Tesis sobre el tema "Hydrophobic ion"

Les ions de taille nanométrique (nano-ions), tels que les clusters ioniques de bore, les polyoxométalates (POM) et les grands ions organiques, ont suscité un intérêt remarquable ces dernières années en raison de leur capacité à s’adsorber ou se lier à des systèmes chimiques électriquement neutres, tels que les molécules hôtes macrocycliques, les nanoparticules, les tensioactifs et les polymères, etc. Il a été démontré que ces processus d'adsorption ou de liaison sont induits par un phénomène médié par solvant, l'effet chaotropique, qui pousse le nano-ion de la masse d'eau vers une interface. Ainsi, l'eau d'hydratation de l'ion et de l'interface est libérée dans la masse d'eau, ce qui entraîne une restitution de la structure intrinsèque de l'eau. Cet effet est particulièrement fort pour les nano-ions. Ils sont par conséquent appelés ions superchaotropiques ou hydrophobes dans le prolongement des ions classiques (faiblement) chaotropiques tels que le SCN-. Tous les superchaotropes couramment étudiés, bien que chimiquement divers, partagent des caractéristiques physiques telles qu'une faible densité de charge et une grande polarisabilité. Les effets des nano-ions sur les auto-assemblages de tensioactifs non ioniques éthoxylés, les phases micellaires et bicouches, sont ici élucidés pour tirer des conclusions sur leur nature chaotropique et/ou hydrophobe. En combinant la diffusion aux petits angles des neutrons et des rayons X (SANS et SAXS), et les diagrammes de phase, les systèmes tensioactifs non ioniques/nano-ion sont examinés et comparés, du nanomètre à l'échelle macroscopique. Ainsi, il est montré que tous les nano-ions étudiés induisent un chargement électrique des assemblages de tensioactifs ainsi qu'une déshydratation des têtes de tensioactif non-ionique. En outre, les ions chaotropiques ou hydrophobes diffèrent dans leurs effets sur la forme micellaire. Les ions chaotropiques entraînent les micelles allongées de tensioactif non-ionique vers les micelles sphériques (augmentation de la courbure), tandis que les ions hydrophobes provoquent une transition vers les phases bicouches (diminution de la courbure). Il est conclu que les nano-ions superchaotropiques agissent comme des tensioactifs ioniques car leur ajout à des systèmes de tensioactifs non ioniques provoque un effet de charge. Cependant, les nano-ions et les tensioactifs ioniques sont fondamentalement différents par leur association avec l'ensemble des tensioactifs non ioniques. Le nano-ion s'adsorbe sur les têtes des tensioactifs non ioniques par effet chaotropique, tandis que le tensioactif ionique s'ancre dans les micelles entre les queues des tensioactifs non ioniques par effet hydrophobe. La comparaison des effets de l'ajout de nano-ions ou de tensioactifs ioniques à des tensioactifs non ioniques a été approfondie sur les mousses. Les mousses ont été étudiées en ce qui concerne l'épaisseur du film de mousse, le drainage dans le temps et la stabilité, respectivement en utilisant la SANS, l'analyse d'image et la conductométrie. Le POM superchaotropique testé (SiW12O404-, SiW) ne mousse pas dans l'eau contrairement au SDS classique de tensioactif ionique. Néanmoins, l'ajout de petites quantités de SiW ou de SDS à une solution moussante de tensioactif non ionique a permis d'obtenir des mousses plus humides avec une durée de vie plus longue. Entre-temps, l'épaisseur du film de mousse (déterminée en SANS) est augmentée en raison de la charge électrique des monocouches de tensioactifs non ioniques dans le film de mousse. Il est conclu que le comportement remarquable des nano-ions - ici sur les systèmes tensioactifs non ioniques - peut être étendu aux systèmes colloïdaux, tels que les mousses, les polymères, les protéines ou les nanoparticules. Cette thèse démontre que le comportement superchaotropique des nano-ions est un outil polyvalent qui peut être utilisé dans de nouvelles formulations de matériaux et d'applications de la matière molle
Nanometer-sized ions (nano-ions), such as ionic boron clusters, polyoxometalates (POMs) and large organic ions, have spawned remarkable interest in recent years due to their ability to adsorb or bind to electrically neutral chemical systems, such as macrocyclic host molecules, colloidal nano-particles, surfactants and polymers etc. The underlying adsorption or binding processes were shown to be driven by a solvent-mediated phenomenon, the chaotropic effect, which drives the nano-ion from the water bulk towards an interface. Thus, hydration water of the ion and the interface is released into the bulk resulting in a bulk water structure recovery. This effect is particularly strong for nano-ions. Therefore, they were termed superchaotropic or hydrophobic ions as an extension to classical (weakly) chaotropic ions such as SCN-. All commonly studied superchaotropes, though chemically diverse, share physical characteristics such as low charge density and high polarizability. Herein, the effects of nano-ions on ethoxylated non-ionic surfactant self-assemblies, micellar and bilayer phases, are elucidated to draw conclusions on their chaotropic and/or hydrophobic nature. By combining small angle scattering of neutrons and x-rays (SANS and SAXS), and phase diagrams, non-ionic surfactant/nano-ion systems are examined and compared, from the nanometer to the macroscopic scale. Thus, all studied nano-ions are found to induce a charging of the surfactant assemblies along with a dehydration of the non-ionic surfactant head groups. Furthermore, chaotropic and hydrophobic ions differ in their effects on the micellar shape. Superchaotropic ions drive the elongated non-ionic surfactant micelles towards spherical micelles (increase in curvature), whereas hydrophobic ions cause a transition towards bilayer phases (decrease in curvature). It is concluded that superchaotropic nano-ions act like ionic surfactants because their addition to non-ionic surfactant systems causes a charging effect. However, nano-ions and ionic surfactants are fundamentally different by their association with the non-ionic surfactant assembly. The nano-ion adsorbs to the non-ionic surfactant heads by the chaotropic effect, while the ionic surfactant anchors into the micelles between the non-ionic surfactant tails by the hydrophobic effect. The comparison of the effects of adding nano-ions or ionic surfactant to non-ionic surfactant was further investigated on foams. The foams were investigated regarding foam film thickness, drainage over time and stability, respectively using SANS, image analysis and conductometry. The tested superchaotropic POM (SiW12O404-, SiW) does not foam in water in contrast to the classical ionic surfactant SDS. Nevertheless, addition of small amounts of SiW or SDS to a non-ionic surfactant foaming solution resulted in wetter foams with longer lifetimes. Meanwhile, the foam film thickness (determined in SANS) is increased due to the electric charging of the non-ionic surfactant monolayers in the foam film. It is concluded that the remarkable behavior of nano-ions – herein on non-ionic surfactant systems – can be extended to colloidal systems, such as foams, polymers, proteins or nanoparticles. This thesis demonstrates that the superchaotropic behavior of nano-ions is a versatile tool to be used in novel formulations of soft matter materials and applications

