RESUMO
Molecular dynamics simulations of liquid quinoline have been performed at experimental densities corresponding to the temperature range 276-320 K. The intermolecular potential is a simple effective two-body potential between rigid molecules having 17 atomic Lennard-Jones and electrostatic Coulomb interaction sites. The vaporization enthalpy is overestimated by 8-9% with respect to the experimental value. The translational diffusion coefficient exhibits a small non-Arrhenius behavior with a change in temperatures near 290 and 303 K. The rotational diffusion tensor is rotated around the z axis perpendicular to the molecular plane by an angle of 4-6° with respect to the frame of reference defined by the principal axes of inertia. The rotational diffusion tensor presents a significant anisotropy with D(rot,y)/D(rot,x) ≃ 0.6-0.5 and D(rot,z)/D(rot,x) ≃ 1.6-1.3 between 276 and 320 K when the x axis is defined as the long molecular axis and the y axis is situated nearly along the central C-C bond. The rotational diffusion coefficients, the reorientational correlation times of the C-H vectors, and the T1(13)C NMR relaxation times present a non-Arrhenius break around 288-290 K in agreement with several experimental results. In addition, a non-Arrhenius break can also be observed at 303 K for these properties. It has been found that the structure evolves smoothly in the studied temperature range. Center of mass-center of mass and atom-atom radial distribution functions show a monotonous evolution with temperature. Various types of first-neighbor dimers have been defined, and their population analysis has revealed a continuous monotonous evolution with temperature. Thus, the non-Arrhenius behavior observed for translational and rotational diffusion is correlated with the monotonous evolution of the population of first-neighbor dimers at a microscopic level and not with a sharp structural transition.
RESUMO
Plasticised poly(vinyl chloride)-based membranes containing the ionophores (α-, ß- and γ-cyclodextrins (CD), dibenzo-18-crown-6 (DB18C6) and dibenzo-30-crown-10 (DB30C10) were evaluated for their potentiometric response towards promethazine (PM) in a flow injection analysis (FIA) set-up. Good responses were obtained when ß- and γ-CDs, and DB30C10 were used. The performance characteristics were further improved when tetrakis(4-chlorophenyl) borate (KTPB) was added to the membrane. The sensor based on ß-CD, bis(2-ethylhexyl) adipate (BEHA) and KTPB exhibited the best performance among the eighteen sensor compositions that were tested. The response was linear from 1 × 10(-5) to 1 × 10(-2) M, slope was 61.3 mV decade(-1), the pH independent region ranged from 4.5 to 7.0, a limit of detection of 5.3 × 10(-6) M was possible and a lifetime of more than a month was observed when used in the FIA system. Other plasticisers such as dioctyl phenylphosphonate and tributyl phosphate do not show significant improvements in the quality of the sensors. The promising sensors were further tested for the effects of foreign ions (Li(+), Na(+), K(+), Mg(2+), Ca(2+), Co(2+), Cu(2+), Cr(3+), Fe(3+), glucose, fructose). FIA conditions (e.g., effects of flow rate, injection volume, pH of the carrier stream) were also studied when the best sensor was used (based on ß-CD). The sensor was applied to the determination of PM in four pharmaceutical preparations and human urine that were spiked with different levels of PM. Good agreement between the sensor and the manufacturer's claimed values (for pharmaceutical preparations) was obtained, while mean recoveries of 98.6% were obtained for spiked urine samples. The molecular recognition features of the sensors as revealed by molecular modelling were rationalised by the nature of the interactions and complexation energies between the host and guest molecules.
