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Cetyltrimethylammonium Halide-Coated Electrodes for the Detection of Dopamine in the Presence of InterferentsYeary, Amber J. 13 December 2011 (has links)
No description available.
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NMR studies of complex fluids and solids formed by surfactantsHedin, Niklas January 2000 (has links)
NMR methods have been designed and employed in studying ofcomplex liquids and solids formed by surfactants. PGSE NMRexperiments are easily biased by convection; this artifact canbe avoided by changing the sample holder and by usingconvection-compensated pulse sequences. The temperaturedistribution within samples was controlled using thetemperature dependent order parameter for CBr2H2dissolved in a thermotropic nematic solvent.Electronic ringing that often spoils accurate NMR experimentsfor broad lines was removed by the using composite pulses andquadrupole echo sequences with appropriate phase cycles. Field-dependent81Br and35Cl NMR relaxation studies in micellar solutions ofC16TAX surfactants showed that the structure ordynamics of the hydration shell is more influenced by thesurfactant cation for bromide than for chloride, in agreementwith their position in the Hoffmeister series. The presence ofa small but significant frequency-dependent relaxation showedthat the lateral self diffusion of the anions may be reduced ascompared to its bulk value in diluted solutions but only with afactor of 1.0 - 2.5. The ions are clearly not "bound" to thesurface. A field-dependent2H NMR relaxation study on the CTABr-α-d2and benzene-d6showed an initial one-dimensional micellargrowth followed by the appearance of microemulsion droplets onaddition of benzene. The local mobility of the benzene wasreduced when solubilized in small amounts, consistent with aninitial average location of benzene at the micellar interface.The surfactant diffusion coefficients fromconvection-compensated PGSE NMR experiments in the C12E8-D2O system showed monotonous growth of the micellesupon increasing temperature. Emulsion droplets in the C12E5-decane-D2O system where shown to coarsen according to theOstwald ripening theory after being brought out of equilibriumby a temperature drop. X-ray scattering and2H NMR line-shape and relaxation experimentssuggested that complex solids formed by a partly-sulfatedpolysaccharide and CnTAB exhibit regular ordering at both microscopicand mesoscopic length scales. <b>Keywords</b>: CTAB, CTAC, C12E8, C12E5, decane, benzene, CBr2H2, polysaccharide, micelle, microemulsion, emulsion,Ostwald ripening, NMR,81Br,35Cl,2H, field- dependent spin relaxation, PGSE, selfdiffusion, convection, ringing, thermometer, generalized Blochequations, EXORCYCLE, quadrupole echo, SAXS, WAXS, cryo-TEM.
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NMR studies of complex fluids and solids formed by surfactantsHedin, Niklas January 2000 (has links)
<p>NMR methods have been designed and employed in studying ofcomplex liquids and solids formed by surfactants. PGSE NMRexperiments are easily biased by convection; this artifact canbe avoided by changing the sample holder and by usingconvection-compensated pulse sequences. The temperaturedistribution within samples was controlled using thetemperature dependent order parameter for CBr<sub>2</sub>H<sub>2</sub>dissolved in a thermotropic nematic solvent.Electronic ringing that often spoils accurate NMR experimentsfor broad lines was removed by the using composite pulses andquadrupole echo sequences with appropriate phase cycles.</p><p>Field-dependent<sup>81</sup>Br and<sup>35</sup>Cl NMR relaxation studies in micellar solutions ofC<sub>16</sub>TAX surfactants showed that the structure ordynamics of the hydration shell is more influenced by thesurfactant cation for bromide than for chloride, in agreementwith their position in the Hoffmeister series. The presence ofa small but significant frequency-dependent relaxation showedthat the lateral self diffusion of the anions may be reduced ascompared to its bulk value in diluted solutions but only with afactor of 1.0 - 2.5. The ions are clearly not "bound" to thesurface. A field-dependent<sup>2</sup>H NMR relaxation study on the CTABr-α-<i>d</i><i>2</i>and benzene-<i>d</i><i>6</i>showed an initial one-dimensional micellargrowth followed by the appearance of microemulsion droplets onaddition of benzene. The local mobility of the benzene wasreduced when solubilized in small amounts, consistent with aninitial average location of benzene at the micellar interface.The surfactant diffusion coefficients fromconvection-compensated PGSE NMR experiments in the C<sub>12</sub>E<sub>8</sub>-D<sub>2</sub>O system showed monotonous growth of the micellesupon increasing temperature. Emulsion droplets in the C<sub>12</sub>E<sub>5</sub>-decane-D<sub>2</sub>O system where shown to coarsen according to theOstwald ripening theory after being brought out of equilibriumby a temperature drop. X-ray scattering and<sup>2</sup>H NMR line-shape and relaxation experimentssuggested that complex solids formed by a partly-sulfatedpolysaccharide and C<sub>n</sub>TAB exhibit regular ordering at both microscopicand mesoscopic length scales.</p><p><b>Keywords</b>: CTAB, CTAC, C<sub>12</sub>E<sub>8</sub>, C<sub>12</sub>E<sub>5</sub>, decane, benzene, CBr<sub>2</sub>H<sub>2</sub>, polysaccharide, micelle, microemulsion, emulsion,Ostwald ripening, NMR,<sup>81</sup>Br,<sup>35</sup>Cl,<sup>2</sup>H, field- dependent spin relaxation, PGSE, selfdiffusion, convection, ringing, thermometer, generalized Blochequations, EXORCYCLE, quadrupole echo, SAXS, WAXS, cryo-TEM.</p>
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Phase Phenomena in Polymer Networks : Empirical Studies on the Influence of Hydrophobicity, Charge Density and Crosslinks on Macroion-Induced Phase Transitions in Polyelectrolyte GelsAndersson, Martin January 2011 (has links)
The thesis concerns polyelectrolyte gels in contact with oppositely charged proteins and surfactant micelles, and includes of four papers (I-IV). In paper I confocal Raman spectroscopy was introduced as a method to trace micelles and investigate the structure of gel-surfactant complexes, in phase separated gel spheres. In paper II, the binding of surfactants to microspheres (~50-100 µm) was investigated by means of a micromanipulator-assisted microscopy method. The two surfactants were found to display qualitative difference respect to degree of swelling, surfactant distribution in the gels, and the difference is discussed in terms of absence/presence of hydrophobic attraction to the polyelectrolyte gel network. Kinetics of volume change in gels were analyzed. Aggregation numbers of micelles in polystyrenesulfonate (PSS) solutions, obtained from fluorescence quenching measurements, are presented. In paper III, phase behaviour, protein assembly and diffusion, was studied in PSS gel microspheres. Interpretation of results was aided by measurements of osmotic swelling of individual gel networks, and by combining the results with studies of protein diffusion in macroscopic (cm-sized) gel spheres. Complexes formed were further analyzed with small angle x-ray spectroscopy. In paper IV phase behaviour of mixed ionic/nonionic surfactant micelles is investigated in cm-sized gel spheres. The coexistence of three phases, the formation of dense shells in the bulk of the gels and other phenomena are described for the first time, and the results are presented along with discussion on the charge-density of spherical micelles and of network induced hysteresis effects in gels. The composition and microstructure of phases are investigated by confocal Raman spectroscopy and small-angle x-ray scattering respectively. The results are interpreted with aid of highly detailed theoretical model calculations.
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