Wen Jie Lan

Pressure-dependent ion current rectification in conical-shaped glass nanopores

Ion current rectification that occurs in conical-shaped glass nanopores in low ionic strength solutions is shown to be dependent on the rate of pressure-driven electrolyte flow through the nanopore, decreasing with increasing flow rate. The dependence of the i-V response on pressure is due to the disruption of cation and anion distributions at equilibrium within the nanopore. Because the flow rate is proportional to the third power of the nanopore orifice radius, the pressure-driven flow can eliminate rectification in nanopores with radii of ∼200 nm but has a negligible influence on rectification in a smaller nanopore with a radius of ∼30 nm. The experimental results are in qualitative agreement with predictions based on finite-element simulations used to solve simultaneously the Nernst-Planck, Poisson, and Navier-Stokes equations for ion fluxes in a moving electrolyte within a conical nanopore.

Designed Post-Self-Assembly Structural and Functional Modifications of a Truncated Tetrahedron

Post-self-assembly modifications of a discrete metal-organic supramolecular structure have been developed. Such modifications allow the properties of the self-assembled supramolecular species to be changed in a simple and efficient manner (>90% yield). Initiated by the application of chemical stimuli, the post-self-assembly modifications described herein result in three distinct changes to the supramolecular system: an individual building-block component change, an overall structural modification, and a functional evolution of a [6+4] metal-organic supramolecular structure. The three modifications have been carefully examined by a range of characterization methods, including NMR and UV-vis spectroscopy, electrospray ionization mass spectrometry, pulsed field gradient spin echo NMR measurements, electrochemical analysis, and computational simulations.

Post-Self-Assembly Covalent Chemistry of Discrete Multicomponent Metallosupramolecular Hexagonal Prisms

The multicomponent coordination-driven self-assembly of hexakis[4-(4-pyridyl)phenyl]benzene, cis-(PEt(3))(2)Pt(II)(OTf)(2), and amine- or maleimide-functionalized isophthalate forms discrete hexagonal prisms as single reaction products. The amino or maleimide groups decorating the isophthalate pillars of the prisms provide reactive sites for post-self-asssembly modifications. In this communication, we demonstrate that the hexagonal prisms can be functionalized without disrupting the prismatic cores, enabling the incorporation of new functionalities under mild conditions.

Diffusional Motion of a Particle Translocating through a Nanopore

The influence of diffusional motion on the capture and release of individual nanoparticles as they are driven through a conical-shaped glass nanopore membrane (GNM) by pressure-induced flow is reported. In these experiments, one to several hundred particles are driven through the orifice of the nanopore. Following the initial translocation, the pressure is reversed and the particles are driven through the GNM orifice in the reverse direction. The resistive-pulse technique is used to monitor the temporal sequence of particle capture and release translocations. The size of the particles (120-160 nm) and the direction of translocation can be determined from the pulse amplitude and shape. The stochastic influence of diffusion on particle trajectories has been investigated, including instantaneous transfer rate, release probability, and cumulative release success rate. We demonstrate that the sequence of particle translocations in the capture step (a, b, c... where the letters represent different particles) is largely preserved and can be read out by resistive-pulse signature during the release translocations (...c, b, a). The observed stochastic events are in good agreement with a convective diffusion model of particle trajectory within the confined geometry of the nanopore. The pressure-reversal technique opens new avenues for chemical analysis of particles using resistive-pulse methods.

Resistive-Pulse Analysis of Nanoparticles

The development of nanopore fabrication methods during the past decade has led to the resurgence of resistive-pulse analysis of nanoparticles. The newly developed resistive-pulse methods enable researchers to simultaneously study properties of a single nanoparticle and statistics of a large ensemble of nanoparticles. This review covers the basic theory and recent advances in applying resistive-pulse analysis and extends to more complex transport motion (e.g., stochastic thermal motion of a single nanoparticle) and unusual electrical responses (e.g., resistive-pulse response sensitive to surface charge), followed by a brief summary of numerical simulations performed in this field. We emphasize the forces within a nanopore governing translocation of low-aspect-ratio, nondeformable particles but conclude by also considering soft materials such as liposomes and microgels.

Electrical signature of the deformation and dehydration of microgels during translocation through nanopores

The resistive-pulse sensing technique was used to investigate the deformation and dehydration of individual 570 nm radius poly(N-isopropylacrylamide-co-acrylic acid) microgels during their translocation through a glass membrane containing a single conical nanopore with orfice radii ranging from 200 to 700 nm. Microgel translocation rates were found to be dependent on both the applied pressure and the pore radius, and a translocation threshold pressure was found to be a function of the pore size. Importantly, current–time traces resulting from translocation events demonstrate changes in the conductivity of the microgel, due to compression and partial dehydration during translocation. A minimum nanopore-to-microgel radius ratio of ∼0.4 is observed for translocation, suggesting a theoretical limit imposed by the compressibility of the microgel and Columbic repulsion with the pore walls. Our results provide fundamental insight into microgels including their compressibility and conductivity, as well as the ability of soft particles to permeate porous membranes and pass through voids of dimensions smaller than the particles themselves.

Tunable negative differential electrolyte resistance in a conical nanopore in glass.

Liquid-phase negative differential resistance (NDR) is observed in the i-V behavior of a conical nanopore (~300 nm orifice radius) in a glass membrane that separates an external low-conductivity 5 mM KCl solution of dimethylsulfoxide (DMSO)/water (v/v 3:1) from an internal high-conductivity 5 mM KCl aqueous solution. NDR appears in the i-V curve of the negatively charged nanopore as the voltage-dependent electro-osmotic force opposes an externally applied pressure force, continuously moving the location of the interfacial zone between the two miscible solutions to a position just inside the nanopore orifice. An ~80% decrease in the ionic current occurs over less that a ~10 mV increase in applied voltage. The NDR turn-on voltage was found to be tunable over a ~1 V window by adjusting the applied external pressure from 0 to 50 mmHg. Finite-element simulations based on solution of Navier-Stokes, Poisson, and convective Nernst-Planck equations for mixed solvent electrolytes within a negatively charged nanopore yield predictions of the NDR behavior that are in qualitative agreement with the experimental observations. Applications in chemical sensing of a tunable, solution-based electrical switch based on the NDR effect are discussed.