No / Ten different mathematical models representing the electrophoretic mobility of analytes in capillary electrophoresis in mixed solvents of different composition have been compared using 32 experimental data sets. The solvents are binary mixtures of water-methanol, water-ethanol and methanol-ethanol, respectively. Mean percentage deviation (MPD), overall MPD (OMPD) and individual percentage deviation (IPD) have been considered as comparison criteria. The results showed that a reorganized solution model, namely the combined nearly ideal binary solvent/Redlich-Kister equation, is the most accurate model among other similar models concerning both correlation ability and prediction capability

<p>The thesis deals partly with methodology including construction</p><p>of hardware and new pulse sequences in the field of electrophoretic</p><p>NMR, and partly with practical use of ENMR and</p><p>diffusion NMR in the investigation of charged colloidal systems.</p><p>Several sources of artefacts are investigated, including gas production</p><p>at the electrodes, electroosmosis and Joule heating</p><p>effects that can cause convection. The electrophoretic double</p><p>stimulated-echo pulse sequence is introduced to suppress these</p><p>artefacts and to increase the feasible measuring range to higher</p><p>electric fields and conductivities.</p><p>The interaction between the non-ionic polymer poly(ethylene</p><p>oxide) PEO and differently charged surfactants is investigated</p><p>using the above mentioned methods. The investigated surfactants</p><p>are the anionic sodium dodecyl sulphate (SDS) and</p><p>potassium laurate (KC12), the cationic dodecyltrimethylammonium</p><p>bromide (CTAB) and the non-ionic octyl β-D-glucoside.</p><p>ENMR is also used to investigate two different mixed micelle</p><p>systems, with SDS as the charged surfactant component and</p><p>dodecyl malono-bis-N-methylglucamide (C12BNMG) respectively</p><p>tetra(ethylene oxide) dodecyl ether (C12EO4) as the nonionic</p><p>surfactant component. A method to calculate the degree</p><p>of counter-ion dissociation, αdissociation, as a function of composition</p><p>is demonstrated.</p><p>Finally diffusion NMR is used to compare transport dynamics</p><p>in gel electrolyte systems based on two differently grafted polymers;</p><p>one amphiphilic system containing polymethacrylate</p><p>grafted partly with polyethylene oxide and partly with fluorocarbons</p><p>and the corresponding nonamphiphilic system grafted</p><p>with only polyethylene oxide. Both systems contain the electrolyte</p><p>lithium bis(trifluoromethylsulfonyl) imide salt dissolved in</p><p>γ-butyrolactone. The results show that the system based on the</p><p>amphiphilic polymer has better transport dynamics and therefore</p><p>is more suited as material for battery</p>

Après le génome, le nouveau défi est celui du protéome. Nous avons progressé vers la mise au point de la séparation électrophorétique des protéines membranaires dans un milieu qui leur conviendrait, type bicouche lipidique supportée. La grandeur principale, mesurée par FRAPP, a été le coefficient de diffusion de lipides ainsi que des protéines. L'étude du comportement de la bicouche supportée a permis de mettre en évidence, pour certains supports et dans certaines conditions de température, la formation d'une phase ondulée (ou ripple) malgré la proximité du support. La diminution de la portée des interactions coulombiennes par adjonction de sel se traduit par une augmentation de plusieurs ordres de grandeur du coefficient de diffusion, approchant au final le comportement d'une bicouche libre, tout en conservant les étapes caractéristiques de la transition gel/fluide. L'ordre de grandeur de ces énergies d'interactions a été estimé à partir des courbes D= f(T) et validé par une étude préliminaire originale de DSC sur des bicouches lipidiques supportées. L'&#945;-Hémolysine s'insère spontanément sous forme d'un pore heptamérique dans nos bicouches supportées et diffuse librement. En l'incubant en phase mixte (zones gel+ zones fluide), nous observons la formation de complexes de protéines. La dépendance du coefficient de diffusion avec la taille de l'objet est en 1/R2, R étant le rayon équivalent de la partie insérée de l'objet. L'application