Combining a sensor and a pH-gated nanopore based on an avidin-biotin system.

Here we propose a new approach to tailor nanopores, which combines both pH gating and sensing properties. This strategy is based on PEG like-avidin grafting in nanopores designed by atomic layer deposition (ALD). Below pH 5 the nanopore is blocked. We show that the PEG chains are at the origin of these properties.

DNA-modified polymer pores allow pH- and voltage-gated control of channel flux.

Biological channels embedded in cell membranes regulate ionic transport by responding to external stimuli such as pH, voltage, and molecular binding. Mimicking the gating properties of these biological structures would be instrumental in the preparation of smart membranes used in biosensing, drug delivery, and ionic circuit construction. Here we present a new concept for building synthetic nanopores that can simultaneously respond to pH and transmembrane potential changes. DNA oligomers containing protonatable A and C bases are attached at the narrow opening of an asymmetric nanopore. Lowering the pH to 5.5 causes the positively charged DNA molecules to bind to other strands with negative backbones, thereby creating an electrostatic mesh that closes the pore to unprecedentedly high resistances of several tens of gigaohms. At neutral pH values, voltage switching causes the isolated DNA strands to undergo nanomechanical movement, as seen by a reversible current modulation. We provide evidence that the pH-dependent reversible closing mechanism is robust and applicable for nanopores with opening diameters of up to 14 nm. The concept of creating an electrostatic mesh may also be applied to different organic polymers.

DNA strands attached inside single conical nanopores: ionic pore characteristics and insight into DNA biophysics.

Single nanopores attract a great deal of scientific interest as a basis for biosensors and as a system to study the interactions and behavior of molecules in a confined volume. Tuning the geometry and surface chemistry of nanopores helps create devices that control transport of ions and molecules in solution. Here, we present single conically shaped nanopores whose narrow opening of 8 or 12 nm is modified with single-stranded DNA molecules. We find that the DNA occludes the narrow opening of nanopores and that the blockade extent decreases with the ionic strength of the background electrolyte. The results are explained by the ionic strength dependence of the persistence length of DNA. At low KCl concentrations (10 mM) the molecules assume an extended and rigid conformation, thereby blocking the pore lumen and reducing the flow of ionic current to a greater extent than compacted DNA at high salt concentrations. Attaching flexible polymers to the pore walls hence creates a system with tunable opening diameters in order to regulate transport of both neutral and charged species.

Comparison of bipolar and unipolar ionic diodes.

Nanoporous ionic diodes, as well as devices for manipulating ions and molecules in a solution, have attracted a great deal of interest from researchers in various fields from the fundamental point of view. Ionic diodes allow the ions to be transported in one direction and block the transport in the other. There are two types of diodes that have been realized experimentally. A bipolar diode contains a junction between two zones of the pore walls with positive and negative surface charges. A unipolar diode contains a zone that is neutral and a zone that is charged. In this paper we discuss differences in operation of the diodes with a special emphasis on the sensitivity of their performance to the lengths of the charged and neutral zones. We also show that a bipolar diode offers more asymmetric current-voltage curves than a unipolar diode.