Molecular Design Strategies to Enhance the Electroresponse of Polyelectrolyte Brushes: Effects of Charge Fraction and Chain Length Dispersity.

Polyelectrolyte brushes are functional surface coatings that react to external stimuli. The response of these brushes in electric fields is nearly immediate as the field acts directly on the charges in the polyion, while the response to bulk stimuli such as temperature, acidity, and ionic composition is intrinsically capped by transport limitations. However, the response of fully charged brushes is limited because large field strengths are required to achieve a response. This limits the application of these brushes to architectures such as small pores or nanojunctions because small biases can generate large field strengths over small distances. Here, we propose a design strategy that enhances the response and lowers the field strength required in these applications. Our coarse-grained simulations highlight two approaches to increase the electroresponse of polyelectrolyte brushes: dispersity in the chain length enhances the electroresponse and a reduction in the number of charged monomers does the same. With these approaches, we increase the relative brush height variation from only 28% to as much as 227% since in partially charged brushes, more chains need to respond to screen the imposed field and the longer chains in disperse brushes can reorganize over large distances. Additionally, we find that disperse brushes show a stratified response where short chains collapse first and long chains stretch first because this stratification minimizes the change in conformational energy. We envision that our insights will enable the application of electroresponsive polyelectrolyte brushes in larger architectures or in small architectures using smaller biases, which could enable a stimulus-responsive pore size modulation that could be used for filtration and molecular separations.