Modulating ion current rectification generating high energy output in a single glass conical nanopore channel by concentration gradient

Inspired by biological systems that have the inherent skill to generate considerable bioelectricity from the salt content in fluids with highly selective ion channels and pumps on cell membranes,herein,a fully abiotic,single glass conical nanopores energy-harvesting is demonstrated.Ion current rectification(ICR)in negatively charged glass conical nanopores is shown to be controlled by the electrolyte concentration gradient depending on the direction of ion diffusion.The degree of ICR is enhanced with the increasing forward concentration difference.An unusual rectification inversion is observed when the concentration gradient is reversely applied.The maximum power output with the individual nanopore approaches10~4pW.This facile and cost-efficient energy-harvesting system has the potential to power tiny biomedical devices or construct future clean-energy recovery plants.     

Concentration-gradient-dependent ion current rectification in charged conical nanopores

Ion current rectification (ICR) in negatively charged conical nanopores is shown to be controlled by the electrolyte concentration gradient depending on the direction of ion diffusion. The degree of ICR is enhanced with the increasing forward concentration difference. An unusual rectification inversion is observed when the concentration gradient is reversely applied. A numerical simulation based on the coupled Poisson and Nernst-Planck (PNP) equations is proposed to solve the ion distribution and ionic flux in the charged and structurally asymmetric nanofluidic channel with diffusive ion flow. Simulation results qualitatively describe the diffusion-induced ICR behavior in conical nanopores suggested by the experimental data. The concentration-gradient-dependent ICR enhancement and inversion is attributed to the cooperation and competition between geometry-induced asymmetric ion transport and the diffusive ion flow. The present study improves our understanding of the ICR in asymmetric nanofluidic channels associated with the ion concentration difference and provides insight into the rectifying biological ion channels.     

Scan-rate-dependent ion current rectification and rectification inversion in charged conical nanopores

Herein we report a theoretical study of diode-like behavior of negatively charged (e.g., glass or silica) nanopores at different potential scan rates (1-1000 V·s(-1)). Finite element simulations were used to determine current-voltage characteristics of conical nanopores at various electrolyte concentrations. This study demonstrates that significant changes in rectification behavior can be observed at high scan rates because the mass transport of ionic species appears sluggish on the time scale of the voltage scan. In particular, it explains the influence of the potential scan rate on the nanopore rectifying properties in the cases of classical rectification, rectification inversion, and the "transition" rectification domain where the rectification direction in the nanopore could be modulated according to the applied scan rate.     

Surface charge density determination of single conical nanopores based on normalized ion current rectification

Current rectification is well known in ion transport through nanoscale pores and channel devices. The measured current is affected by both the geometry and fixed interfacial charges of the nanodevices. In this article, an interesting trend is observed in steady-state current-potential measurements using single conical nanopores. A threshold low-conductivity state is observed upon the dilution of electrolyte concentration. Correspondingly, the normalized current at positive bias potentials drastically increases and contributes to different degrees of rectification. This novel trend at opposite bias polarities is employed to differentiate the ion flux affected by the fixed charges at the substrate-solution interface (surface effect), with respect to the constant asymmetric geometry (volume effect). The surface charge density (SCD) of individual nanopores, an important physical parameter that is challenging to measure experimentally and is known to vary from one nanopore to another, is directly quantified by solving Poisson and Nernst-Planck equations in the simulation of the experimental results. The flux distribution inside the nanopore and the SCD of individual nanopores are reported. The respective diffusion and migration translocations are found to vary at different positions inside the nanopore. This knowledge is believed to be important for resistive pulse sensing applications because the detection signal is determined by the perturbation of the ion current by the analytes.     

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.     

Mechanism of electrostatic gating at conical glass nanopore electrodes

The mechanism of molecule-based electrostatic gating of redox fluxes at conical glass nanopore (GNP) electrodes has been investigated using finite-element simulations. The results demonstrate that the fluxes of cationic redox molecules through the nanopore orifice can be reduced to negligibly small values when the surface charge of the nanopore is switched from a negative to a positive value. Electrostatic charge reversal can be affected by ionization of surface-bound moieties in response to environmental stimuli (e.g., photoionization or acid protonation), but only if the negative charge of the glass is included in the analysis. Numerical simulations of the responses of GNP electrodes are based on a simultaneous solution of the Poisson and Nernst-Planck equations and are in excellent agreement with our previously reported experimental results for electrostatic gating of the fluxes of Ru(NH 3) 6 (3+) and Fe(bpy) 3 (2+) at GNP electrodes with orifice radii between 15 and 100 nm. The gating mechanism is discussed in terms of three components: (1) migration of ionic redox species in the depletion layer adjacent to the electrode surface; (2) migrational transport along the charged pore walls; (3) electrostatic rejection of charged molecules at the pore orifice. The numerical results indicate that all three components are operative, but that ion migration along the pore walls is dominant.     