Voltage-gated ion channels play fundamental roles in neural excitability, they are for instance responsible for every single heart beat in our bodies, and dysfunctional channels cause disease that can be even lethal. Understanding how the voltage sensor of these channels function is critical for drug design of compounds targeting neuronal excitability. The opening and closing of the pore in voltage-gated potassium (Kv) channels is caused by the arginine-rich S4 helix of the voltage sensor domain (VSD) moving in response to an external potential. In fact, VSDs are remarkably efficient at turning membrane potential into conformational changes, which likely makes them the smallest existing biological engines. Exactly how this is accomplished is not yet fully known and an area of hot debate, especially due to the lack of structures of the resting and intermediate states along the activation pathway. In this thesis I study how the VSD activation works and show how toxic compounds modulate channel gating through direct interaction with these quite unexplored drug targets. First, I show that a secondary structure transition from alpha- to 3(10)-helix in the S4 helix is an important part of the gating as this helix type is significantly more favorable compared to the -helix in terms of a lower free energy barrier. Second, I present new models for intermediate states along the whole voltage sensor cycle from closed to open and suggest a new gating model for S4, where it moves as a sliding 3(10)-helix. Interestingly, this 3(10)-helix is formed in the region of the single most conserved residue in Kv channels, the phenylalanine F233. Located in the hydrophobic core, it directly faces S4 and creates a structural barrier for the gating charges. Substituting this residue alters the deactivation free energy barrier and can either facilitate the relaxation of the voltage sensor or increase the free energy barrier, depending on the size of the mutant. These results are confirmed by new experimental data that supports that a rigid ring at the phenylalanine position is the rate-limiting factor for the deactivation gating process, while the activation is unaffected. Finally, we study how the activation can be modulated for pharmaceutical reasons. Neurotoxins such as hanatoxin and stromatoxin push S3b towards S4 helix limiting S4's flexibility. This makes it harder for the VSD to activate and might explain the stronger binding affinities in resting state. All these results are highly important both for the general topic of biological macromolecules undergoing functionally critical conformational transitions, as well as the particular case of voltage-gated ion channels where understanding of the gating process is probably the key step to explain the effects of mutations or drug interactions.

