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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
601

Alternating current electrocoagulation (AC/EC) of fine particulate suspensions

Ifill, Roy O. Unknown Date
No description available.
602

Ocular toxoplasmosis : immunopathology and virulence : the influence of parasite virulence on the clinical, biological, and immunological characteristics of ocular toxoplasmosis (OT) in the Old and New World

De la Torre, Ligia Alejandra 18 September 2013 (has links) (PDF)
Ocular involvement, mainly retinochoroiditis, is one of the most severe sequelae of Toxoplasma gondii infection. However, the pathophysiological mechanisms of retinal destruction are poorly understood. Several studies suggested a more frequent and more severe ocular involvement in South American infections compared with European infections, probably due to different T. gondii strains (Type I/III, and atypical vs. Type II). To compare the clinical characteristics and biological and immunological responses in a single study and using the same parameters, in Colombian and French patients with active ocular toxoplasmosis (OT), as well as to study the local cytokinome in aqueous humor of these patients and correlate it with the clinical features. We prospectively collected and compared the clinical features of patients with active OT, evaluated at the Department of Ophthalmology of Strasbourg University Hospital and of Quindio University Health-Center. Results of biological tests in the collected aqueous humor samples were compared between Colombian and French patients: the pattern of protein recognition by immunoblotting (IB); the relative diagnostic sensitivities of IB and Polymerase Chain Reaction (PCR); and the cytokine and chemokine profiles. We found that Colombian and French OT patients presented not only different clinical characteristics but also biological characteristics, and that more virulent South American strains might be responsible for these differences, due to a disruption of the protective effects of interferon gamma (IFN-γ). Retinal lesions were 50% greater in Colombian patients. Macular localization leading to visual impairment was observed in 56% of Colombian cases, compared with 13% of French patients. Moreover, more vitreous inflammation and vasculitis were observed in Colombian patients. However, cytokine assays of the aqueous humor showed upregulation of inflammatory responses in European patients, notably IL-17, which we did not observe in Colombian patients. In a mouse model, intraocular tachyzoite injection of type II and atypical T. gondii strains resulted in differences in parasite multiplication and pathology similar to those observed in human infections. Production of IL-17 and other inflammatory markers, like IL-6, MCP-1, and the Th17 transcription factor ROR-γt was observed upon infection with the type II PRU strain, but was much less with the atypical LEF strain. In a previous work, the cytokine and mRNA patterns showed an upregulation of Th1 responses, notably IFN-γ production, in French patients, and anti-IL-17A antibody markedly diminished clinical damage and retinal inflammation, and also diminished parasite proliferation. In contrast to these previous findings in French patients, the cytokinome of aqueous humor of OT Colombian patients showed a downregulation of Th1 and Th17 responses and an upregulation of the Th2 response. Correlation between the clinical characteristics of Colombian patients with active OT and the levels of cytokines in aqueous humor (AH) showed that local production of cytokines differed between patients with OT, and particular cytokine levels were related to more severe clinical characteristics. Some cytokines were related to a higher number of recurrences.There are clinical and biological differences between Colombian and French patients with OT. There seem to be strain-specific differences in IL-17 and IFN-γ induction, which play an important role in the pathogenesis of this disease. These differences should be considered when thinking in perspectives of any possible immune-modulatory treatment in OT.
603

Simulation studies of molecular transport across the liquid-gas interface

Somasundaram, Theepaharan January 2000 (has links)
No description available.
604

Effects of Aqueous Organic Coatings on the Interfacial Transport of Atmospheric Species

