Evidence that self-similar microrheology of highly entangled polymeric solutions scales robustly with, and is tunable by, polymer concentration

Abstract

We report observations of a remarkable scaling behavior with respect to concentration in the passive microbead rheology of two highly entangled polymeric solutions, polyethylene oxide (PEO) and hyaluronic acid (HA). This behavior was reported previously [Hill et al., PLOS ONE (2014)] for human lung mucus, a complex biological hydrogel, motivating the current study for synthetic polymeric solutions PEO and HA. The strategy is to identify, and focus within, a wide range of lag times $\tau$ for which passive micron diameter beads exhibit self-similar (fractional, power law) mean-squared-displacement (MSD) statistics. For lung mucus, PEO at three different molecular weights (Mw), and HA at one Mw, we find ensemble-averaged MSDs of the form $⟨\Delta r^2(\tau )⟩=4D_{\alpha }{\tau }^{\alpha }$, all within a common band, [1/60 sec, 3 sec], of lag times $\tau$. We employ the MSD power law parameters $(D_{\alpha },\alpha )$ to classify each polymeric solution over a range of highly entangled concentrations. By the generalized Stokes-Einstein relation, power law MSD implies power law elastic $G^{\prime }(\omega )$ and viscous $G^{\prime \prime }(\omega )$ moduli for frequencies $1/\tau$, [0.33 sec${}^{-1}$, 60 sec${}^{-1}$]. A natural question surrounds the polymeric properties that dictate $D_{\alpha }$ and $\alpha$, e.g. polymer concentration c, Mw, and stiffness (persistence length). In [Hill et al., PLOS ONE (2014)], we showed the MSD exponent $\alpha$ varies linearly, while the pre-factor $D_{\alpha }$ varies exponentially, with concentration, i.e. the semi-log plot, $(log(D_{\alpha }),\alpha )(c)$ of the classifier data is collinear. Here we show the same result for three distinct Mw PEO and HA at a single Mw. Future studies are required to explore the generality of these results for polymeric solutions, and to understand this scaling behavior with polymer concentration.

35 pages, 10 figures