QC 20121115

Herein two novel synthetic strategies for the synthesis of sub-millimetre sized core–shell particles comprising a polyelectrolyte core and a porous hydrophobic shell are presented. In the first method, a water-in-oil-in-water (W/O/W) double-emulsion was used as a template for the simultaneous polymerisation of both the internal aqueous and the intermediate oil phases, via suspension polymerisation, leading to the formation of a cross-linked poly(acrylic acid-co-bisacrylamide) core contained in a porous poly(4-tert-butylstyrene-co-divinylbenzene) shell. It was found that the formation of core–shell morphology was favoured by the effect of acrylic acid which was responsible for the selective destabilization of the internal aqueous/oil (W/O) interface. It was found that rapid internal phase coarsening promoted the formation of single-core structures. A rapid gel-point of the oil phase, on the other hand, reduced the internal aqueous phase diffusion towards the external phase. The detrimental effect over internal emulsion stability was replicated using ethanol, 2-propanol, n-butanol and propionic acid which were used as a co-solvent in the internal aqueous phase to promote core/shell morphology formation. The second method involved the use of a flow-focusing device for the formation of monodisperse W/O/W emulsion droplets which were photo-polymerised. Anionic poly(sodium acrylate), poly(sodium vinyl sulfonate), and cationic poly(3-acrylamidopropyl)trimethylammonium chloride) hydrogels were encapsulated within a porous poly(trimethylolpropane triacrylate-co-methyl methacrylate) shell. Control over both particle diameter and shell thickness was achieved by tuning the flow rates of the different phases. The use of these novel hydrogel core/shell particles as novel material for environmental applications, including the scavenging of radionuclides, was investigated. It was found that hydrophilic substances including dyes and metal ions were rapidly adsorbed and encapsulated within the core region after diffusing through the permeable porous shell. Part of the results obtained in this work have been published in the article J. Mater. Chem. A, 2013, 1, 12553-12559.

Voltage-gated ion channels play fundamental roles in neural excitability and thus dysfunctional channels can cause disease. Understanding how the voltage-sensor of these channels activate and inactivate could potentially be useful in future drug design of compounds targeting neuronal excitability. The opening and closing of the pore in voltage-gated ion channels is caused by the arginine-rich S4 helix of the voltage sensor domain (VSD) moving in response to an external potential. Exactly how this movement is accomplished is not yet fully known and an area of hot debate. In this thesis I study how the opening and closing in voltage-gated potassium (Kv) channels occurs. Recently, both experimental and computational results have pointed to the possibility of a secondary structure transition from α- to 3(10)-helix in S4 being an important part of the gating. First, I show that the 3(10)-helix structure in the S4 helix of a Kv1.2-2.1 chimera protein is significantly more favorable compared to the α-helix in terms of a lower free energy barrier during the gating motion. Additional I suggest a new gating model for S4, moving as sliding 310-helix. Interestingly, the single most conserved residue in voltage- gated ion channels is a phenylalanine located in the hydrophobic core and directly facing S4 causing a barrier for the gating charges. In a second study, I address the problem of the energy barrier and show that mutations of the phenylalanine directly alter the free energy barrier of the open to closed transition for S4. Mutations can either facilitate the relaxation of the voltage-sensor or increase the free energy barrier, depending on the size of the mutant. These results are confirmed by new experimental data that supports that a rigid, cyclic ring at the phenylalanine position is the determining rate-limiting factor for the voltage sensor gating process.
QC 20110616

A method is described for preset-count irradiations between 1 and 100 ions singling-out individual ions from an ion beam with more than a billion ions arriving per second. The ion tracks are etched in a conductometric system with real-time evaluation of the acquired data. The etch process can be interrupted when reaching a preset channel diameter. Cylindrical channels are obtained by adding surfactants to the etch solution forming a self-assembled barrier between etching medium and polymer. Asymmetric etching of single ion tracks leads to pH sensitive conical pores with diode-like properties. Using etched channels as template, homogeneous and multilayer magnetic single-wires are electrodeposited. The magnetoresistivity of the wires is studied. Single-track applications comprise critical apertures (cylindric, conic, necked), asymmetric pores (pH sensitive, biospecific), Giant Magneto Resistance sensors, and spintronic devices. On the basis of studies with individual ion tracks we tackled tilted multiporous systems such as ion beam lithography with a masked ion beam leading to micro-structures with inclined walls and anisotropic superhydrophobic ion track textures, analogous to biological shingle structures on butterfly wings. We demonstrated qualitatively, that the asymmetry of the texture translates into motion under ultrasonic agitation. This could lead to the development of rotary drives.