Reeser, Dorea Irma 14 January 2014 (has links)
Species must interact with air—aqueous interfaces in order to transport between either phase, however organic coated water surfaces are ubiquitous in the environment, and the physical and chemical processes that occur at organic coated aqueous surfaces are often different than those at pure air—water interfaces. Three studies were performed investigating the transport of species across air—aqueous interfaces with organic coatings in an effort to gain further insight into these processes. Gas and solution phase absorption spectroscopy were used to study the effect of octanol coatings on the formation of molecular iodine (I2) by the heterogeneous ozonation of iodide and its partitioning between phases. Compared to uncoated solutions, the presence of octanol monolayers had a minor effect on the total amount of I2 produced, however, it did significantly enhance the gas to solution partitioning of I2. Incoherent broadband cavity-enhanced absorption spectroscopy (IBBC-EAS) was used to measure the gas-phase nitrogen dioxide (NO2) evolved via photolysis of aqueous nitrate solutions either uncoated or containing octanol, octanoic acid and stearic acid monolayers. Both octanol and stearic acid reduced the rate of gaseous NO2 evolution, and octanol also decreased the steady-state amount of gaseous NO2. Alternatively, octanoic acid enhanced the rate of gaseous NO2 evolution. Finally, the loss of aqueous carbon dioxide (CO2) from aqueous solutions saturated with CO2 was measured using a CO2 electrode in the absence and presence of stearic acid monolayers and octanol coatings, and a greenhouse gas analyzer was used to measure the evolution of gaseous CO2 from solutios with octanol monolayers. Enhanced losses of aqueous and evolved gaseous CO2 were observed with organic coated solutions compared to those uncoated. The results of these studies suggest that organic coatings influence the transport of I2, NO2 and CO2 via one, or a combination of: barrier effects, surface tension effects, chemistry effects and aqueous – surface – gas partitioning effects. These results, particularly the enhanced partitioning of these species to octanol coated aqueous surfaces, have important implications for species transport at air—aqueous interfaces, and may provide useful insight for future studies and parameters for atmospheric models of these species.
605

Effects of Aqueous Organic Coatings on the Interfacial Transport of Atmospheric Species

Reeser, Dorea Irma 14 January 2014 (has links)
Species must interact with air—aqueous interfaces in order to transport between either phase, however organic coated water surfaces are ubiquitous in the environment, and the physical and chemical processes that occur at organic coated aqueous surfaces are often different than those at pure air—water interfaces. Three studies were performed investigating the transport of species across air—aqueous interfaces with organic coatings in an effort to gain further insight into these processes. Gas and solution phase absorption spectroscopy were used to study the effect of octanol coatings on the formation of molecular iodine (I2) by the heterogeneous ozonation of iodide and its partitioning between phases. Compared to uncoated solutions, the presence of octanol monolayers had a minor effect on the total amount of I2 produced, however, it did significantly enhance the gas to solution partitioning of I2. Incoherent broadband cavity-enhanced absorption spectroscopy (IBBC-EAS) was used to measure the gas-phase nitrogen dioxide (NO2) evolved via photolysis of aqueous nitrate solutions either uncoated or containing octanol, octanoic acid and stearic acid monolayers. Both octanol and stearic acid reduced the rate of gaseous NO2 evolution, and octanol also decreased the steady-state amount of gaseous NO2. Alternatively, octanoic acid enhanced the rate of gaseous NO2 evolution. Finally, the loss of aqueous carbon dioxide (CO2) from aqueous solutions saturated with CO2 was measured using a CO2 electrode in the absence and presence of stearic acid monolayers and octanol coatings, and a greenhouse gas analyzer was used to measure the evolution of gaseous CO2 from solutios with octanol monolayers. Enhanced losses of aqueous and evolved gaseous CO2 were observed with organic coated solutions compared to those uncoated. The results of these studies suggest that organic coatings influence the transport of I2, NO2 and CO2 via one, or a combination of: barrier effects, surface tension effects, chemistry effects and aqueous – surface – gas partitioning effects. These results, particularly the enhanced partitioning of these species to octanol coated aqueous surfaces, have important implications for species transport at air—aqueous interfaces, and may provide useful insight for future studies and parameters for atmospheric models of these species.
606

Aqueous Solutions as seen through an Electron Spectrometer : Surface Structure, Hydration Motifs and Ultrafast Charge Delocalization Dynamics

