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81.
Alberto Gallardo Stephen Spells Rodrigo Navarro Helmut Reinecke 《Macromolecular rapid communications》2006,27(7):529-536
Summary: A mathematical approach developed to correct depth profiles of wet‐chemically modified polymer films obtained by confocal Raman microscopy is presented which takes into account scattered contributions originated from a diffraction‐limited laser focal volume and the refractive index of the sample. The method is demonstrated in both virtual and real samples where it is shown that considerable differences between apparent and corrected depth profiles exist at the surface, especially when profiles with strong concentration gradients are dealt with or an instrument with poor depth resolution is used.
82.
Alberto Gallardo Stephen Spells Rodrigo Navarro Helmut Reinecke 《Journal of Raman spectroscopy : JRS》2007,38(7):880-884
A new approach to obtain corrected depth profiles by confocal Raman microscopy, which considers diffraction and refraction effects is presented. The problem of diffraction effects encountered intrinsically in the confocal configuration can be described using a linear Fredholm integral equation of the first kind, which correlates apparent and true Raman intensities with the depth resolution curve of the instrument. Refractive index differences between air and the polymer sample, which cause further errors in the obtained depth profile due to strong aberration effects have been considered. This has been carried out using an empirical variation of the depth resolution function, which is able to simulate the broadening of the depth of focus with depth and also the discrepancy between nominal and measured depth scales. It is shown that considerable differences between apparent and corrected depth profiles exist at the surface and that these depend on the gradient of the profile and the depth resolution of the Raman microscope. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
83.
84.
85.
Hugo Gallardo Fernando R. Bryk André A. Vieira Tiago E. Frizon Gilmar Conte Bruno S. Souza 《Liquid crystals》2013,40(8):839-845
The thermal and optical properties of two series of unsymmetrical liquid crystalline compounds based on an isoxazole ring are described. Of these materials, 3–7 and 8–12 displayed strong absorption at 285 nm and a weak blue fluorescence in solution at around 377 nm, even with the presence of a high conjugated core. The fluorescence quantum yields observed varied from low to moderate (Φ F ?=?1–62%), with large Stokes shifts (60–178 nm). All compounds exhibited liquid crystalline behaviour with a wide mesomorphism temperature range and characteristic phases of calamitic compounds, among them smectic A (SmA), smectic C (SmC) and nematic (N) phases. Their phases were characterised using polarising optical microscopy and differential scanning calorimetry. In addition, with X-ray diffraction experiments, layer spacing of 33.3–40.0 Å were observed for the smectic phases. 相似文献
86.
Charge in ionic micelles determines the trends of their stability and their practical applications. Charge can be calculated from zeta potential (zeta) measurements, which, in turn, can be obtained by Doppler microelectrophoresis. In this study, the electrophoretic properties of dodecyltrimethylammonium bromide (DTAB) in KBr aqueous solution (0-6 mM) were determined by Doppler microelectrophoresis. At very low surfactant concentrations (up to 6 mM), zeta potential was quite constant and due to the ionized monomers (DTA+). Above 6 mM, zeta potential increased to a maximum at surfactant concentrations still below the critical micellar concentration (CMC). This increase could be explained by a formation of nonmicellar aggregates of DTAB. Then, above the CMC, zeta potential underwent an abrupt reduction, which was dependent qualitatively and quantitatively on KBr concentration, and which could be due to an increase of the number of counterions adsorbed on the micelle surface. Calculation of effective micellar charge from zeta potential gave the surface charge density. Comparing this value with the theoretical, obtained from geometrical considerations, a fraction of 0.29 of charged micellar headgroups was obtained when DTAB was in aqueous solution, which is consistent with the value obtained by conductivity measurements. 相似文献
87.
Ricardo O. Silva Ricardo A. W. Neves Filho Rodrigo Azevedo Rajendra M. Srivastava Hugo Gallardo 《Structural chemistry》2010,21(3):485-494
In this article, we describe the complete 1H and 13C NMR signal assignments of four 1,2,4-oxadiazoles possessing light-emitting liquid crystal properties. These results were
obtained by using one- and two-dimensional NMR techniques as well as GIAO (PCM) calculations at B3LYP/6-311++G(d,p) level
for compounds 1 and 2a–d. The computed values are in good agreement with the ones obtained experimentally. In addition, some previously unexplained
thermotropic features of compounds 2a–d could be clarified with the help of the geometry optimization calculations carried out by us. 相似文献
88.
89.
Flasiński M Broniatowski M Romeu NV Dynarowicz-Łatka P Moreno AG Vilas AM Martín ML 《The journal of physical chemistry. B》2008,112(15):4620-4628
Commercially available amphiphilic cyclodextrins, namely per-6-O-(tert-butyldimethylsilyl) alpha, beta and gamma cyclodextrins (TBDMS-alpha-, -beta-, and -gamma-CDs) were subjected to a thorough Langmuir monolayer characterization, using both traditional methods of surface manometry (pi/A isotherms, stability experiments) and modern micrometer/nanometer resolution (BAM, AFM) surface techniques. It has been found that inconsistent behavior regarding the isotherms reproducibility obtained upon compression of TBDMS-beta-CDs is due to the aggregation of the investigated molecules in chloroform and hexane, while good reproducibility ensured a mixed spreading solvent system of hexane/isopropanol 7:3 (v/v). Although the stability of films dropped from chloroform and hexane/isopropanol solvents below the equilibrium surface pressure (ESP) was comparable, pronounced differences were observed at pressures above ESP. The investigated TBDMS-CDs were successfully transferred onto cadmium stearate covered mica substrates. AFM images confirmed the presence of discontinuous multilayered films (10 nm heights) spread from chloroform versus monomolecular dispersion achieved in hexane/isopropanol. 相似文献
90.
Using classical density functional theory (DFT) we analyze the structure of the density profiles and solvation pressures of negatively charged colloids confined in slit pores. The considered model, which was already successfully employed to study a real colloidal (silica) suspension [S. H. L. Klapp et al., Phys. Rev. Lett. 100, 118303 (2008)], involves only the macroions which interact via the effective Derjaguin-Landau-Verwey-Overbeek (DLVO) potential supplemented by a hard core interaction. The solvent enters implicitly via the screening length of the DLVO interaction. The free energy functional describing the colloidal suspension consists of a hard sphere contribution obtained from fundamental measure theory and a long range contribution which is treated using two types of approximations. One of them is the mean field approximation (MFA) and the remaining is based on Rosenfeld's perturbative method for constructing the Helmholtz energy functional. These theoretical calculations are carried out at different bulk densities and wall separations to compare finally to grand canonical Monte Carlo simulations. We also consider the impact of charged walls. Our results show that the perturbative DFT method yields generally qualitatively consistent and, for some systems, also quantitatively reliable results. In MFA, on the other hand, the neglect of charge-induced correlations leads to a breakdown of this approach in a broad range of densities. 相似文献