Previous studies in Dr. Yang’s laboratory have established a grafting, design, and subdomain approach in order to investigate the properties behind Ca2+-binding sites located in Ca2+-binding proteins by employing engineered proteins. These approaches have not only enabled us to isolate Ca2+-binding sites and obtain their Ca2+-binding affinities, but also to investigate conformational changes and cooperativity effects upon Ca2+ binding. The focus of my thesis pertains to optimizing the expression and purification of engineered proteins with tailored functions. Proteins were expressed in E. coli using different cell strains, vectors, temperatures, and inducer concentrations. After rigorous expression optimization procedures, proteins were further purified using chromatographic and/or refolding techniques. Expression and purification optimization of proteins is essential for further analyses, since the techniques used for these studies require high protein concentrations and purity. Evaluated proteins had yields between 5-70 mg/L and purities of 80-90% as confirmed by SDS-PAGE electrophoresis.

In this thesis, conventional and unconventional technologies have been studied and combined in order to make heterogeneous microfluidics with potential advantages, especially in biological applications. Many conventional materials, like silicon, glass, thermoplastic polymers, polyimide and polydimethylsiloxane (PDMS) have been combined in building heterogeneous microfluidic devices or demonstrators. Aside from these materials, unconventional materials for microfluidics such as stainless steel and the fluoroelastomer Viton have been explored. The advantages of the heterogeneous technologies presented were demonstrated in several examples: (1) For instance, in cell biology, surface properties play an important role. Different functions were achieved by combining microengineering and surface modification. Two examples were made by depositing a Teflon-like film: a) a non-textured surface was made hydrophobic to allow higher pressures for cell migration studies and b) a surface textured by ion track technology was even made super-hydrophobic. (2) In microfluidics, microactuators used for fluid handling are important, e.g. in valves and pumps. Here, microactuators that can handle high-pressures were presented, which may allow miniaturization of high performance bioanalyses that until now have been restricted to larger instruments. (3) In some applications the elastomer PDMS cannot be used due to its high permeability and poor solvent resistivity. Viton can be a good replacement when elasticity is needed, like in the demonstrated paraffin actuated membrane.(4) Sensing of bio-molecules in aquatic solutions has potential in diagnostics on-site. A proof-of-principle demonstration of a potentially highly sensitive biosensor was made by integrating a robust solidly mounted resonator in a PDMS based microfluidic system. It is concluded that heterogeneous technologies are important for microfluidic systems like micro total analysis systems (µTAS) and lab-on-chip (LOC) devices.

Oscillations of the electrical potential and interfacial tension have been studied during mass transfer in water/dichloromethane biphasic systems: CTAB/picric acid and SDS/TAAB for which, the chain length of the tetraalkylammonium was varied (from ethyl to butyl). A detailed analysis of the signals recorded allowed us to confirm the hydrodynamic origin (Marangoni instability) of the oscillations. We have determined the physico-chemical properties of all species involved (partition and adsorption constant, molecular area, and association constant of the ion pairs). For this, measurements of the surface tension, UV/Visible spectrophotometry and mass spectrometry have been performed. For the SDS/TAAB system, we have observed increasing association of TAADS ion pairs with chain length. We have also carried out theoretical calculations (DFT, Ab-initio) to highlight a geometry supporting the hydrophobic interactions between the two ions.