Ottosson, Niklas January 2011 (has links)
In spite of their high abundance and importance, aqueous systems are enigmatic on the microscopic scale. In order to obtain information about their geometrical and electronic structure, simple aqueous solutions have been studied experimentally by photo- and Auger electron spectroscopy using the novel liquid micro-jet technique in conjunction with synchrotron radiation. The thesis is thematically divided into three parts. In the first part we utilize the surface sensitivity of photoelectron spectroscopy to probe the distributions of solutes near the water surface. In agreement with recent theoretical predictions we find that large polarizable anions, such as I- and ClO4-, display enhanced surface propensities compared to smaller rigid ions. Surface effects arising from ion-ion interactions at higher electrolyte concentrations and as function of pH are investigated. Studies of linear mono-carboxylic acids and benzoic acid show that the neutral molecular forms of such weak acids are better stabilized at the water surface than their respective conjugate base forms. The second part examines what type of information core-electron spectra can yield about the chemical state and hydration structure of small organic molecules in water. We demonstrate that the method is sensitive to the protonation state of titratable functional groups and that core-level lineshapes are dependent on local water hydration configurations. Using a combination of photoelectron and X-ray absorption spectroscopy we also show that the electronic re-arrangement upon hydrolysis of aldehydes yields characteristic fingerprints in core-level spectra. In the last part of this thesis we study ultrafast charge delocalization dynamics in aqueous solutions using resonant and off-resonant Auger spectroscopy. Intermolecular Coulombic decay (ICD) is found to occur in a number of core-excited solutions where excess energy is transferred between the solvent and the solute. The rate of ultrafast electron delocalization between hydrogen bonded water molecules upon oxygen 1s resonant core-excitation is found to decrease upon solvation of inorganic ions. The presented work is illustrative of how core-level photoelectron spectroscopy can be valuable in the study of fundamental phenomena in aqueous solutions.
607

Aprofitament de residus vegetals per a la concentració i separació d'ions metàl·lics de solucions aquoses