A glass nanopore electrode for single molecule detection

<正>We have developed a simple method for fabricating robust and low noise glass nanopore electrodes with pore size 10±5 nm to detect single molecules.β-Cyclodextrin was used as model compound for characterization.In 1.0 mol/L NaCl solution,the molecules generated current pulses of 2-5 pA with noise level less than 0.8 pA.A slide mode and a plug mode were suggested for the way ofβ-cyclodextrin single molecule moving into the glass nanopores.     

Predicting the DNA sequence dependence of nanopore ion current using atomic-resolution Brownian dynamics

It has become possible to distinguish DNA molecules of different nucleotide sequences by measuring ion current passing through a narrow pore containing DNA. To assist experimentalists in interpreting the results of such measurements and to improve the DNA sequence detection method, we have developed a computational approach that has both the atomic-scale accuracy and the computational efficiency required to predict DNA sequence-specific differences in the nanopore ion current. In our Brownian dynamics method, the interaction between the ions and DNA is described by three-dimensional potential of mean force maps determined to a 0.03 nm resolution from all-atom molecular dynamics simulations. While this atomic-resolution Brownian dynamics method produces results with orders of magnitude less computational effort than all-atom molecular dynamics requires, we show here that the ion distributions and ion currents predicted by the two methods agree. Finally, using our Brownian dynamics method, we find that a small change in the sequence of DNA within a pore can cause a large change in the ion current, and validate this result with all-atom molecular dynamics.     

Covalent modification of temperature-sensitive breathable polyurethane with carbon nanotubes

Intelligent breathable polyurethane (PU) that is easily allowable for vapor transmission at critical temperature would have significant implication for numerous applications; however, fabrication of such materials has proven to be tremendously challenging. Herein, we reported novel breathable polyurethane material covalently modified with carbon nanotubes (CNTs). When an optimal amount of CNTs (0.5 wt%) was added, the resultant PU film presented high waterproofness with hydrostatic pressure up to 10.9 kPa, as well as enhanced mechanical properties with a tensile strength of 22.2 kPa and elongation at break of 990%. This smart PU film has a significant increase in water vapor transmission rate between 18°C (1400 g/(m²·d)) and 38°C (3440 g/(m²·d)). The type of intelligent polyurethane material is a promising candidate for applications in areas such as protective clothing, separator media, and wearable electronics.     

Nucleobase recognition at alkaline pH and apparent pKa of single DNA bases immobilised within a biological nanopore

The four DNA bases are recognized in immobilized DNA strands at high alkaline pH by nanopore current recordings. Ionic currents through the biological nanopores are also employed to measure the apparent pK(a) values of single nucleobases within the immobilised DNA strands.     

Covalent modification of natural graphite with lithium benzoate multilayers via diazonium chemistry and their application in lithium ion batteries

In this study, we present an alternative pathway for the surface modification of anode materials of lithium ion batteries via molecular design. Aromatic multilayers of lithium benzoate were covalently attached to the surface of natural graphite through diazonium chemistry, and the resulting graphite exhibited superior electrochemical performance as anode material of lithium ion batteries. The mechanism responsible for the improved electrochemical behavior was ascribed to the formation of a stable and compact passive film that can accommodate the volume change of graphite particles. Due to the diversity and reliability of diazonium chemistry, this study may provide a new strategy to modify the conventional anode or even cathode materials of lithium ion batteries.     

On-line pH modification of carbonate eluents using an electrolytic potassium hydroxide generator for ion chromatography

Classical gradient elution, based on the application of a gradient pump used for mixing two or more prepared eluent components in pre-determined concentrations, was replaced by a chromatography system equipped with an isocratic pump and an electrolytic KOH generator. The isocratic pump delivered a constant concentration eluent composed of pure hydrogencarbonate solution. Carbonate ions, the main component of carbonate/hydrogencarbonate-based eluents, were formed by titration of hydrogencarbonate with KOH formed on-line in the electrolytic KOH generator. By changing the concentration of electrolytically-generated KOH, the eluent composition could be changed from pure hydrogencarbonate to a carbonate/hydrogencarbonate buffer, and finally to a carbonate/hydroxide-based eluent. The described system was tested to achieve pH-based changes of retention behavior of phosphate under constant inflow eluent composition conditions.     

Kinetic lattice grand canonical Monte Carlo simulation for ion current calculations in a model ion channel system

An algorithm in which kinetic lattice grand canonical Monte Carlo simulations are combined with mean field theory (KLGCMC/MF) is presented to calculate ion currents in a model ion channel system. In this simulation, the relevant region of the system is treated by KLGCMC simulations, while the rest of the system is described by modified Poisson-Boltzmann mean field theory. Calculation of reaction field due to induced charges on the channel/water and membrane/water boundaries is carried out using a basis-set expansion method [Im and Roux, J. Chem. Phys. 115, 4850 (2001)]. Calculation of ion currents, electrostatic potentials, and ion concentrations, as obtained from the KLGCMC/MF simulations, shows good agreement with Poisson-Nernst-Planck (PNP) theory predictions when the channel and membrane have the same dielectric constant as water. If the channel and membrane have a lower dielectric constant than water, however, there is a considerable difference between the KLGCMC/MF and PNP predictions. This difference is attributed to the reaction field, which is missing in PNP theory. It is demonstrated that the reaction field as well as fixed charges in the channel play key roles in selective ion transport. Limitations and further development of the current KLGCMC/MF approach are also discussed.     

