Poly (N-isopropylacrylamide) microgel-based assemblies for organic dye removal from water.

Poly(N-isopropylacrylamide)-co-acrylic acid (pNIPAm-co-AAc) microgel assemblies (aggregates) were synthesized via polymerization of the cross-linker N,N'-methylenebisacrylamide (BIS) in the presence of microgels in solution. In this case, the microgels were entrapped in the polymerized cross-linker network. The aggregates were investigated for their ability to remove the organic, azo dye molecule 4-(2-hydroxy-1-napthylazo) benzenesulfonic acid sodium salt (Orange II) from water at both room and elevated temperatures. These results were compared with unaggregated microgels that were previously reported (Parasuraman, D.; Serpe, M. J. ACS. Appl. Mater. Interfaces 2011, 3, 2732.). It was found that the removal efficiency increased at elevated temperature, most likely due to the thermoresponsive nature of the pNIPAm-based aggregates, which expel water of solvation and deswell at higher temperature and reswell when they are cooled back to room temperature. Furthermore, increasing the number of cycles the aggregates are heated and cooled enhanced the percent removal of the dye from water. We also evaluated the effect of increasing cross-linker concentration on the removal efficiency, where we found the removal efficiency to increase with increasing cross-linker concentration in the aggregates. The maximum removal efficiency reached by the microgel aggregates at elevated temperatures was calculated to be 73.1%. This enhanced uptake is due to the presence of larger internal volume between the microgels in the aggregates, which the individual microgels lack. Control studies reveal that the structure and hydrophobicity of the aggregates lead to the enhanced uptake efficiencies and is not due to the presence of BIS alone. We determined that aggregates leak 75.6% of the dye that was originally removed from solution. The removal of Orange II by the aggregates at room temperature was fit by a Langmuir sorption isotherm.