La presente tesis doctoral titulada ¿Materiales funcionales híbridos para el reconocimiento óptico de explosivos nitroaromáticos mediante interacciones supramoleculares¿ se basa en la combinación de principios de Química Supramolecular y de Ciencia de los Materiales para el diseño y desarrollo de nuevos materiales híbridos orgánico-inorgánicos funcionales capaces de detectar explosivos nitroaromáticos en disolución. En primer lugar se realizó una búsqueda bibliográfica exhaustiva de todos los sensores ópticos (cromogénicos y fluorogénicos) descritos en la bibliografía y que abarca el periodo desde 1947 hasta 2011. Los resultados de la búsqueda están reflejados en el capítulo 2 de esta tesis. El primer material híbrido preparado está basado en la aplicación de la aproximación de los canales iónicos y, para ello, emplea nanopartículas de sílice funcionalizadas con unidades reactivas y unidades coordinantes (ver capítulo 3). Este soporte inorgánico se funcionaliza con tioles (unidad reactiva) y una poliamina lineal (unidad coordinante) y se estudia el transporte de una escuaridina (colorante) a la superficie de la nanopartícula en presencia de diferentes explosivos. En ausencia de explosivos, la escuaridina (color azul y fluorescencia intensa) es capaz de reaccionar con los tioles anclados en la superficie decolorando la disolución. En presencia de explosivos nitroaromáticos se produce una inhibición de la reacción escuaridinatiol y la suspensión permanece azul. Esta inhibición es debida a la formación de complejos de transferencia de carga entre las poliaminas y los explosivos nitroaromáticos. En la segunda parte de esta tesis doctoral se han preparado materiales híbridos con cavidades biomiméticas basados en el empleo de MCM-41 como soporte inorgánico mesoporoso (ver capítulo 4). Para ello se ha procedido al anclaje de tres fluoróforos (pireno, dansilo y fluoresceína) en el interior de los poros del soporte inorgánico y, posteriormente, se ha hidrofobado el interior de material mediante la reacción de los silanoles superficiales con 1,1,1,3,3,3-hexametildisilazano. Mediante este procedimiento se consiguen cavidades hidrófobas que tienen en su interior los fluoróforos. Estos materiales son fluorescentes cuando se suspenden en acetonitrilo mientras que cuando se añaden explosivos nitroaromáticos a estas suspensiones se observa una desactivación de la emisión muy marcada. Esta desactivación de la emisión es debida a la inclusión de los explosivos nitroaromáticos en la cavidad biomimética y a la interacción de estas moléculas (mediante interacciones de ¿- stacking) con el fluoróforo. Una característica importante de estos materiales híbridos sensores es que pueden ser reutilizados después de la extracción del explosivo de las cavidades hidrofóbicas. En la última parte de esta tesis doctoral se han desarrollado materiales híbridos orgánicoinorgánicos funcionalizados con ¿puertas moleculares¿ que han sido empleados también para detectar explosivos nitroaromáticos (ver capítulo 5). Para la preparación de estos materiales también se ha empleado MCM-41 como soporte inorgánico. En primer lugar, los poros del soporte inorgánico se cargan con un colorante/fluoróforo seleccionado. En una segunda etapa, la superficie externa del material cargado se ha funcionalizado con ciertas moléculas con carácter electrón dador (pireno y ciertos derivados del tetratiafulvaleno). Estas moléculas ricas en electrones forman una monocapa muy densa (debida a las interacciones dipolo-dipolo entre estas especies) alrededor de los poros que inhibe la liberación del colorante. En presencia de explosivos nitroaromáticos se produce la ruptura de la monocapa, debido a interacciones de ¿-stacking con las moléculas ricas en electrones, con la consecuencia de una liberación del colorante atrapado en el interior de los poros observándose una respuesta cromo-fluorogénica
Salinas Soler, Y. (2013). Functional hybrid materials for the optical recognition of nitroaromatic explosives involving supramolecular interactions [Tesis doctoral]. Editorial Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/31663
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The research presented in this dissertation is focused on the construction of complex molecular structures on planar gold and silicon dioxide surfaces using a variety of surface modification techniques, along with thorough surface characterization at each modification step. The dissertation is structured into six separate chapters. In Chapter 1, an introduction to the importance and implications of molecular level surface modification, commonly employed surface modification methods, and available surface characterization techniques is presented. Chapter 2 shows applications of novel methodologies for the functionalization of gold surfaces using alkane dithiol self-assembled monolayers and thiol-ene click chemistry. The resulting functionalized gold substrates demonstrate higher chemical stability than alkanethiol self-assembled monolayers alone and allow spatially controlled functionalization of gold surfaces with light. In Chapter 3, work on tunable hydrophobic surfaces is presented. These surfaces are prepared using a combination of organosilane chemistry, layer-by-layer polyelectrolyte deposition, and thiol-ene chemistry. These hydrophobic surfaces demonstrate high mechanical and chemical stability, even at low pH (1.68). The pinning of water droplets could be tuned on them by the extent of their thermal treatment. Comprehensive surface characterization using X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), spectroscopic ellipsometry, atomic force microscopy, and water contact angles was carried out on the molecular assemblies prepared on gold and silicon dioxide surfaces. Chapters 4 and 5 are focused on the application, data interpretation, and enhancement in sensitivity of different surface characterization methods. In Chapter 4, XPS, ToF-SIMS, and principal components analysis are used to probe a real world corrosion-type problem. This systemic study showed the destruction of a protective coating composed of a nitrilotris(methylene)triphosphonic acid by a low-intensity fluorine plasma. In Chapter 5, enhancement in ToF-SIMS signals is shown via bismuth metal deposition. These surfaces are also probed by spectroscopic ellipsometry using the interference enhancement method. Finally, Chapter 6 concludes this dissertation by describing possible future work.

