Preparation of Soft Hydrogel Nanoparticles with PNIPAm Hair and Characterization of Their Temperature-Induced Aggregation

There exists a great number Of publications concerning lie synthesis of core-shell and/or hairy particles by means of controlled/living polymerization. Nevertheless, how to fabricate ultrafine nanosized hairy particles, especially polymeric soft hairy particles, remains a significant challenge. This paper presents a simple self-developed approach consisting of a two-step photoinduced polymerization of cross-linked polyacrylamide (CLPAM) soft hydrogel nanoparticles (5-10 nm in diameter) grafted with poly(N-isopropylcarylamide) (PNIPAm) chains. The architecture of such ultrafine soft water-swollen CLPAM@PNIPAm core/shell nanoparticles (20-35 rim in diameter) demonstrated very specific temperature sensitive behaviors. During heating a fast association process was observed at approximately 33-34 degrees C and the singular hairy particles with 34 nm diameters clustered into aggregates that were similar to 120 nm in diameter. Raising the temperature further, however, led to a decrease in size to about 100 nm at 45 degrees C. This behavior was attributed to the formation of hydrophobic shell layers accompanying the shrinkage of PNIPAm chains with chain polar transformations. With the contraction pressure produced by further shrinkage of the hydrophobic shell layers, the soft fully swollen PAM cores expelled water and diminished in size. During the cooling process, these contracted cores that were trapped in the aggregates gave rise to all early dissociation. The hydrophilic hairy CLPAM@PNIPAm particles are believed to be potentially useful as carriers to specific target regions, e.g., cells for controlled drug delivery and other smart biomaterial applications.