Negative memory capacitance and ionic filtering effects in asymmetric nanopores

The pervasive model for a solvated, ion-filled nanopore is often a resistor in parallel with a capacitor. For conical nanopore geometries, here we propose the inclusion of a Warburg-like element, which is necessary to explain otherwise anomalous observations such as negative capacitance and low-pass filtering of translocation events (we term this phenomenon as Warburg filtering). The negative capacitance observed here has long equilibration times and memory (that is, mem-capacitance) at negative voltages. We used the transient occlusion of the pore using λ-DNA and 10 kbp DNA to test whether events are being attenuated by purely ionic phenomena when there is sufficient amplifier bandwidth. We argue here that both phenomena can be explained by the inclusion of the Warburg-like element, which is mechanistically linked to concentration polarization and activation energy to generate and maintain localized concentration gradients. We conclude the study with insights into the transduction of molecular translocations into electrical signals, which is not simply based on pulse-like resistance changes but instead on the complex and nonlinear storage of ions that enter dis-equilibrium during molecular transit.