Ce memoire porte sur l'utilisation de solutions concentrees de nafion (gels hydrophobes de nafion) pour l'immobilisation de la glucose oxydase (god) a la surface d'electrodes. Dans un premier temps, l'oxydase est contenue au sein d'une pate de carbone aqueuse, le gel du ionomere realisant un interface selectif entre systeme enzymatique immobilise et milieu de dosage. Cette separation des deux intervenants est imposee par leur incompatibilite, la confrontation de la god et de la solution hydrophobe du polymere conduisant a une perte des proprietes catalytiques de l'enzyme. L'etude du comportement de ce dispositif permet d'en degager les caracteristiques et de mettre en evidences ses principales limitations: mauvaise immobilisation du mediateur (espece electroactive chargee du transport d'electrons entre enzyme et electrode), inhibition de la reaction d'oxydation du glucose, miniaturisation poussee impossible. Ce travail est complete par une etude cinetique, realisee au moyen d'une electrode tournante, grace a laquelle la permeation du glucose au sein des gels peut etre quantifiee. La plupart des problemes de la precedente electrode etant imputables a son organisation en couches successives, nous cherchons dans un deuxieme temps a associer de facon plus intime god et solution hydrophobe du polymere. L'inclusion de l'enzyme dans des gels dont les solvants sont des alcools d'assez faible poids moleculaire, puis dans des gels prealablement hydrates, donne des gels ou le pouvoir catalytique de la god est conserve. Ces materiaux enzymatiques sont aisement deposes a la surface d'electrodes, realisant des dispositifs dont les dimensions peuvent etre reduites et dont la structure permet d'eviter l'inhibition de la glucose oxydase lors du dosage du glucose. Deux strategies d'immobilisation du mediateur dans ces capteurs amperometriques sont envisagees, la premiere est fondee sur l'affinite de quelques ferrocenes pour le solvant hydrophobe constitutif du gel, la seconde sur l'affinite de l'oxygene pour les chaines perfluorees du nafion

Nous avons étudié par simulations de dynamique moléculaire la solvatation de molécules hydrophobes chargées dans des liquides purs et à des interfaces liquide / liquide.
La première partie concerne l'hypothèse TATB qui suppose que les deux ions AsΦ4+ (TA+) et BΦ4- (TB-) ont la même énergie de solvatation dans tout solvant. Nous avons montré que les deux ions étaient solvatés différemment dans des liquides purs (eau, chloroforme, acétonitrile) ainsi qu'à une interface chloroforme / eau. Des calculs de différences d'énergie libre de transfert ont confirmé cette tendance, de même que des simulations sur des ions "hypothétiques" S+ et S-, analogues sphériques de AsΦ4+ et BΦ4- qui répondent exactement aux critères de l'hypothèse. De nombreux tests méthodologiques ont été effectués et ont permis de montrer l'importance (i) d'une description correcte des interactions à "longue distance", (ii) de la répartition précise des charges atomiques et (iii) du modèle de solvant utilisé notamment pour l'eau, sur la différence de solvatation de "gros" ions hydrophobes selon leur charge.
La seconde partie décrit les premières simulations avec le CO2 supercritique dans le cadre de l'extraction liquide / liquide de cations métalliques. Nous avons étudié le comportement d'ions (Cs+, UO22+, Eu3+), de molécules extractantes (tri-n-butylphosphate, calixarène), de complexes de ces cations avec ces molécules extractantes et d'acide nitrique à une interface préformée CO2 / eau et lors de simulations de séparation de phase, en partant de solutions binaires homogènes CO2 / eau. Ces études démontrent l'importance des phénomènes interfaciaux, des conditions de simulations, ainsi que de la concentration en acide et en extractant, dans les processus d'extraction vers le CO2 supercritique.

