Accelerated Nanocomposite Hydrogel Gelation Times Independent of Gold Nanoparticle Ligand Functionality.

The expansive use of hydrogels in healthcare relies on carefully tuned properties in dynamic environments with predictable behavior, including time sensitive biological systems and biomedical applications. To meet demands in these settings, nanomaterials are often introduced to a hydrogel matrix which simultaneously elevates potential applications while adding complexity to fundamental characteristics. With respect to drug delivery, gold nanoparticles have modifiable surfaces to carry an array of targeted drug treatments. However, different molecules acting as capping ligands possess different chemical structures that can impact gelation times. To understand the influence of capping ligand chemistry on polyacrylamide (PAM) based nanocomposite hydrogel radical gelation time, gold nanoparticle (Au NP) capping ligands were selected to encompass varying functional groups and molecular weights: citrate, cetyltrimethylammonium bromide, polyvinylpyrrolidone, and poly(acrylic acid). Gelation times were quantified as the storage-loss moduli crossover point in rheological time sweeps at constant strain and frequency. The dominating factor for gelation time was the presence of Au NPs, independent of a diverse range of capping ligand structures. The gelation times were also markedly faster than the same capping ligand structures used as stand-alone molecular additives. The accelerated Au NP gelation times, under 2 min, are attributed to the Au NPs acting as a cross-linker, promoting gelation. These results bolster the potential implementation of Au NP nanocomposite hydrogels in time-sensitive biomedical applications as robust drug carriers.