Fiol Santaló, Núria 08 February 2005 (has links)
La adsorció sobre carbó actiu és un tractament habitual para a l'eliminació de metalls contaminants d'afluents aquosos. Amb la finalitat de reduir el cost dels tractament actuals s'està estudiant la utilització d'adsorbents de baix cost com a substituts dels sorbents convencionals que s'utilitzen usualment en els tractaments d'aigües. En aquesta tesi s'ha avaluat la possibilitat d'aprofitar diversos residus vegetals procedents de processos agrícoles o residus industrials, com a sorbents per a l'eliminació de metalls de solucions aquoses. En concret, el treball s'ha centrat en assolir dos grans objectius, primer de tot, conèixer la possibilitat d'utilitzar el pinyol d'oliva com a adsorbent de metalls divalents de solucions aquoses, com són el Cd(II), Cu(II), Ni(II) i Pb(II), i en segon lloc, avaluar la utilització de quatre residus vegetals (escorça de yohimbe, rapa de raïm, suro i pinyol d'oliva) per a l'extracció de Cr(VI) de solucions aquoses i utilitzar el residu vegetal més apropiat com a base per tal d'obtenir un nou sorbent, amb més bona morfologia per ser utilitzat en sistemes d'eliminació de Cr(VI) en continu. Les dades cinètiques d'adsorció es van tractar amb el model cinètic de pseudo-segon ordre, amb el que es van determinar la velocitat inicial d'adsorció dels metalls. Els models d'isotermes d'equilibri de Langmuir i Freundlich es van utilitzar per descriure els equilibris d'adsorció i calcular els paràmetres de les isotermes. En els assajos amb mescles binàries de metalls, els resultats es van tractar amb el model ampliat de Langmuir.En aquest treball s'ha determinat, primerament, que el pinyol d'oliva és un bon sorbent dels metalls divalents estudiats. S'ha determinat que l'adsorció dels metalls varia amb el pH de la solució i que la presència de sals en la solució provoca una davallada en l'adsorció. També es va determinar la competència en l'adsorció entre els metalls al realitzar assajos en mescles binàries.Amb els estudis d'extracció de Cr(VI) amb els quatre materials s'ha determinat que aquests vegetals poden adsorbir el Cr(VI) en solució, tot i que la rapa i la yohimbe són els materials que presenten unes capacitats d'adsorció més elevades. Les anàlisis amb espectroscòpia electrònica de Raig-X realitzats en la rapa de raïm i la yohimbe en contacte amb Cr(VI) varen demostrar la presència del metall en els dos estats d'oxidació, Cr(VI) i Cr(III), evidenciant la participació del mecanisme de reducció de Cr(VI) en l'adsorció del metall sobre els materials.Amb l'encapsulació de la rapa de raïm es va incrementar significativament la capacitat d'adsorció del metall respecta a la seva utilització en la forma original. Les dades experimentals es van tractar amb un model de difusió i es va determinar el coeficient de difusió en l'adsorció en el sorbent amb diferent percentatge de rapa en l'interior.Finalment s'han realitzat estudis preliminars d'adsorció de crom hexavalent en continu utilitzant columnes de petites dimensions farcides amb el sorbent format per boles de rapa encapsulada en alginat càlcic. En aquests assajos s'ha determinat l'efecte en l'adsorció de metall de diversos paràmetres d'operació, com la concentració inicial de metall, el cabal i l'alçada de llit. El model de transferència de matèria i difusió en columna emprat pel tractament de les dades experimentals va mostrar l'efecte de la concentració inicial i del cabal en els coeficients de difusió i transferència de matèria. El model BDST no va predir correctament el temps de servei en els diferents paràmetres d'operació experimentats a causa de la complexitat del procés d'adsorció. Amb aquests assajos preliminars s'han establert les bases de l'adsorció de Cr(VI) amb el nou sorbent en sistemes en continu amb la finalitat de realitzar estudis posteriors d'eliminació del metall en columnes de majors dimensions. / Adsorption with activated carbon is a usual treatment to remove metals from wastewater. In order to reduce the cost of the treatment, several studies have been carried out to evaluate the use of low cost sorbents as an alternative to conventional sorbents used in wastewater treatment. In this work, the use of different vegetable wastes from agricultural or industrial processes has been evaluated as sorbents for metal removal from aqueous solutions. The aim of this work was to study first, the usefulness of olive stones as a sorbent for divalent metals such as Cd(II), Cu(II), Ni(II) and Pb(II) from aqueous solutions and then the use of four vegetable wastes (yohimbe bark, grape stalks, cork and olive stones) for the removal of Cr(VI) from aqueous solutions. The vegetable waste powder was encapsulated in calcium alginate to obtain spherical gel beads that were used in continuous flow process for Cr(VI) removal.In all sorption experiments, kinetic data were modeled by the pseudo-second order kinetic equation and determine the constants sorption rates. Langmuir and Freundlich model isotherms were use to describe sorption equilibrium data and to obtain the isotherm parameters. In binary mixtures, the extended Langmuir isotherm model was used. The results showed that olive stones are a good sorbent for studied divalent metal. Metal uptake was pH dependent and the presence of salts in solution provokes a decrease in metal uptake. A clear competence between metals to be adsorbed on the waste was observed in metal binary mixtures. Although results obtained in Cr(VI) removal studies show that the four studied wastes can adsorb Cr(VI), grape stalks and yohimbe bark wastes showed the best chromium sorption capacity. X-Ray Photoelectron Spectroscopy analysis on grape stalks and yohimbe chromium loaded samples put into evidence that both Cr(VI) and Cr(III) were sorbed on wastes surface indicating that Cr(VI) sorption process involves a redox reaction. The gel beads obtained when encapsulating grape stalks in calcium alginate showed a significant increase in Cr(VI) sorption capacity compared to the original grape stalks waste. A diffusion model was used to analyze the experimental data and to determine the diffusion coefficient for Cr(VI) sorption by beads containing different percentage of grape stalks encapsulated in calcium alginate. Finally, preliminary studies of Cr(VI) removal in continuous flow using the beads containing grape stalks powder gel in laboratory columns have been carried out. The effect of operating parameters such as feed metal concentration, flow rate and bed depth was studied. The mass transfer and diffusion model used to describe column data showed the effect of feed metal concentration and flow rate in both, diffusion and mass transfer coefficients, respectively. The bed depth service time model (BDST) failed in predicting the service time when changing operating parameters due to the complexity of the sorption process. With these preliminary column experiments we established the basis for Cr(VI) sorption by the proposed sorbent in continuous flow process for further development of the process to be used in higher scale columns.
608

Spirocyclisation de céto-sulfonylynamides : vers la synthèse d'azacycles fonctionnalisés / Spirocyclization of ketosulfonylynamides : toward the synthesis of functionalized azacycles