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

acase@tulane.edu
Deep-cavity cavitands are a class of molecules that can be used for multiple applications, including: regioselective reactions, catalysis, separations & selectivity, and kinetic protection. They have also proven useful as models for studying the Hofmeister and hydrophobic effects, in context. Herein, the synthesis of these molecules will be outlined, highlighting novel approaches for molecular diversity with the synthesis of inherently positively charged hosts, protic hosts, neutral and negatively charged hosts. The effect of structure modification to the rim of the hosts will be discussed with a supramolecular ion-responsive dimer-to-tetramer system. This system also demonstrates cation selectivity and the importance of discussing ion-ion and ion-hydrophobic interactions in context. Finally, two systems with octa-cationic hosts will be presented. The change of charge on the host has dramatic consequences to their assembly properties, with salting-in salts stabilizing them.
1
Matthew B Hillyer

Specific ion effects on protein interfaces have been observed for many years, but yet comprehensive explanations regarding the mechanism by which ions interact with proteins and more general aqueous interfaces are still under investigation. Realistically, ion specificity on protein stability is due to numerous contributions and interactions between the solution and protein. However, the most important contribution is arguably the hydrophobic effect, specifically the change in free energy when water molecules are liberated from the interfacial region upon protein folding. In the work presented here, the effects of different ions on the critical micelle concentration (CMC) of 1, 2 –Hexanediol were examined to study salt effects on hydrophobicity by the means of fluorescence spectroscopy. Our results show that anions and cations do exhibit the specific effects on hydrophobic interactions. However, the origin of these specific ion effects different for cations and anions. Cation specific effects are caused by their ability to form cavities in solution, while anion specific effects arise from their ability to interact with the interface. These results are of interest to the researchers in the protein folding field, providing significant experimental hydrophobicity data necessary for theoretical biologists that are attempting to predict protein structures.
February 2015

碩士
國立中央大學
化學工程與材料工程研究所
90
Abstract The interaction mechanism of proteins with various commercial available cation exchangers at different binding conditions were studied. The aim of this research is the study of the hydrophobic effect of the ion exchanger ligands on protein binding behavior at high ionic strength. In this investigation, proteins, Lysozyme and Myoglobin, were bound to the absorbents which were selected to encompass the hydrophobic effects of three different ion exchanger ligand groups (CM Sepharose, SP Sepharose and SOURCE 30S). Under these experiment were modulated with different types of salt and at high ionic strength. The adsorption behavior were analyzed with batch isotherm and adsorption enthalpies, directly measured by isothermal titration calorimeter. Experimental results indicated that the adsorption mechanism mainly by hydrophobic interaction occurs at high ionic strength and the binding enthalpies confirm this suggestion. In high ionic strength conditions, the enthalpy play a unfavior role in driving the process and the adsorption is driven by entropy gained from the dehydration and desolvation processes. In addition, binding affinities and enthalpies were found to be ligand-dependent, and the most hydrophobic lgands (CM Sepharose) has the highest binding affinitiy among the ligands studied. The presented data shed light on the influence of the hydrophobic effect of the ion exchanger ligands on the protein binding at high ionic strength condition.

碩士
國立中正大學
化學工程研究所
88
Abstract Enzyme immobilization is one of the most important techniques for enzyme application and protein separation in biotechnology. In this study, non-porous particles containing hydrophobic and immobilized metal-ion groups were prepared. The particles conatining two different functional groups were applied for enzyme immobilization. In this study, monomers of methyl acrylate (MMA) and glycidyl methacrylate (GMA) were copolymerized by the method of dispersion polymerization. Copolymer particles of MMA-co-GMA have a diameter of less than 4μm and epoxy groups on the surface. According to the results from Micrometitics (ASAP2000), the prepared particles were proved to be non-porous. The expoxy groups on the particle surface were successfully converted to aldehyde groups by periodic acid. The particles with aldehyde group on the surface were then chemically modified with iminodiacetic acid (IDA) and n-octylamine, separately or concurrently. The resultsant particles were incubated with the solution of copper ions. The adsorption results indicate that praticles conatining chelate group and chelate/hydrophobic groups both possess a specific binding to metal ions. But particles containing hydrophobic group don’t possess a specific binding to metal ions. The results suggest that the functional groups are coupled on to the surface of partices certainly. These three kinds of particles were applied to immobilize DNase I. The results of adsorption indicate that the particles containing immobilized metal-ions groups have a stronger adsorption than mixed-mode particles containing both immobilized metal-ions and hydrophobic groups. But the results of desorption and stability study indicate that the particles containing both immobilized metal-ions and hydrophobic groups have a stronger desorption and stability than the particles containing immobilized metal-ions group only. On the other hand, although the particles conatining hydrophobic groups only have a stronger desorption than the mixed-mode particles, the mixed-mode particles have a stronger adsorption than the particles conatining hydrophobic groups only. In summary, the results obtained in this work indicate the mixed mode particles have many advantages for enzyme immobilization.

