Highly sensitive gating in pH-responsive nanochannels as a result of ionic bridging and nanoconfinement

Sensitive switching between OFF and ON states is a desirable feature in stimuli-responsive nanopores and nanochannels. In this work, we show that nanogates modified with weak polyelectrolytes can be controlled by multivalent counterions and, more remarkably, can exhibit sensitive pH-gating due to an interplay between ionic bridging and nanoconfinement. We demonstrate these general features by systematically studying the effects of Ca2+ binding on the molecular organization and transport properties of poly(acrylic acid)-functionalized nanochannels. To this end, we extend and apply a molecular theory that has been successfully used in the past to describe and predict the behavior of pH-responsive polymers. Two main results emerge from the present study: First, the addition of Ca2+ to the bulk solution changes—in a concentration-dependent manner—both the ionization and structural state of the end-tethered polymers, affecting, respectively, the ionic conductivity and physical opening of the nanochannel. Second, in the presence of Ca2+ and under specific nanoconfinement conditions, the grafted channel can exhibit a sensitive response to pH in the transition between closed and open states. We attribute this sensitivity to bistability in the system. Our results also indicate that the polymer layer can undergo a microphase separation when the brush collapses on the nanochannel walls. Taken together, these findings suggest the possibility of designing nanogates that can respond to marginal changes in pH or multivalent ion concentration. Such nanodevices may be used as logic gates or for any application that requires a sensitive control over the ions, molecules, or nanoparticles flowing through them.