d'un champ électrique montre un transport électrophorétique dont la direction et l'importance sont modulées par la charge de l'objet. La mobilité électrophorétique varie également en 1/R2. / After the genome, the new challenge is the proteome. We have progressed toward electrophoretic separation of membrane proteins in a medium that they love, a supported lipid bilayer. The main parameter, measured by FRAPP, was the diffusion coefficient of different objects (lipids, proteins). Studying bilayer behaviour has showed that, on particular supports and in a given temperature range, ripple phase can exist, despite the proximity of the support. Adding salt decreases coulombic interactions which turns to increase the diffusion coefficient over several orders of magnitude, reaching the value for a free-standing bilayer in the fluid phase, meanwhile the main characteristic steps of the global gel/fluid transition are still observed. Estimation of the value of the interaction energy has been made and compared to results of a preliminary DSC study. &#945;-Hémolysin self-inserts spontaneously as an heptameric pore in supported bilayers and diffuses freely. Incubating in a gel/fluid mixture leads to protein complex formation. Diffusion varies with size as 1/R2, R being the equivalent radius of the inserted part of the object. Applying an electric field results in an electrophoretic motion where direction and magnitude are modulated by the charge of the object. Electrophoretic mobility varies also as 1/R2. Size dependence, magnitude of mobilities and a simple building protocol allow to hope carrying out soon a real electrophoretic separation of a protein mixture.

O presente trabalho tem como proposição investigar a hipótese de que a diminuição da tensão superficial do líquido favorece o comportamento reológico de suspensões concentradas, uma vez que as partículas estão mais próximas e a contribuição da força de capilaridade possivelmente aumenta. Como suspensões concentradas tendem ao comportamento viscoelástico, investigou-se métodos reológicos propícios para analisar possíveis consequências devido à alteração da tensão superficial da água. Foram utilizados dois carbonatos de cálcio equivalentes (P1 e P5) que se diferenciam pela distribuição granulométrica. Utilizou-se dois dispersantes de mercado e etilenoglicol como modificadores de tensão superficial. A análise de superfície pelo ensaio de potencial zeta, revelou carga superficial positiva. Embora os pós sejam equivalentes, a mobilidade eletroforética do P5 é menor. Verificou-se que o íon cálcio é determinante do potencial. Verificou-se contribuição eletrostática apenas dos dispersantes. O ensaio de gota pendente constatou diminuição da tensão superficial da água com os três aditivos. Ensaios de ascensão capilar pelo método de Washburn revelaram maiores ângulos de contato para ensaios com aditivos, sendo menor para P5. Avaliou-se geometrias e métodos reológicos a fim de selecionar bom conjunto para medidas de viscoelasticidade, sendo oscilatório de tensão e geometria vane escolhidos. O acréscimo dos dispersantes resultou em menores valores de G\' e tensões de escoamento, enquanto o etilenoglicol resultou em maiores. Não há relação clara entre valores calculados de ângulo de contato e mobilidade eletroforética. Os ensaio reológicos e de mobilidade relacionaram-se apenas para os dispersantes. A hipótese foi verificada pelos valores de tensão de escoamento e IPS. Para os dispersantes, foi possível observar comportamento próximo à hipótese, quanto menor foi a tensão superficial do líquido, menores valores de tensão para menores IPS. Explorou-se também a hipótese pelos ensaios de ângulo de contato, observou-se novamente curva próxima a hipótese. Embora necessidade de mais ensaios, o presente trabalho contribuiu para metodologia de exploração de características de superfície, dispersão e reológicas de suspensões concentradas. / The proposition of the present work is to investigate the hypothesis that the reduction of the surface tension of the liquid favors the rheological behavior of concentrated suspensions, since the particles are closer and the contribution of capillarity forces possibly increases. As concentrated suspensions tend to viscoelastic behavior, rheological methods