Programming Ionic Pore Accessibility in Zwitterionic Polymer Modified Nanopores.

Creating switchable and gradually tunable pores or channels that display transport control similar to biological pores remains a major challenge in nanotechnology. It requires the generation and manipulation of complex charge situations at the nanoscale and the understanding of how confinement influences chemistry and transport. Here, two different pore sizes, ∼100 nm and less than 10 nm, functionalized with varying amounts of responsive zwitterionic polycarboxybetaine methyl acrylate (PCBMA) give fascinating insight into the confinement controlled ionic transport of pores functionalized with pH-dependent zwitterionic polymers. Under basic conditions, the zwitterionic state offers complex, strongly pore-size-dependent ionic permselectivity characteristics. For mesoporous films with pore sizes smaller than 10 nm, complete ion exclusion is observed after reaching a critical zwitterionic polymer amount, clearly indicating an electrostatic behavior of "bipolar charged" pores. This ion exclusion is not observed for pore diameters of ∼100 nm. In addition, the solution pH of equal pore accessibility for oppositely charged ions and pore sizes smaller than 10 nm shifts with increasing polymer amount from a pH of 2.5 to 8.2, and the quantity of ions accessing the pores depends on the pore size. These observations clearly show the potential of controlling pore accessibility based on controlled functional composition at the nanoscale without changing the components themselves as well as the influence of spatial confinement on pore accessibility in the presence of complex (zwitterionic) charged states.