Plasmonic nanopore to monitor in-pore chemistry

TL;DR

This paper demonstrates how plasmonic nanopores can be used to monitor reversible in-pore chemical reactions, specifically metal phosphate precipitation and dissolution, with high spatial resolution using surface-enhanced Raman scattering.

Contribution

It introduces a plasmonic nanopore platform that enables real-time, in-situ monitoring of chemical reactions within nanopores during gating processes.

Findings

Reversible pore gating achieved via cyclic precipitation and dissolution of metal phosphates.

Surface-enhanced Raman scattering validates in-pore chemical reactions.

Plasmonic nanopores enable high-resolution monitoring of nanoscale chemistry.

Abstract

In solid-state nanopores, achieving reliable control over pore aperture opening and closing (gating) remains a major challenge. Gating can be driven by the applied voltage involving electrically tunable chemical reactions, achieved by selecting appropriate compounds within the nanopore volume. In particular, cyclic precipitation and dissolution of metal phosphates can be triggered by regulating cation transport through an applied transmembrane voltage, thereby enabling reversible pore gating. Under negative bias, metal phosphate precipitates form inside the pore, obstructing ion flow and reducing current. Switching the polarity dissolves the precipitates, restoring ionic conductance. This process effectively produces a nanofluidic diode characterized by a remarkably high rectification ratio. To probe these localized chemical reactions more directly, we employed a plasmonic nanopore that generates strong confined fields, enabling surface-enhanced Raman scattering (SERS) measurements within the nanopore volume during cyclic gating. These measurements not only validate the proposed in-pore chemistry but also highlight the potential of plasmonic nanopores as powerful tools for monitoring nanoscale chemical processes with high spatial resolution.