Beltran, Frédéric 28 September 2018 (has links)
Les travaux décrits dans ce manuscrit de thèse ont porté d'une part sur le développement de nouvelles méthodes de spirocyclisation de céto-ynamides et d'autre part sur la réactivité de spiroénamides tertiaires. Les céto-sulfonamides en présence de bromoalcynes et de carbonate de césium conduisent à la formation de spiro-énamides par réaction de spirocyclisation via un intermédiaire céto-ynamide activé. Une grande variété de cycloalcanones et de bromoalcynes électroattracteurs sont tolérés.Les céto-ynamides conduisent à la formation de dérivés spiro-énamides par traitement avec du Triton B. La spirocyclisation tolère de nombreuses cycloalcanones et différents substituants aryles sur l'ynamide, et opère avec un bon stéréocontrôle de l'énamide. Une version en milieu micellaire aqueux de cette spirocyclisation a également été développée. Deux réactions dominos assistées par l'énamide tertiaire spirocyclique ont ensuite été développées. En présence de tétrachlorure de zirconium, la réaction domino permet d'obtenir des tétracycles de façon diastéréosélective tandis qu'avec le tétrachlorure de titane des pentacycles sont obtenus à partir du spiro-énamide avec un excellent régio- et diastéréocontrôle. / The work described in this manuscript involved the development of new spirocyclization methods starting from keto-ynamides, and the reactivity of tertiary spiro-enamides.Keto-sulfonamides led to spiro-enamides in the presence of cesium carbonate by spirocyclization reaction via an activated keto-ynamide intermediate. A wide range of cycloalkanones and electronwithdrawing bromoalkynes are tolerated. The spirocyclization reaction starting from keto-ynamides afforded spiro-enamide by treatment with Triton B. Various cycloalkanones, as well as a wide range of aryl substituents on the ynamide moiety, were suitable and provided good stereocontrol of the enamide formed. The spirocyclization reaction was also studied in aqueous micellar media. Two domino reactions assisted by the spirocyclic tertiary enamide were next developed. In the presence of zirconium tetrachloride, the domino reaction provided tetracyclic fused ring systems in a diastereoselective manner, whereas in the case of titanium tetrachloride, pentacyclic systems were obtained starting from the spiro-enamide with excellent regio- and diastereocontrol.
609

Ab Initio Molecular Dynamics Studies of Bronsted Acid-Base Chemistry in Aqueous Solutions

