Electric-field-enhanced transport in polyacrylamide hydrogel nano-composites

TL;DR

This study develops a mathematical model to predict electroosmotic flux enhancement in charged colloid-embedded polyacrylamide hydrogels, linking microstructure characteristics to macro-scale transport improvements for biosensing applications.

Contribution

It introduces a physics-based model that accurately predicts flux enhancement without fitting parameters, connecting microstructure to electroosmotic transport in hydrogel nanocomposites.

Findings

Predicted flux enhancement within a factor of two of experiments

Fitted Brinkman screening length between 0.9-1.6 nm

Ion migration hindrance improves model accuracy

Abstract

Electroosmotic pumping through uncharged hydrogels can be achieved by embedding the polymer network with charged colloidal inclusions. Matos and co-workers (2006) recently used the concept to enhance the diffusion-limited flux of uncharged molecules across polyacrylamide hydrogel membraness for the purpose of improving the performance of biosensors. This paper seeks to link their reported macroscale diagnostics to physicochemical characteristics of the composite microstructure. A mathematical model for the bulk electroosmotically enhanced tracer flux is proposed, which is combined with the electrokinetic model to ascertain the electroosmotic pumping velocity from measured flux enhancements. Because the experiments are performed with a known current density, but unknown bulk conductivity and electric field strength, theoretical estimates of the bulk electrical conductivity are adopted. These account for nano-particle polarization, added counterions, and non-specific adsorption. Theoretical predictions of the flux enhancement, achieved without any fitting parameters, are within a factor of two of the experiments. Alternatively, if the Brinkman screening length of the polymer skeleton is treated as a fitting parameter, then the best-fit values are bounded by the range 0.9-1.6 nm, depending on the inclusion size and volume fraction. Independent pressure-driven flow experiments reported in the literature for polyacrylamide gels without inclusions suggest 0.4 or 0.8 nm. The comparison can be improved by allowing for hindered ion migration, while uncertainties regarding the inclusion surface charge are demonstrated to have a negligible influence on the electroosmotic flow.