Mechanisms of adsorption of alkaline copper quat (ACQ) components in wood were investigated with emphasis on: copper chemisorption, copper physisorption, and quat adsorption. Various factors were investigated that could affect the adsorption of individual ACQ components in red pine wood. Copper chemisorption in wood was affected by ligand types coordinating with Cu and the stability of the Cu-ligand complexes in solution. For Cu-monoethanolamine (Cu-Mea) system, the prevailing active solvent species at the solution pH, [Cu(Mea)2-H]+ complexes with wood acid sites and loses one Mea molecule through a ligand exchange reaction. The amount of adsorbed Cu was closely related to the cation exchange capacity of wood. An increase in Mea/Cu ratio increased the proportion of the uncharged Cu-Mea complex and resulted in decreased Cu chemisorption in wood. Copper precipitation is also an important Cu fixation mechanisms of Cu-amine treated wood. X-ray diffraction analysis revealed that in vitro precipitated Cu was a mixture of copper carbonates (azurite and malachite) and possibly Cu2O. Higher concentration Cu-amine solutions retarded the Cu precipitation to a lower pH because of higher free amine in the preservative-wood system. The changes in zeta potential of wood in relationship to the quaternary ammonium (alkyldimethylbenzylammonium chloride: ADBAC) adsorption isotherm showed two different adsorption mechanisms for quat in wood: ion exchange reaction at low concentration and additional aggregation form of adsorption by hydrophobic interaction at high concentration. Because of the aggregation effect, when wood was treated with ACQ, high amounts of ADBAC were concentrated near the surface creating a steep gradient with depth. This aggregated ADBAC was easily leached out while the ion exchanged ADBAC had high leaching resistance. Free Mea and Cu of ACQ components appeared to compete with ADBAC for the same bonding sites in wood.

Raman multivariate curve resolution (Raman-MCR) spectroscopy is used to study water-mediated interactions by decomposing Raman spectra of aqueous solutions into bulk water and solute-correlated (SC) spectral components. The SC spectra are minimum-area difference spectra that reveal solute-induced perturbations of water structure, including changes in water hydrogen-bonding strength, tetrahedral structure, and formation of dangling (non-hydrogen-bonded) OH defects in a solute's hydration shell. Additionally, Raman-active intramolecular vibrational modes of the solute may be used to uncover complementary information regarding solute--solute interactions. Herein, Raman-MCR is applied to address fundamental questions related to: (1) confined cavity water and its connection to host-guest binding, (2) hydrophobic hydration of fluorinated solutes, (3) specific ion effects on nonionic micelle formation, and (4) ion pairing in aqueous solutions.

Previous studies of short DNA hairpins have revealed that loop and stem sequences can significantly affect the thermodynamic stability of short DNA hairpins. Nevertheless, there has not been sufficient investigation into the pressure-temperature stability of DNA hairpins, and the current thermodynamic knowledge of DNA hairpins’ stability is limited to the temperature domain. In this work, we report the effect of hydrostatic pressure on the helix-coil transition temperature (TM) for eleven short DNA hairpins at different salt concentrations by performing UV-monitored melting. The studied hairpins form by intramolecular folding of 16-base self-complementary DNA oligo¬deoxy¬ribonucleotides. Model dependent (van’t Hoff) transition parameters such as ΔHvH and transition volume (ΔV) were estimated from analysis of optical melting transitions. Experiments revealed the ΔV for denaturation of these molecules range from -2.35 to +6.74 cm3mol-1. The difference in the volume change for this transition is related to differences in the hydration of these molecules.