The interaction between rhodamine 6G and different polyelectrolytes is analyzed. Structural aspects differentiate these polyelectrolytes, such as the presence of aromatic groups and the number and localization of their respective charges, which may be directly attached to the aromatic groups or to the polymeric main chain. In the case of poly(sodium acrylate), which does not bear aromatic groups, the polyelectrolyte induces cooperative self-stacking between the dyes which is highly sensitive to the ionic strength, due to the predominance of long-range electrostatic interactions between the polymer and the dye. In the case of poly(sodium 4-styrenesulfonate), whose charge is directly attached to the aromatic groups, a high dispersant ability of the dyes is found and the interaction is less dependent on the ionic strength, due to the predominance of short-range aromatic-aromatic interactions between the dye and the polymer. Among the two polyelectrolytes studied for which the polymeric charge is directly attached to the main chain, and separated from the aromatic group, poly(styrene-alt-maleic acid) shows a lower dependence of the interaction on the ionic strength than poly(N-phenylmaleimide-co-acrylic acid) at a comonomer composition of 1:2, due to a higher linear aromatic density and a lower linear charge density, indicating the importance of hydrophobic forces. Both copolymers exhibit a high ability to induce cooperative self-aggregation of the dye.
This work is focused on the removal of Cr(VI) ions from aqueous solution using polymer-enhanced ultrafiltration (PEUF) techniques with water-soluble poly(N,Ndimethylaminoethyl methacrylate), PDMAEMA, used as sorbent. The polymer was prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization at different reaction times, characterized by size exclusion chromatography (SEC) and proton nuclear magnetic resonance (1 H-NMR). The sorption of Cr(VI) was studied by PEUF as a function of pH, the polymer:Cr(VI) molar ratio, and the presence of interfering ions. The PEUF-enrichment mode was used to saturate the polymer and further determine the release of Cr(VI) and regeneration of the polymer using sorption-desorption process. The RAFT polymerization showed a yield in the range 46% to 79% (determined by 1 H-NMR) for polymers with molecular weight (M n) between 28 to 195 kg mol-1. The polydispersity estimated by SEC was between 1.1 and 1.8. The capacity of PDMAEMA as sorbent of Cr(VI), by the PEUF technique showed an efficient removal of Cr(VI) (100%, 25 mg L-1 in the feed) at pH 4 using polymer:Cr molar ratio of 40:1. The presence of interfering ions does not significantly decrease the retention capacity of PDMAEMA. Finally the results indicated that PDMAEMA can release Cr(VI) and be regenerated.
Poly(ethylene glycol) diacrylate (PEGDA) of different molecular weights (Mn = 575 and 700) was used as crosslinking agent for the photopolymerization of 2-hydroxyethyl methacrylate (HEMA) in order to obtain HEMA/PEGDA-based hydrogels. Composites were synthesized in situ employing a new methodology that implies the addition of different quantities of silver nitrate aqueous solution to the monomer mixture with the finality to obtain hydrogels with different silver nanoparticles' spatial density and distribution. Samples were characterized by thermal, optical, spectroscopic and structural/morphological methods. Thermal studies showed that the increase of PEGDA molecular weight and the AgNO 3 concentration in the reaction mixture enhance the glass transition temperature and the thermal stability of the composites. This behavior could be related to the silver coordination with the polymer network. Infrared spectroscopy with Fourier transform and Raman analyses were realized in order to corroborate the sample chemical structure by the identification of specific functional groups. Surface hydrogel morphology was visualized with scanning electron microscopy analysis, detecting a homogeneous micro-porous surface for the samples obtained from high molecular weight PEGDA. Presence of silver nanoparticles was established by X-ray fluorescence spectroscopy and UV/Vis methods. In this last case, the characteristic silver nanoparticle plasmon was observed. Using Transmission Electron Microscopy it was possible to visualize a homogeneous spatial distribution of spherical silver nanoparticles with very narrow
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