were examined to analyze possible consequences due to changes of surface tension of the water. Two equivalent calcium carbonates (P1 and P5) were used and differ by particle-size distribution. Two market dispersants and ethylene glycol were used as surfactant. Surface analysis by the zeta potential test revealed positive surface charge and, although the powders are equivalent, the electrophoretic mobility of P5 is lower. The reults show that calcium is potential determining ion. Electrostatic contribution was found only for the dispersants. Pendant drop test showed a decrease in the surface tension of the water with the three additives. Washburn capillary rise technique estimated greater contact angles for tests with additives and lower ones for P5. Rheological geometries and methods were evaluated in order to select good set for viscoelasticity measurements, choosing oscillatory stress sweep and vane geometry. The addition of the dispersants resulted in lower values G \'and yield stress, while ethylene glycol resulted in higher values. There is no clear relation between contact angle and electrophoretic mobility. The rheological and eletrophoretic mobility showed relation only for dispersants. The hypothesis was verified by the values yield stress and IPS. For the dispersants, it was possible to observe behavior close to the hypothesis, the lower the surface tension of the liquid, the lower the yield stress for lower IPS. The hypothesis was also explored by the contact angle tests, a curve next to the hypothesis was observed again. Although the need for more tests, the present work contributed to the methodology of exploration of surface characteristics, dispersion and rheological characteristics of concentrated suspensions.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O objetivo do presente trabalho foi estudar o comportamento dos potenciais superficiais e do perfil de potencial atraves da membrana de eritr ocito em func ao da forca i onica e das cargas superficiais, usando um modelo que leva em conta as cargas el etricas do glicoc alix e das prote&#305;nas citoplasm aticas, al em das cargas superficiais da bicamada lip&#305;dica e os efeitos dos eletr olitos divalentes. Programas espec&#305;ficos em linguagem C foram elaborados para o c alculo desses potenciais, tomando como dados num ericos resultados experimentais de medidas de mobilidade eletrofor etica de eritr ocitos para diferentes valores de forca i onica. Neste c alculo, o metodo para tratamento dos dados eletrofor eticos indicado por Hsu et al.[57] foi inclu&#305;do em nosso modelo. A equac ao de Poisson-Boltzmann nao linear foi resolvida por computac ao num erica, usando o metodo de Runge-Kutta de quarta ordem, obtendo-se os perfis de potencial. Os resultados mostraram que a estimativa da densidade de carga el etrica na superf&#305;cie de c elulas usando a equac ao cl assica de Helmholtz-Smoluchowski conduz a valores que nao conseguem refletir as forcas que regem o comportamento eletrofor etico das mesmas. O presente modelo gerou valores de potenciais superficiais e perfis de potencial para a membrana do eritr ocito bem distintos daqueles obtidos anteriormente para um modelo descrito por uma equac ao de Poisson-Boltzmann linear. Nossos resultados confirmam que a avaliac ao de parametros el etricos superficiais da membrana de eritr ocito, envolvendo dados oriundos de eletroforese, deve incluir c alculos hidrodin amicos al em de eletroest aticos, como sugerido por Hsu et al. [57]. / The aim of present work was to study the behavior of the surface potentials and the potential profile across erythrocyte membrane in function of ionic strength and surface charge, using a model which takes into account electrical charges on glycocalyx and citoplasmatic proteins, in addition surface charges on lipid bylayer and effects due to mono and divalent electrolytes. Programs in C language were build to estimate the surface potentials, and experimental values of electrophoretic mobilities of erythrocytes for different ionic strength were applied. For this calculation, the method indicated by Hsu et al. [57] for treating electrophoretic data was included in our model. The non linear Poisson-Boltzmann equation was solved by numerical computation, using the forth