Specific Ion and Electric Field Controlled Diverse Ion Distribution and Electroosmotic Transport in a Polyelectrolyte Brush Grafted Nanochannel

Controlling ion distribution inside a charged nanochannel is central to using such channels in diverse applications. Here, we show the possibility of using a charged polyelectrolyte (PE) brush-grafted nanochannel for triggering diverse nanoscopic ion distribution and nanofluidic electroosmotic transport by controlling the valence and size of the counterions (that screen the charges of the PE brushes) and the strength of an externally applied axial electric field. We atomistically simulate separate cases of fully charged polyacrylic acid (PAA) brush functionalized nanochannels with Na⁺, Cs⁺, Ca²⁺, Ba²⁺, and Y³⁺ counterions screening the PE charges. Four key findings emerge from our simulations. First, we find that the counterions with a greater valence and a smaller size prefer to remain localized inside the brush layer. Second, for the case where there is an added chloride salt with the same cation (as the screening counterions), there are more coions (Cl^- ions) in the brush-free bulk than counterions (for counterions Na⁺, Ca²⁺, Ba²⁺, Y³⁺): this is a manifestation of the overscreening (OS) of the PE brush layer. Contrastingly, the number of Cs⁺ ions remain higher than the Cl^- ions inside the brush-free bulk, ensuring that there is no OS effect for this case. Third, large applied electric field enables a few Na⁺, Cs⁺, and Ba²⁺ counterions to leave the brush layer and to go to the bulk: this makes the OS of the PE brush layer disappear for the cases of PE brushes being screened by the Na⁺ and Ba²⁺ ions. On the other hand, no such electric-field-mediated disappearance of OS is observed for the cases of Ca²⁺ and Y³⁺ screening counterions; we attribute this to the firm attachment of these counterions to the negatively charged monomers. Free energy associated with a counterion binding to a PE chain corroborates this diversity in the counterion-specific response to the applied electric field. Finally, we demonstrate that such diverse ion distributions, along with specific electric-field-strength-dependent ion properties, lead to (1) electroosmotic (EOS) transport in nanochannels grafted with PAA brushes screened with Cs⁺ ions to be always counterion dominated, (2) EOS transport in nanochannels grafted with PAA brushes screened with Ca²⁺ and Y³⁺ ions to be always coion-dominated, and (3) EOS transport in nanochannels grafted with PAA brushes screened with Na⁺ and Ba²⁺ ions to be coion dominated for smaller electric fields and counterion dominated for larger electric fields.