Comparative study of guest charge-charge interactions within silica sol-gel.
ABSTRACT We investigated the effect of charge-charge interactions on the mobilities of rhodamine 6G (R6G), Nile Red, sulforhodamine B, and Oregon Green 514 (ORG) guest molecules within a silica sol-gel host as the guest charge progressed from positive to neutral to negative. Through classification of the mobility as fixed, tumbling, or intermediate behavior, we were able to distinguish differences in surface attraction as the guest charge was varied. On the basis of our results, an attractive charge (as tested by cationic R6G) does not contribute significantly to mobility within dry films. However, an increase in the cationic influence is observed in water-equilibrated environments. A comparison of ORG in dry and water- and phosphate-buffer-equilibrated films indicates that charge repulsion does significantly increase dye rotational mobility (to a maximum of 24 +/- 3% tumbling molecules). However, in view of the percentage of tumbling molecules found, charge-charge interactions do not appear to be the dominant force controlling guest mobility.
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ABSTRACT: This study reports on the development and characterization of bacterial cellulose (BCNW) films coated with hydrophobic layers, presenting enhanced barrier properties. Pure BCNW films showed good transparency and thermal stability, high rigidity and extremely low oxygen permeability at 0%RH. The dramatic increase in oxygen permeability at 80%RH, due to the hydrophilic character of BCNW, was counteracted through coating the films with annealed PLA electrospun nanostructured fibres or hydrophobic silanes. The use of electrospinning was crucial to attain a good adhesion between the hydrophilic BCNW and the hydrophobic PLA layer. After electrospinning, the fibres were homogenised by annealing, thus obtaining a uniform and continuous coating. Coated systems showed a hydrophobic surface and protected the BCNW from moisture, thus reducing ca. 70% the water permeability and up to 97% the oxygen permeability at 80%RH. Furthermore, this novel approach was seen to protect BCNW films from moisture more efficiently than coating with hydrophobic silanes.Carbohydrate polymers. 10/2013; 98(1):1072-82.
- 02/2007: pages 277-309;
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ABSTRACT: The [Ru(bpy)3]2+ ion was encapsulated in a silica based sol–gel thin film, and the luminescence decay time constant of the photo-excited 3MLCT (metal-ligand-charge-transfer) was examined when this thin film was immersed in water, methanol, ethanol, 2-propanol, and glycerol. The luminescence decays of the films in the methanol, 2-propanol, and glycerol were better explained by a KWW model, while the luminescence decay of film immersed in water and ethanol were both well explained by a single exponential decay. Intriguingly, the dynamics of the dopants immersed in water, ethanol as well as in sol–gel bulk deviated from a single exponential fit and began to better explained by the the KWW model as temperature increased. The energy gap, ΔE(sol–gel film) and ΔE(solution), between the lowest 3MLCT state and atom localized 3 dd state for dopants under the presence of all solvents tested in this study were extracted from the temperature dependence study of the luminescence decay time constant. Generally, the ΔE(sol–gel film) values of ethanol and water were reduced from ΔE(solution), and ΔE(sol–gel film) value in all solvents matched the value of ΔE for sol–gel bulk. The effect on the dynamics in solvent over three weeks was investigated, and the films immersed in water presented the most remarkable monotonic increase in relaxation rates finally approaching the asymptotic value observed in the water solution. This phenomenon was considered to correspond to a trapping environment change due to a hydrophilic interaction through sequential intrusion of water or ethanol solvent into sol–gel pores.Journal of Sol-Gel Science and Technology 07/2007; 43(2):259-268. · 1.66 Impact Factor