethyl-3-methylimidiazolium ethylsulfate, [EMIM][EtSO 4], as a model IL. Polyethylene glycol (PEG) dissolves in [EMIM][EtSO 4] above ∼60°C, the neat polymer's melting temperature, and if concentration and molecular weight are high enough, the solution transforms into a semi-transparent gel at lower temperature. Thermoreversible gelation is traced to kinetically frustrated polymer crystallization, a mechanism established previously for many pairings of crystallizable polymer with aqueous or organic solvent. Negatively and positively charged polymers dissolve in [EMIM][EtSO 4], typically over long time periods, and solution chain properties are measured using common physiochemical techniques. Electrostatic interactions of sodium poly(styrene sulfonate) are screened without the need of added salt due to the presence of the charged solvent and size-molecular weight relationships indicate sodium poly(styrene sulfonate) assumes a coiled conformation in solution. Lysozyme dissolves in [EMIM][EtSO4] assuming an expanded conformation with compromised secondary structure, the unfolded structure stabilized by the IL. Preferential solvation of dissolved lysozyme in mixed [EMIM][EtSO 4]/H2O solvents prevents lysozyme aggregation above its denaturation temperature.

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46

Swain, Litun. "Interaction between ionic liquid and lysozyme: a conformational and stability aspect." Thesis, 2014. http://ethesis.nitrkl.ac.in/6411/1/E-91.pdf.

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Fourier Transform InfraRed (FTIR) spectroscopy is introduced to analyze the secondary structures of Lysozyme. Here, we studied the conformational changes in lysozyme protein in the presence of different concentrations of various ionic liquids, like 1-ethyl-3-methylimidazolium chloride (EMImCl), 1-butyl-3-methylimidazolium chloride (BMImCl) and 1-hexyl-3-methylimidazolium chloride (HMImCl), as well as in varying the alkyl chain lengths attached to the cationic moiety, and also, the thermal stability of lysozyme at different concentrations of BMImCl are investigated by temperature-dependant absorbance study using UV-visible spectrophotometer. Moreover, the overall objective of our research is to qualitatively exploit the effect of ILs on protein conformation and stability. However, the findings reveals an inversely proportionality relationship between Lysozyme stability/conformational change and ionic liquid concentration/alkyl chain length.

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47

Liu, Ting-Wei, and 劉挺緯. "Studies of the interaction between ionic liquid and solvents by Natural Bond Orbital method." Thesis, 2006. http://ndltd.ncl.edu.tw/handle/69866971398746268306.

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碩士
國立成功大學
化學系碩博士班
94
Bond orbital analysis performed on EMI+ and various Lewis bases reveals that the Weinhold’s “counterbalance effects of rehybridization and hyperconjugation” are valid for the most polar C-H (EMI+) bonding orbitals and are not suitable for the lone-pair bonding orbital of the bases. Only when alkyl C-H BOs are involved in hyperconjugative interactions with the base, chloride or bromide anions under this research, the hyperconjugation effect prevails over rehybridization effect and H-bonding results in a strengthened C(3)-H bond. The self-diffusing BMI-PF6 in neat ionic liquid (IL) state have been found, in the presence of aprotic organic solvent (AOS), associated to different extents, which can be explained by B3LYP/3-21G* calculated binding energies for the adducts of AOS and PF6 anion. These results are consistent with the very recent nitrogen NMR studies performed on ionic liquids, which infer that solvent-anion interactions dominate modified physical properties. The NBO second-order perturbation energy analysis provides orbital-based explanations for the unusually up-field shifts of 19F NMR resonances in propylene carbonate and the relative solvent-IL effects .

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48

Chen, Mei-Hung, and 陳美宏. "Studies of the interaction between ionic liquid and solvents by Natural Bond Orbital method (II)." Thesis, 2007. http://ndltd.ncl.edu.tw/handle/92028099328769138657.

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碩士
國立成功大學
化學系專班
95
Under the neat ionic liquid condition, it is observed that the cation and anion diffused respectively. In recently, there were also papers about cation’s 1H and 19F NMR spectrum pointed out that the HAP (hyper anion preference) is more than the HCP (hyper cation preference) under the different temperature and the different organic solvent ratio. Which reason actually affects the intermolecular relative function in the ionic liquid and the solvent? And which reaslly affects the hyper anion preference, is the major research motive of this paper. We use the B3LYP/6-31G* method to calculate the solvent molecule and binding energy tendency between the cation and anion. And using the computational E(2) value to explaine the NMR experimental T1-19F and T1-1H results (relaxation time). The first part of this paper (adding solvents to the ionic liquid system), the computational results meet the NMR experimental results. In the second part of this paper (hyper ion preference), the theoretical calculation results are unable to explain the results of the NMR experiment. Regarding this unable explained phenomenon, we try to use the following formula to explain that, �� G = H－TS ……… (1) When G = 0, H = TS �� T = H/S ……… (2) Where, H is equal to the theoretical calculated stability energy (SE). In formula 2, the temperature (T) is inverse proportion with entropy change (S) but direct proportion with enthalpy change (H). Thought the calculated H values have not much difference between hyper anion and hyper cation, we explain that regarding the next conclusion: Under the gaseous state ionic liquid, the entropy change (S), in fact, is the most influence.

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49

Liao, Wei-Chen, and 廖維宸. "Application of High Pressure Technique and Infrared Spectroscopy to Study the Interaction of Ionic Liquid and Lignin." Thesis, 2017. http://ndltd.ncl.edu.tw/handle/f8b8a6.

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50

LEONG, YUN-YI, and 梁婉怡. "Study of Crown Ether Based Polymer for the Application of Enantioselective Sensors and Interaction with Ionic-liquid." Thesis, 2017. http://ndltd.ncl.edu.tw/handle/53711782223986957507.

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