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With the resistive-pulse technique (RPT), nanopores serve as the nanofluidic sensors of various analytes for their many physical and chemical properties. Here, we focus on the size measurement and its theoretical prediction for sub-200 nm nanoparticles with RPT. Through systematical investigation of the current blockade of nanoparticles across cylindrical nanopores with simulations, Maxwell method considering the shape coefficient and access resistances agrees well with simulation results. However, the widely used integration method of the resistance has distinct deviations in various cases. With the introduction of a correction factor \b{eta} to the integration method, our revised equations can provide good predictions for simulation results. \b{eta} shows a strong dependence on the diameter ratio (d over D) of the nanoparticle and nanopore. Following the same strategy, modified equations are provided for the accurate size prediction for nanoparticles across conical nanopores, where the integration method is the default convenient way. The correction factor \b{eta}' relates to \b{eta} in cylindrical nanopores. \b{eta}' exhibits independence on the pore geometry parameters and diameters of nanoparticles, but dependence on the surface charge density of conical nanopores. Our improved equations can provide theoretical predictions for the accurate size detection of 100-200 nm diameter nanoparticles across cylindrical and conical nanopores., Comment: 29 pages 7 figures

High-performance osmotic energy conversion (OEC) with perm-selective porous membrane requires both high ionic selectivity and permeability simultaneously. Here, hydrodynamic slip is considered on surfaces of nanopores to break the tradeoff between ionic selectivity and permeability, because it decreases the viscous friction at solid-liquid interfaces which can promote ionic diffusion during OEC. Taking advantage of simulations, influences from individual slipping surfaces on the OEC performance have been investigated, i.e. the slipping inner surface (surfaceinner) and exterior surfaces on the low- and high-concentration sides (surfaceL and surfaceH). Results show that the slipping surfaceL is crucial for high-performance OEC. For nanopores with various lengths, the slipping surfaceL simultaneously increases both ionic permeability and selectivity of nanopores, which results in both significantly enhanced electric power and energy conversion efficiency. While for nanopores longer than 30 nm, the slipping surfaceinner plays a dominant role in the increase of electric power, which induces a considerable decrease in energy conversion efficiency due to enhanced transport of both cations and anions. Considering the difficulty in hydrodynamic slip modification to the surfaceinner of nanopores, the surface modification to the surfaceL may be a better choice to achieve high-performance OEC. Our results provide feasible guidance to the design of porous membranes for high-performance osmotic energy harvesting., Comment: 25 pages, 7 figures

High-performance osmotic energy conversion (OEC) requires both high ionic selectivity and permeability in nanopores. Here, through systematical explorations of influences from individual charged nanopore surfaces on the performance of OEC, we find that the charged exterior surface on the low-concentration side (surfaceL) is essential to achieve high-performance osmotic power generation, which can significantly improve the ionic selectivity and permeability simultaneously. Detailed investigation of ionic transport indicates that electric double layers near charged surfaces provide high-speed passages for counterions. The charged surfaceL enhances cation diffusion through enlarging the effective diffusive area, and inhibits anion transport by electrostatic repulsion. Different areas of charged exterior surfaces have been considered to mimic membranes with different porosities in practical applications. Through adjusting the width of the charged ring region on the surfaceL, electric power in single nanopores increases from 0.3 to 3.4 pW with a plateau at the width of ~200 nm. The power density increases from 4200 to 4900 W/m2 and then decreases monotonously that reaches the commercial benchmark at the charged width of ~480 nm. While, energy conversion efficiency can be promoted from 4% to 26%. Our results provide useful guide in the design of nanoporous membranes for high-performance osmotic energy harvesting., Comment: 30 pages and 7 figures

Nanopores that exhibit ionic current rectification (ICR) behave like diodes, such that they transport ions more efficiently in one direction than the other. Conical nanopores have been shown to rectify ionic current, but only those with at least 500 nm in length exhibit significant ICR. Here, through the finite element method, we show how ICR of conical nanopores with length below 200 nm can be tuned by controlling individual charged surfaces i.e. inner pore surface (surface_inner), and exterior pore surfaces on the tip and base side (surface_tip and surface_base). The charged surface_inner and surface_tip can induce obvious ICR individually, while the effects of the charged surface_base on ICR can be ignored. The fully charged surface_inner alone could render the nanopore counterion-selective and induces significant ion concentration polarization in the tip region, which causes reverse ICR compared to nanopores with all surface charged. In addition, the direction and degree of rectification can be further tuned by the depth of the charged surface_inner. When considering the exterior membrane surface only, the charged surface_tip causes intra-pore ionic enrichment and depletion under opposite biases which results in significant ICR. Its effective region is within ~40 nm beyond the tip orifice. We also found that individual charged parts of the pore system contributed to ICR in an additive way due to the additive effect on the ion concentration regulation along the pore axis. With various combinations of fully/partially charged surface_inner and surface_tip, diverse ICR ratios from ~2 to ~170 can be achieved. Our findings shed light on the mechanism of ionic current rectification in ultra-short conical nanopores, and provide a useful guide to the design and modification of ultra-short conical nanopores in ionic circuits and nanofluidic sensors., Comment: 25 pages, 8 figures