Dynamics of Acrylamide Hydrogels, Polymers, and Monomers in Water Measured with Optical Heterodyne-Detected Optical Kerr Effect Spectroscopy.

The ultrafast dynamics of acrylamide monomers (AAm), polyacrylamide (PAAm), and polyacrylamide hydrogels (PAAm-HG) in water were studied using optical heterodyne-detected optical Kerr effect (OHD-OKE) spectroscopy. Previous ultrafast infrared (IR) measurements of the water dynamics showed that at the same concentration of the acrylamide moiety, AAm, PAAm, and PAAm-HG exhibited identical water dynamics and that these dynamics slowed with increasing concentration. In contrast to the IR measurements, OHD-OKE experiments measure the dynamics of both the water and the acrylamide species, which occur on different time scales. In this study, the dynamics of all the acrylamide systems slowed with increasing concentration. We found that AAm exhibits tetraexponential decays, the longest component of which followed Debye-Stokes-Einstein behavior except for the highest concentration, 40% (w/v). Low concentrations of PAAm followed a single power law decay, while high concentrations of PAAm and all concentrations of PAAm-HG decayed with two power laws. The highest concentrations, 25% and 40%, of PAAm and PAAm-HG showed nearly identical dynamics. We interpreted this result as reflecting a similar extent of chain-chain interactions. At low concentrations, PAAm displays non-Markovian, single-chain dynamics (single power law), but PAAm displays entangled chain-chain interactions at high concentrations (two power laws). PAAm-HG has chain-chain interactions at all concentrations that arise from the cross-linking. At high concentrations, the dynamics of the entangled of PAAm become identical within error as those of the cross-linked PAAm-HG.