Influence of cationic cellulose structure on its interactions with sodium dodecylsulfate: implications on the properties of the aqueous dispersions and hydrogels.
The interactions of sodium dodecylsulfate (SDS) with the aqueous dispersions and the chemically cross-linked hydrogels of two cationic hydroxyethylcelluloses, polyquaternium-4 (PQ-4) and polyquaternium-10 (PQ-10), commonly used in cosmetics and in topical drug delivery devices, were analyzed. This surfactant was chosen not only for its interest as excipient, but also as a model of the amphiphilic behavior shown by many drugs. In aqueous dispersions, the interaction process was studied through transmittance, surface tension, fluorescence, microcalorimetry titration, viscosity and oscillatory rheometry measurements. The ammonium/sulfate groups ratios at the critical aggregation concentration (0.05% SDS) were 2.61 for PQ-4 and 4.02 for PQ-10; while at the saturation concentration (0.25% SDS), these ratios decreased to 0.52 and 0.80, respectively. The binding process, through ionic and hydrophobic interactions, was strongly exothermic in both water and aqueous NaCl 0.9% solution, which indicates that the salt did not modify the interaction. PQ-4/SDS dispersions had, for all SDS concentrations, higher viscous (G") and, especially, elastic (G') moduli than the polymer solution. The maxima in G' and G" (four orders of magnitude greater than PQ-4 only solutions) were observed at the SDS concentrations in which the ammonium/sulfate groups ratio is close to 1. PQ-10/SDS dispersions behaved very differently and, near the neutralization point, the precipitation of the system caused G" to decrease abruptly, and G' to disappear. The contrasting behavior of the two cationic celluloses may be attributed to their structural differences; PQ-4 has less ammonium groups, in small chains grafted to the cellulose backbone, and more free hydroxyethyl substituents than PQ-10. Therefore, although the neutralization of charges causes the formation of a neutral polyampholyte, the presence of the free hydrophilic hydroxyethyl groups in PQ-4 avoids the precipitation of the aggregates and contributes to the establishment of a three-dimensional network. In contrast, in PQ-10, the ammonium groups are directly bonded to the hydroxyethyl substituents and, in the aggregation process, they may be included in the polyampholyte complex, contributing to the precipitation. This different behavior was easily seen in the surfactant-induced shrinking of the hydrogels around the charges neutralization. Although the SDS binding isotherms were very similar, PQ-10 hydrogels decreased their volume up to 20 times at the neutralization point, while PQ-4 hydrogels reduced their initial volume only three times under the same conditions. These results suggest that the phase transitions of the hydrogels may be used as quick predictors of the behavior of the polymer dispersions.
Rodríguez
R
R
Departamento de Farmacia y Tecnología Farmacéutica, Universidad de Santiago de Compostela, Santiago de Compostela, Spain.
Alvarez-Lorenzo
C
C
Concheiro
A
A
D002412:Cations; D002482:Cellulose / Q000031:analogs & derivatives* / Q000737:chemistry*; D003432:Cross-Linking Reagents / Q000737:chemistry; D020100:Hydrogels / Q000737:chemistry*; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D012212:Rheology; D012967:Sodium Dodecyl Sulfate / Q000737:chemistry*; D013329:Structure-Activity Relationship; D013499:Surface Properties; D013501:Surface-Active Agents / Q000737:chemistry*; D014867:Water / Q000737:chemistry
D002412:Cations; D003432:Cross-Linking Reagents; D020100:Hydrogels; D000644:Quaternary Ammonium Compounds; D013501:Surface-Active Agents; D014867:Water; D012967:Sodium Dodecyl Sulfate; D002482:Cellulose; C002283:hydroxyethylcellulose