order Range-Kutta method, to give the potential profiles. Results showed that values of electric charge on cellular surface obtained by applying the classical Helmholtz-Smoluchowski equation were not able to represent the forces involved in the electrophoretic behavior of cells. The present model generate values for surface potentials and potential profiles different from those obtained in previous work for a model described by linear Poisson- Boltzmann equation. According to our results, the estimation of surface electric parameters for the erythrocyte membrane from electrophoretic data must ese hydrodynamics and electrostatics calculations, as suggested by Hsu et al. [57]

The thesis deals partly with methodology including construction of hardware and new pulse sequences in the field of electrophoretic NMR, and partly with practical use of ENMR and diffusion NMR in the investigation of charged colloidal systems. Several sources of artefacts are investigated, including gas production at the electrodes, electroosmosis and Joule heating effects that can cause convection. The electrophoretic double stimulated-echo pulse sequence is introduced to suppress these artefacts and to increase the feasible measuring range to higher electric fields and conductivities. The interaction between the non-ionic polymer poly(ethylene oxide) PEO and differently charged surfactants is investigated using the above mentioned methods. The investigated surfactants are the anionic sodium dodecyl sulphate (SDS) and potassium laurate (KC12), the cationic dodecyltrimethylammonium bromide (CTAB) and the non-ionic octyl β-D-glucoside. ENMR is also used to investigate two different mixed micelle systems, with SDS as the charged surfactant component and dodecyl malono-bis-N-methylglucamide (C12BNMG) respectively tetra(ethylene oxide) dodecyl ether (C12EO4) as the nonionic surfactant component. A method to calculate the degree of counter-ion dissociation, αdissociation, as a function of composition is demonstrated. Finally diffusion NMR is used to compare transport dynamics in gel electrolyte systems based on two differently grafted polymers; one amphiphilic system containing polymethacrylate grafted partly with polyethylene oxide and partly with fluorocarbons and the corresponding nonamphiphilic system grafted with only polyethylene oxide. Both systems contain the electrolyte lithium bis(trifluoromethylsulfonyl) imide salt dissolved in γ-butyrolactone. The results show that the system based on the amphiphilic polymer has better transport dynamics and therefore is more suited as material for battery

This thesis studies the formation of mobile and surface-bound electric charges in nonpolar liquids. Unlike aqueous media with their natural abundance of charged species, liquids of low dielectric constant do not readily accommodate charges, but can do so in the presence of certain surfactant additives. Surfactant-mediated charging in nonpolar oils has long been exploited industrially, but the underlying charging mechanisms are far from understood. The present work seeks clarification by comparing the effect of ionic and nonionic surfactants on the conductivity of nonpolar solutions and the electrophoretically observable surface charge of suspended polymer particles. Both types of surfactant are found to generate mobile ions in solution as well as particle charge; and in the more surprising case of nonionic surfactants, the occurrence of particle charge and screening ions is confirmed independently by measurements of the electrostatic particle interaction energy. A systematic variation of the particle material and functionalization, the residual water content, and the surfactant concentration above and below the critical micelle concentration provides insights about the possible charging pathways. Reverse surfactant micelles are explored not only as charging agents, but also as reactors and templates for the synthesis of novel nanogels with promise for drug delivery. Synthesis via copper-free Click chemistry is shown to allow for better control of the particle size than a more conventional polymerization scheme, while avoiding metal catalysts and free radicals that are considered hazardous for most biomedical applications.

No description available.