Rapid Covalent Method for Fabrication of Optical pH Sensitive Membranes

ABSTRACT

A new method for covalent immobilization of pH indicators was developed.

Indicators, containing amino groups, are immobilized covalently on transparent hydrolyzed acet[ydot]lcellulose membranes. All the steps were performed at ambient temperature. The method was rapid and allows for preparation of the final membranes within one day.     

Covalent modification of mushroom tyrosinase with different amphiphic polymers for pharmaceutical and biocatalysis applications

Two different poly(ethylene glycol) derivatives (linear, mol wt 5000 and a branched form, mol wt 10000) and a new polymer (poly [acryloylmorfoline], mol wt 5500) were covalently bound to the enzyme tyrosinase. The polymer-protein conjugates were studied with a view to their potential pharmaceutical application and to their use for the bioconversion of phenolic substrates in organic solvents.V _max andK _m for the dopa-dopaquinone conversion, thermostability, stability toward inactivation by dopa oxidation products, half-life in blood circulation, and behavior in organic solvents for the different adducts were investi gated. Arrhenius plots for the dopa-dopaquinone conversion were also obtained in order to study the effects of temperature on the different enzyme forms. Covalent attachment of the polymers increased enzyme stability in aqueous solution and the solubility in organic solvents. However, organic solvent solubilization brought about loss of enzyme conformation as assessed by CD measurements, which is accompanied by a nonreversible loss of catalytic activity.     

Transmission of extramembrane conformational change into current: construction of metal-gated ion channel

Interaction with Fe(III) induces the reversible conformational switch of the extramembrane segment in the artificial receptor channel, which is transmitted into membranes as an increase in channel current (ion flux).     

Covalent modification of multiwalled carbon nanotubes with a low molecular weight chitosan

Covalent modification of shortened multiwalled carbon nanotubes (MWNTs) with a natural low molecular weight chitosan (LMCS) was accomplished by the nucleophilic substitution reaction. The LMCS modified MWNTs (MWNT-LMCS) were characterized by FTIR, solid-state 13C NMR, and XPS spectroscopies, thermogravimetric analysis, and transmission electron microscopy. The results revealed that amino and primary hydroxyl groups of the LMCS participated mainly in the formation of the MWNT-LMCS conjugates. The MWNT-LMCS consists of 58 wt.% LMCS, and about four molecular chains of the LMCS were attached to 1000 carbon atoms of the nanotube sidewalls. As a novel derivative of the MWNTs, the MWNT-LMCS not only solved in DMF, DMAc and DMSO, but also in aqueous acetic acid solution.     

Polymerized planar suspended lipid bilayers for single ion channel recordings: comparison of several dienoyl lipids

The stabilization of suspended planar lipid membranes, or black lipid membranes (BLMs), through polymerization of mono- and bis-functionalized dienoyl lipids was investigated. Electrical properties, including capacitance, conductance, and dielectric breakdown voltage, were determined for BLMs composed of mono-DenPC, bis-DenPC, mono-SorbPC, and bis-SorbPC both prior to and following photopolymerization, with diphytanoyl phosphocholine (DPhPC) serving as a control. Poly(lipid) BLMs exhibited significantly longer lifetimes and increased the stability of air-water transfers. BLM stability followed the order bis-DenPC > mono-DenPC ≈ mono-SorbPC > bis-SorbPC. The conductance of bis-SorbPC BLMs was significantly higher than that of the other lipids, which is attributed to a high density of hydrophilic pores, resulting in relatively unstable membranes. The use of poly(lipid) BLMs as matrices for supporting the activity of an ion channel protein (IC) was explored using α-hemolysin (α-HL), a model IC. Characteristic i-V plots of α-HL were maintained following photopolymerization of bis-DenPC, mono-DenPC, and mono-SorbPC, demonstrating the utility of these materials for preparing more durable BLMs for single-channel recordings of reconstituted ICs.     

Detection of single ion channel activity on a chip using tethered bilayer membranes

Membrane-bound ion channels are promising biological receptors since they allow for the stochastic detection of analytes at high sensitivity. For stochastic sensing, it is necessary to measure the ion currents associated with single ion channel opening and closing events. However, this calls for stability, high reproducibility, and long lifetimes. A critical issue to overcome is the low stability of the ion channel environment, that is, the bilayer membrane. A promising technique to surmount this is to connect the lower part of the membrane to a surface forming a tethered bilayer membrane. By reconstituting the synthetic ion channel, gramicidin A, into a tethered bilayer as part of a microchip design, we have been able to record the activity of single ion channels. The observed activity was compared with that obtained by a conventional electrophysiology method, tip dipping, to confirm its authenticity. These findings allow for the construction of stable biosensors based on ion channels and provide a novel technique for the characterization of ion channel activity.