Tummanapelli, Anil Kumar January 2015 (has links) (PDF)
Knowledge of the dissociation constants of the ionizable protons of weak acids in aqueous media is of fundamental importance in many areas of chemistry and biochemistry. The pKa value, or equilibrium dissociation constant, of a molecule determines the relative concentration of its protonated and deprotonated forms at a specified pH and is therefore an important descriptor of its chemical reactivity. Considerable efforts have been devoted to the determination of pKa values by deferent experimental techniques. Although in most cases the determination of pKa values from experimental is straightforward, there are situations where interpretation is difficult and the results ambiguous. It is, therefore, not surprising that the capability to provide accurate estimates of the pKa value has been a central goal in theoretical chemistry and there has been a large effort in developing methodologies for predicting pKa values for a variety of chemical systems by differing quantum chemical techniques. A prediction accuracy within 0.5 pKa units of experiment is the desirable level of accuracy. This is a non-trivial exercise, for an error of 1 kcal/mol in estimates of the free energy value would result in an error of 0.74 pKa units. In this thesis ab initio Car-Parrinello molecular dynamics (CPMD) has been used for investigating the Brϕnsted acid-base chemistry of weak acids in aqueous solution. A key issue in any dissociation event is how the solvating water molecules arrange themselves spatially and dynamically around the neutral and dissociated acid molecule. Ab initio methods have the advantage that all solvent water molecules can, in principle, be con- sidered explicitly. One of the factors that has inhibited the widespread use of ab initio MD methods to study the dissociation reaction is that dissociation of weak acids are rare events that require extremely long simulation times before one is observed. The metady- namics formalism provides a solution to this conundrum by preventing the system from revisiting regions of configuration space where it has been in the past. The formalism allows the system to escape the free-energy minima by biasing the dynamics with a history dependent potential (or force) that acts on select degrees of freedom, referred to as collective variables. The bias potentials, modeled by repulsive inverted Gaussians that are dropped during propagation, drive the system out of any free-energy minima and allow it to explore the configuration space by a relatively quick and efficient sampling. The the- sis deals with a detailed investigation of the Brϕnsted acid-base chemistry of weak acids in aqueous solutions by the CPMD-metadynamics procedure. In Chapter 1, current approaches for the theoretical estimation of pKa values are summarized while in Chapter 2 the simulation methodology and the metadynamics sampling techniques used in thisstudy are described. The potential of the CPMD-metadynamics procedure to provide estimates of the acid dissociation constant (pKa) is explored in Chapter 3, using acetic acid as a test sys- tem. Using the bond-distance dependent coordination number of protons bound to the dissociating carboxylic groups as the collective variable, the free-energy profile for the dissociation reaction of acetic acid in water was computed. Convergence of the free-energy profiles and barriers for the simulations parameters is demonstrated. The free-energy profiles exhibit two distinct minima corresponding to the dissociated and neutral states of the acid and the deference in their values provides the estimate for pKa. The estimated value of pKa for acetic acid from the simulations, 4.80, is in good agreement with the experiment at value of 4.76. It is shown that the good agreement with experiment is a consequence of the cancellation of errors, as the pKa values are computed as the difference in the free energy values at the minima corresponding to the neutral and dissociated state. The chapter further explores the critical factors required for obtaining accurate estimates of the pKa values by the CPMD-metadynamics procedure. It is shown that having water molecules sufficient to complete three hydration shells as well as maintaining water density in the simulation cell as close to unity is important. In Chapter 4, the CPMD-metadynamics procedure described in Chapter-3 has been used to investigate the dissociation of a series of weak organic acids in aqueous solutions. The acids studied were chosen to highlight some of the major factors that influence the dissociation constant. These include the influence of the inductive effect, the stabilization of the dissociated anion by H-bonding as well as the presence of multiple ionizable groups. The acids investigated were aliphatic carboxylic acids, chlorine-substituted carboxylic acids, cid and trans-butenedioic, the isomers of hydroxybenzoic acid and phthalic acids and its isomers. It was found that in each of these examples the CPMD-metadynamics procedure correctly estimates the pKa values, indicating that the formulism is capable of capturing these influences and equally importantly indicating that the cancellation of errors is indeed universal. Further, it is shown that the procedure can provide accurate estimates of the successive pKa values of polypro tic acids as well as the subtle deference in their values for deterrent isomers of the acid molecule. Changes in protonation-deprotonation of amino acid residues in proteins play a key role in many biological processes and pathways. It is shown that CPMD simulations in conjunction with metadynamics calculations of the free energy profile of the protonation- deprotonation reaction can provide estimates of the multiple pKa values of the 20 canonical α-amino acids in aqueous solutions in good agreement with experiment (Chapter 5). The distance-dependent coordination number of the protons bound to the hydroxyl oxygen of the carboxylic and the amine groups is used as the collective variable to explore the free energy profiles of the Brϕnsted acid-base chemistry of amino acids in aqueous solutions. Water molecules, sufficient to complete three hydration shells surrounding the acid molecule were included explicitly in the computation procedure. The method works equally well for amino acids with neutral, acidic and basic side chains and provides estimates of the multiple pKa values with a mean relative error with respect to experimental results, of 0.2 pKa units. The tripeptide Glutathione (GSH) is one of the most abundant peptides and the major repository for non-protein sulfur in both animal and plant cells. It plays a critical role in intracellular oxidative stress management by the reversible formation of glutathione disulfide with the thioldisulfide pair acting as a redox buffer. The state of charge of the ionizable groups of GSH can influences the redox couple and hence the pKa value of the cysteine residue of GSH is critical to its functioning. In Chapter 6, it has been reported that ab initio Car-Parrinello Molecular Dynamics simulations of glutathione solvated by 200 water molecules, all of which are considered in the simulation. It is shown that the free-energy landscape for the protonation - deprotonation reaction of the cysteine residue of GSH computed using metadynamics sampling provides accurate estimates of the pKa and correctly predicts the shift in the dissociation constant values as compared to the isolated cysteine amino acid. The dissociation constants of weak acids are commonly determined from pH-titration curves. For simple acids the determination of the pKa from the titration curves using the Henderson-Hasselbalch equation is relatively straightforward. There are situations, however, especially in polypro tic acids with closely spaced dissociation constants, where titration curves do not exhibit clear inflexion and equivalence stages and consequently the estimation of multiple pKa values from a single titration curve is no longer straightfor- ward resulting in uncertainties in the determined pKa values. In Chapter 7, the multiple dissociation constant of the hexapeptide glutathione disulfide (GSSG) with six ionizable groups and six associated dissociation constants has been investigated. The six pKa values of GSSG were estimated using the CPMD-metadynamics procedure from the free-energy profiles for each dissociation reaction computed using the appropriate collective variable. The six pKa values of GSSG were estimated and the theoretical pH-titration curve was then compared with the experimentally measured pH-titration curve and found to be in excellent agreement. The object of the exercise was to establish whether interpretation of pH-titration curves of complex molecules with multiple ionizable groups could be facilitated using results of ab initio molecular dynamics simulations.
610