abstract: How water behaves at interfaces is relevant to many scientific and technological applications; however, many subtle phenomena are unknown in aqueous solutions. In this work, interfacial structural transition in hydration shells of a polarizable solute at critical polarizabilities is discovered. The transition is manifested in maximum water response, the reorientation of the water dipoles at the interface, and an increase in the density of dangling OH bonds. This work also addresses the role of polarizability of the active site of proteins in biological catalytic reactions. For proteins, the hydration shell becomes very heterogeneous and involves a relatively large number of water molecules. The molecular dynamics simulations show that the polarizability, along with the atomic charge distribution, needs to be a part of the picture describing how enzymes work. Non Gaussian dynamics in time-resolved linear and nonlinear (correlation) 2D spectra are also analyzed. Additionally, a theoretical formalism is presented to show that when preferential orientations of water dipoles exist at the interface, electrophoretic charges can be produced without free charge carriers, i.e., neutral solutes can move in a constant electric field due to the divergence of polarization at the interface. Furthermore, the concept of interface susceptibility is introduced. It involves the fluctuations of the surface charge density caused by thermal motion and its correlation over the characteristic correlation length with the fluctuations of the solvent charge density. Solvation free energy and interface dielectric constant are formulated accordingly. Unlike previous approaches, the solvation free energy scales quite well in a broad range of ion sizes, namely in the range of 2-14 A° . Interface dielectric constant is defined such that the boundary conditions in the Laplace equation describing a micro- or mesoscopic interface are satisfied. The effective dielectric constant of interfacial water is found to be significantly lower than its bulk value. Molecular dynamics simulation results show that the interface dielectric constant for a TIP3P water model changes from nine to four when the effective solute radius is increased from 5 A° to 18 A° . The small value of the interface dielectric constant of water has potentially dramatic consequences for hydration. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2016

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O objetivo do presente trabalho foi estudar o comportamento dos potenciais superficiais e do perfil de potencial atraves da membrana de eritr ocito em func ao da forca i onica e das cargas superficiais, usando um modelo que leva em conta as cargas el etricas do glicoc alix e das prote&#305;nas citoplasm aticas, al em das cargas superficiais da bicamada lip&#305;dica e os efeitos dos eletr olitos divalentes. Programas espec&#305;ficos em linguagem C foram elaborados para o c alculo desses potenciais, tomando como dados num ericos resultados experimentais de medidas de mobilidade eletrofor etica de eritr ocitos para diferentes valores de forca i onica. Neste c alculo, o metodo para tratamento dos dados eletrofor eticos indicado por Hsu et al.[57] foi inclu&#305;do em nosso modelo. A equac ao de Poisson-Boltzmann nao linear foi resolvida por computac ao num erica, usando o metodo de Runge-Kutta de quarta ordem, obtendo-se os perfis de potencial. Os resultados mostraram que a estimativa da densidade de carga el etrica na superf&#305;cie de c elulas usando a equac ao cl assica de Helmholtz-Smoluchowski conduz a valores que nao conseguem refletir as forcas que regem o comportamento eletrofor etico das mesmas. O presente modelo gerou valores de potenciais superficiais e perfis de potencial para a membrana do eritr ocito bem distintos daqueles obtidos anteriormente para um modelo descrito por uma equac ao de Poisson-Boltzmann linear. Nossos resultados confirmam que a avaliac ao de parametros el etricos superficiais da membrana de eritr ocito, envolvendo dados oriundos de eletroforese, deve incluir c alculos hidrodin amicos al em de eletroest aticos, como sugerido por Hsu et al. [57]. / The aim of present work was to study the behavior of the surface potentials and the potential profile across erythrocyte membrane in function of ionic strength and surface charge, using a model which takes into account electrical charges on glycocalyx and citoplasmatic proteins, in addition surface charges on lipid bylayer and effects due to mono and divalent electrolytes. Programs in C language were build to estimate the surface potentials, and experimental values of electrophoretic mobilities of erythrocytes for different ionic strength were applied. For this calculation, the method indicated by Hsu et al. [57] for treating electrophoretic data was included in our model. The non linear Poisson-Boltzmann equation was solved by numerical computation, using the forth order Range-Kutta method, to give the potential profiles. Results showed that values of electric charge on cellular surface obtained by applying the classical Helmholtz-Smoluchowski equation were not able to represent the forces involved in the electrophoretic behavior of cells. The present model generate values for surface potentials and potential profiles different from those obtained in previous work for a model described by linear Poisson- Boltzmann equation. According to our results, the estimation of surface electric parameters for the erythrocyte membrane from electrophoretic data must ese hydrodynamics and electrostatics calculations, as suggested by Hsu et al. [57]