The ability of poly (N-isopropylacrylamide) (pNIPAm), and pNIPAm-co-acrylic acid (pNIPAm-co-AAc) microgels to remove an organic azo dye molecule, 4-(2-Hydroxy-1-naphthylazo) benzenesulfonic acid sodium salt (Orange II) from aqueous solutions at both room and elevated temperature was assessed. At room temperature, we found that the amount of Orange II removed from water (removal efficiency) increased with increasing AAc and microgel concentration. The removal of Orange II from water was also fit by a Langmuir sorption isotherm model. Furthermore, we found the extent of Orange II removal depended on solution temperature; more Orange II was removed from water at elevated temperature and as the microgels were held at that temperature for longer durations of time. Additionally, by increasing the cycles between high and ambient temperature, the removal of Orange II was enhanced, although this was only true for two temperature cycles. We hypothesize that this is a result of the thermoresponsive nature of pNIPAm-based microgels which deswell at elevated temperature expelling their solvating water and when the microgels are cooled back down they reswell with the Orange II containing water. We also hypothesize that the microgels become saturated after the second heating cycle and so the efficiency of removal did not increase further. Finally, we assessed the ability of the microgels to retain the Orange II after it is removed from the aqueous solution. We determined that the microgels "leak" 25.6% of the Orange II that was originally removed from the 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.

We review our recent efforts utilizing poly(N-isopropylacrylamide)-co-acrylic acid (pNIPAm-co-AAc) microgels and their assemblies for the removal of an azo-dye molecule, 4-(2-Hyrodxy-1-napthylazo) benzenesulfonic acid sodium salt (Orange II), from aqueous solutions. First, the ability of dispersed, single microgels to remove Orange II from aqueous solutions at room temperature is discussed. Uptake efficiency (i.e., the amount of Orange II removed from water) increased with AAc composition in the microgels, yielding a maximum uptake efficiency of 29.5% for pNIPAm microgels with 10% AAc. Assemblies of microgels (aggregates) were also investigated for their removal efficiency, which yielded a maximum uptake efficiency of 44.1% at room temperature. Removal efficiencies for the microgels and their aggregates were also monitored at elevated temperatures, and a maximum of 56.6% removal efficiency was achieved for unaggregated microgels, while aggregates were able to remove 73.1% Orange II. To further explore the impact of the microgel system's structure on function, we investigated the role microgel size in the aggregates plays on the uptake efficiency. Initial observations showed that the aggregates composed of microgels with large diameter yielded improved uptake efficiency over the aggregates composed of small diameter microgels. Langmuir sorption isotherms were fit to the data for the dye removal by the unaggregated and aggregated microgels, which showed good fits in all cases.

Poly (N-isopropylacrylamide)-co-acrylic acid (pNIPAm-co-AAc) microgel based assemblies (aggregates) were synthesized from microgels of various diameters via polymerization of the crosslinker N,N′-methylenebisacrylamide (BIS) in the presence of microgels in solution. We investigated the ability of the respective aggregates 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. The results from the microgel aggregates made from 1.1-μm-diameter [Parasuraman and Serpe. ACS Applied Materials & Interfaces, 2011] microgels were compared to aggregates synthesized from 321-nm and 1.43-μm-diameter microgels. Aggregates made from the same size microgels showed increased uptake efficiency as the concentration of BIS in the aggregates was increased, while for a given BIS concentration, the uptake efficiency increased with increasing microgel size in the aggregate. We attribute this to the "nature" of the aggregates; aggregates have void space between the microgels that can serve as reservoirs for Orange II uptake-the void spaces are hypothesized to increase with larger diameter microgels. By exploiting the thermoresponsive nature of the microgels, and microgel based aggregates, 85.3 % removal efficiencies can be achieved. Finally, all uptake trends for the aggregates, at room temperature, were fit with a Langmuir sorption isotherm model.

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