Estudo do efeito da adição de poli(glicol etilênico-b-glicol propilênico) na formação de dispersões aquosas poliuretânicas à base de poli(glicol propilênico) / Estudo do efeito da adição de poli(glicol etilênico-b-glicol propilênico) na formação de dispersões aquosas poliuretânicas à base de poli(glicol propilênico) / Study of the effects of the addition of poly(ethylene glycol-b-propylene glycol)in the formation of polyurethanics aqueous dispersions with a poly(propylene glycol) basis / Study of the effects of the addition of poly(ethylene glycol-b-propylene glycol)in the formation of polyurethanics aqueous dispersions with a poly(propylene glycol) basis

Rosiléa Braga Luciano de Almeida 06 March 2007 (has links)
Foram produzidas dispersões aquosas não-poluentes e inovadoras de poli(uretano-uréia) à base de poli(glicol propilênico) (PPG) e de copolímeros em bloco, poli(glicol etilênicob-glicol propilênico), (EG-b-PG) com teor de 7% de unidades de glicol etilênico. Os poli(uretano-uréia)s foram preparados, em duas etapas, pelo método do prepolímero. Na primeira etapa, foram obtidos anionômeros, sintetizados em massa, à base do copolímero EG-bPG, PPG, ácido dimetilol propiônico (DMPA) (gerador dos sítios aniônicos) e diisocianato de isoforona (IPDI). Ainda na primeira etapa, os grupos carboxílicos do DMPA foram submetidos à neutralização com trietilamina (TEA). Na segunda etapa, foi realizada a dispersão do prepolímero anionômero e, em seguida, foi conduzida a reação de extensão de cadeia com a hidrazina (HYD). Nas diferentes formulações, foram variadas a razão NCO/OH e as proporções de PPG e do copolímero em bloco EG-b-PG. Além disso, foram obtidas dispersões aquosas programadas para teores de sólidos de 40 e 50%. As dispersões foram avaliadas quanto ao teor de sólidos totais, tamanho médio de partícula e viscosidade. Os filmes, obtidos por vazamento das dispersões, foram avaliados quanto à absorção de água, termogravimetria (TG) e propriedades mecânicas (ensaio de tração). Os filmes vazados e os monômeros foram caracterizados por espectrometria na região de infravermelho (FTIR) As dispersões obtidas se mostraram adequadas para serem aplicadas como revestimento para madeira, metais e vidro / Non-polluting and poly(urethane-urea) aqueous dispersions based on poly(propylene glycol) (PPG) and block copolymers of poly(ethylene glycol-b-propylene glycol) (EG-b-PG) containing 7% of ethylene glycol repeating units, were produced in an innovative way. The poly(urethane-urea)s were prepared, in two steps, by the prepolymer method. In the first step, anionomers, synthesized in bulk, based on EG-b-PG, PPG, dimethylolpropionic acid (DMPA) (anionomer sites generator) and isophorone diisocyanate (IPDI) were obtained. Still in the first step, the DMPA carboxylic groups were neutralized with triethylamine (TEA), generating the anionomer groups. In the second step, the anionomer prepolymer was dispersed in water under vigorous stirring and afterwards was chain extended with hydrazine. Different formulations were obtained by varying the NCO/OH ratio, and the proportions of PPG and EG-b-PG. Besides, poly(urethane-urea) aqueous dispersions with 40% and 50% of solid contents were obtained. The dispersions were evaluated in terms of their solid-contents, particle size and viscosity. The cast films, obtained from the dispersions concernig of water absorption, thermogravimetry (TG) and mechanical properties (stress and elongation at break). The films and monomers were characterized by infrared spectrometry (FTIR). The obtained dispersions were suitable when applied as for wood, metals and glass surfaces

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