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- Science Advances
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- National Science Foundation
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Reproducing the exquisite ion selectivity displayed by biological ion channels in artificial nanopore systems has proven to be one of the most challenging tasks undertaken by the nanopore community, yet a successful achievement of this goal offers immense technological potential. Here, we show a strategy to design solid-state nanopores that selectively transport potassium ions and show negligible conductance for sodium ions. The nanopores contain walls decorated with 4′-aminobenzo-18-crown-6 ether and single-stranded DNA (ssDNA) molecules located at one pore entrance. The ionic selectivity stems from facilitated transport of potassium ions in the pore region containing crown ether, while the highly charged ssDNA plays the role of a cation filter. Achieving potassium selectivity in solid-state nanopores opens new avenues toward advanced separation processes, more efficient biosensing technologies, and novel biomimetic nanopore systems.
Abstract While the electrical models of the membrane-based solid-state nanopores have been well established, silicon-based pyramidal nanopores cannot apply these models due to two distinctive features. One is its 35.3° half cone angle, which brings additional resistance to the moving ions inside the nanopore. The other is its rectangular entrance, which makes calculating the access conductance challenging. Here, we proposed and validated an effective transport model (ETM) for silicon-based pyramidal nanopores by introducing effective conductivity. The impact of half cone angle can be described equivalently using a reduced diffusion coefficient (effective diffusion coefficient). Because the decrease of diffusion coefficient results in a smaller conductivity, effective conductivity is used for the calculation of bulk conductance in ETM. In the classical model, intrinsic conductivity is used. We used the top-down fabrication method for generating the pyramidal silicon nanopores to test the proposed model. Compared with the large error (≥25% in most cases) when using the classical model, the error of ETM in predicting conductance is less than 15%. We also found that the ETM is applicable when the ratio of excess ion concentration and bulk ion concentration is smaller than 0.2. At last, it is proved that ETM can estimate the tipmore »
Elastic Properties of Confined Fluids from Molecular Modeling to Ultrasonic Experiments on Porous SolidsFluids confined in nanopores are ubiquitous in nature and technology. In recent years, the interest in confined fluids has grown, driven by research on unconventional hydrocarbon resources -- shale gas and shale oil, much of which are confined in nanopores. When fluids are confined in nanopores, many of their properties differ from those of the same fluid in the bulk. These properties include density, freezing point, transport coefficients, thermal expansion coefficient, and elastic properties. The elastic moduli of a fluid confined in the pores contribute to the overall elasticity of the fluid-saturated porous medium and determine the speed at which elastic waves traverse through the medium. Wave propagation in fluid-saturated porous media is pivotal for geophysics, as elastic waves are used for characterization of formations and rock samples. In this paper, we present a comprehensive review of experimental works on wave propagation in fluid-saturated nanoporous media, as well as theoretical works focused on calculation of compressibility of fluids in confinement. We discuss models that bridge the gap between experiments and theory, revealing a number of open questions that are both fundamental and applied in nature. While some results were demonstrated both experimentally and theoretically (e.g. the pressure dependence of compressibilitymore »
Potential-induced wetting and dewetting in pH-responsive block copolymer membranes for mass transport controlWetting and dewetting behavior in channel-confined hydrophobic volumes is used in biological membranes to effect selective ion/molecular transport. Artificial biomimetic hydrophobic nanopores have been devised utilizing wetting and dewetting, however, tunable mass transport control utilizing multiple transport modes is required for applications such as controllable release/transport, water separation/purification and energy conversion. Here, we investigate the potential-induced wetting and dewetting behavior in a pH-responsive membrane composed of a polystyrene- b -poly(4-vinylpyridine) (PS- b -P4VP) block copolymer (BCP) when fabricated as a hierarchically-organized sandwich structure on a nanopore electrode array (NEA), i.e. BCP@NEA. At pH < p K a (P4VP) (p K a ∼ 4.8), the BCP acts as an anion-exchange membrane due to the hydrophilic, protonated P4VP cylindrical nanodomains, but at pH > p K a (P4VP), the P4VP domains exhibit charge-neutral, hydrophobic and collapsed structures, blocking mass transport via the hydrophobic membrane. However, when originally prepared in a dewetted condition, mass transport in the BCP membrane may be switched on if sufficiently negative potentials are applied to the BCP@NEA architecture. When the hydrophobic BCP membrane is introduced on top of 2-electrode-embedded nanopore arrays, electrolyte solution in the nanopores is introduced, then isolated, by exploiting the potential-induced wetting and dewetting transitionsmore »
New technologies are emerging which allow us to manipulate and assemble 2-dimensional (2D) building blocks, such as graphene, into synthetic van der Waals (vdW) solids. Assembly of such vdW solids has enabled novel electronic devices and could lead to control over anisotropic thermal properties through tuning of inter-layer coupling and phonon scattering. Here we report the systematic control of heat flow in graphene-based vdW solids assembled in a layer-by-layer (LBL) fashion. In-plane thermal measurements (between 100 K and 400 K) reveal substrate and grain boundary scattering limit thermal transport in vdW solids composed of one to four transferred layers of graphene grown by chemical vapor deposition (CVD). Such films have room temperature in-plane thermal conductivity of ~400 Wm−1 K−1. Cross-plane thermal conductance approaches 15 MWm−2 K−1for graphene-based vdW solids composed of seven layers of graphene films grown by CVD, likely limited by rotational mismatch between layers and trapped particulates remnant from graphene transfer processes. Our results provide fundamental insight into the in-plane and cross-plane heat carrying properties of substrate-supported synthetic vdW solids, with important implications for emerging devices made from artificially stacked 2D materials.