RESUMO
In this investigation, the transient electroosmotic flow of multi-layer immiscible viscoelastic fluids in a slit microchannel is studied. Through an appropriate combination of the momentum equation with the rheological model for Maxwell fluids, an hyperbolic partial differential equation is obtained and semi-analytically solved by using the Laplace transform method to describe the velocity field. In the solution process, different electrostatic conditions and electro-viscous stresses have to be considered in the liquid-liquid interfaces due to the transported fluids content buffer solutions based on symmetrical electrolytes. By adopting a dimensionless mathematical model for the governing and constitutive equations, certain dimensionless parameters that control the start-up of electroosmotic flow appear, as the viscosity ratios, dielectric permittivity ratios, the density ratios, the relaxation times, the electrokinetic parameters and the potential differences. In the results, it is shown that the velocity exhibits an oscillatory behavior in the transient regime as a consequence of the competition between the viscous and elastic forces; also, the flow field is affected by the electrostatic conditions at the liquid-liquid interfaces, producing steep velocity gradients, and finally, the time to reach the steady-state is strongly dependent on the relaxation times, viscosity ratios and the number of fluid layers.
RESUMO
The adsorption of the 5-Fluorouracil (5-FU) molecule on the pristine and Al-doped activated carbon (AC) was investigated by using the Vienna Ab-initio Simulation Package. It is found that the 5-FU molecule is only weakly adsorbed on the pristine AC with high adsorption energy and large surface distance. The adsorption of the 5-FU molecule on pristine AC is highly disfavored. In contrast, the molecule shows strong interactions with the Al-doped AC confirmed by the lesser adsorption energy, the charge transfers on the Al-modified zone and the significant changes in the DOS at the Fermi level. The results of our study suggest that the Al dopant increases the adsorption capacity of AC enhancing its interactions with polar atoms of the adsorbate, hence improving its adsorption properties.
Assuntos
Alumínio/química , Antineoplásicos/química , Carvão Vegetal/química , Fluoruracila/química , Teoria Quântica , Adsorção , Modelos Moleculares , Conformação MolecularRESUMO
UV-vis spectroscopy is a powerful tool to investigate surface phenomena. Surface tension measurements coupled to spectroscopic techniques can help to elucidate how the interface organization influences the electronic properties of molecules. However, appreciable sample volumes are usually necessary to achieve strong signals during conduction of experiments. This study reports on the simultaneous acquisition of surface tension data and UV-vis spectra by axisymmetric drop shape analysis (ADSA) coupled to diffuse reflectance (DRUV) spectrophotometry using a pendant microliter-drop that requires small sample volumes and low analyte concentrations. Three example systems gave evidence of the applicability of this technique: (a) disaggregation of an organic dye driven by surfactant as a function of the surface tension and alterations in the UV-vis spectra, (b) activity of a glycosylphosphatidylinositol anchored enzyme estimated from formation of a colored product, and (c) interaction between this enzyme and biomimetic membrane systems consisting of dipalmitoylphosphaditylcholine and cholestenone. Apart from using smaller sample volume, this coupled technique allowed to investigate interfacial organization in the light of electronic spectra obtained in loco within a shorter acquisition time. This procedure provided precise interfacial information about static and dynamic systems. This has been the first study describing the kinetic activity of an enzyme in the presence of phospholipid monolayers through simultaneous determination of the surface tension and UV-vis spectra.
RESUMO
We carry out a time-averaged contact matrix study to reveal the existence of protein backbone hydrogen bonds (BHBs) whose net persistence in time differs markedly form their corresponding PDB-reported state. We term such interactions as "chameleonic" BHBs, CBHBs, precisely to account for their tendency to change the structural prescription of the PDB for the opposite bonding propensity in solution. We also find a significant enrichment of protein binding sites in CBHBs, relate them to local water exposure and analyze their behavior as ligand/drug targets. Thus, the dynamic analysis of hydrogen bond propensity might lay the foundations for new tools of interest in protein binding-site prediction and in lead optimization for drug design.