Nanofluidic Diode Research Articles

Supramolecular Self-Assembly Induced Adjustable Multiple Gating States of Nanofluidic Diodes.

Artificial nanochannels, inheriting smart gating functions of biological ion channels, promote the development of artificial functional nanofluidic devices for high-performance biosensing and electricity generation. However, gating states of the artificial nanochannels have been mainly realized through chemical modification of the channels with responsive molecules, and their gating states cannot be further regulated once the nanochannel is modified. In this work, we employed a new supramolecular layer-by-layer (LbL) self-assembly method to achieve reversible and adjustable multiple gating features in nanofluidic diodes. Initially, a self-assembly precursor was modified into a single conical nanochannel, then host molecule-cucurbit[8]uril (CB[8]) and guest molecule, a naphthalene derivative, were self-assembled onto the precursor through an LbL method driven by host-enhanced π-π interaction, forming supramolecular monolayer or multilayers on the inner surface of the channel. These self-assemblies with different layer numbers possessed remarkable charge effects and steric effects, exhibiting a capability to regulate the surface charge density and polarity, the effective diameter, and the geometric asymmetry of the single nanochannel, realizing reversible gating of the single nanochannel among multiple rectification and ion-conduction states. As an example of self-assembly of supramolecular networks in nanoconfinements, this work provides a new approach for enhancing functionalities of artificial nanochannels by LbL supramolecular self-assemblies. Meanwhile, since the host molecule, CB[8], used in this work can interact with different kinds of biomolecules and stimuli-responsive chemical species, this work can be further extended to build a novel stable multiple-state research platform for a variety of uses such as sensing and controllable release.

Sequential Vapor Infiltration Treatment Enhances the Ionic Current Rectification Performance of Composite Membranes Based on Mesoporous Silica Confined in Anodic Alumina.

Ionic current rectification of nanofluidic diode membranes has been studied widely in recent years because it is analogous to the functionality of biological ion channels in principle. We report a new method to fabricate ionic current rectification membranes based on mesoporous silica confined in anodic aluminum oxide (AAO) membranes. Two types of mesostructured silica nanocomposites, hexagonal structure and nanoparticle stacked structure, were used to asymmetrically fill nanochannels of AAO membranes by a vapor-phase synthesis (VPS) method with aspiration approach and were further modified via sequence vapor infiltration (SVI) treatment. The ionic current measurements indicated that SVI treatment can modulate the asymmetric ionic transport in prepared membranes, which exhibited clear ionic current rectification phenomenon under optimal conditions. The ionic current rectifying behavior is derived from the asymmetry of surface conformations, silica species components, and hydrophobic wettability, which are created by the asymmetrical filling type, silica depositions on the heterogeneous membranes, and the condensation of silanol groups. This article provides a considerable strategy to fabricate composite membranes with obvious ionic current rectification performance via the cooperation of the VPS method and SVI treatment and opens up the potential of mesoporous silica confined in AAO membranes to mimic fluid transport in biological processes.

Label-free histamine detection with nanofluidic diodes through metal ion displacement mechanism

We design and characterize a nanofluidic device for the label-free specific detection of histamine neurotransmitter based on a metal ion displacement mechanism. The sensor consists of an asymmetric polymer nanopore fabricated via ion track-etching technique. The nanopore sensor surface having metal–nitrilotriacetic (NTA–Ni2+) chelates is obtained by covalent coupling of native carboxylic acid groups with Nα,Nα-bis(carboxymethyl)-l-lysine (BCML), followed by exposure to Ni2+ ion solution. The BCML immobilization and subsequent Ni2+ ion complexation with NTA moieties change the surface charge concentration, which has a significant impact on the current–voltage (I–V) curve after chemical modification of the nanopore. The sensing mechanism is based on the displacement of the metal ion from the NTA–Ni2+ chelates. When the modified pore is exposed to histamine solution, the Ni2+ ion in NTA–Ni2+ chelate recognizes histamine through a metal ion coordination displacement process and formation of stable Ni-histamine complexes, leading to the regeneration of metal-free NTA groups on the pore surface, as shown in the current-voltage characteristics. Nanomolar concentrations of the histamine in the working electrolyte can be detected. On the contrary, other neurotransmitters such as glycine, serotonin, gamma-aminobutyric acid, and dopamine do not provoke significant changes in the nanopore electronic signal due to their inability to displace the metal ion and form a stable complex with Ni2+ ion. The nanofluidic sensor exhibits high sensitivity, specificity and reusability towards histamine detection and can then be used to monitor the concentration of biological important neurotransmitters.

Biomimetic Nanofluidic Diode Composed of Dual Amphoteric Channels Maintains Rectification Direction over a Wide pH Range.

pH-gated ion channels in cell membranes play important roles in the cell's physiological activities. Many artificial nanochannels have been fabricated to mimic the natural phenomenon of pH-gated ion transport. However, these nanochannels show pH sensitivity only within certain pH ranges. Wide-range pH sensitivity has not yet been achieved. Herein, for the first time, we provide a versatile strategy to increase the pH-sensitive range by using dual amphoteric nanochannels. In particular, amphoteric polymeric nanochannels with carboxyl groups derived from a block copolymer (BCP) precursor and nanochannels with hydroxyl groups made from anodic alumina oxide (AAO) were used. Due to a synergistic effect, the hybrid nanochannels exhibit nanofluidic diode properties with single rectification direction over a wide pH range. The novel strategy presented here is a scalable, low-cost, and robust alternative for the construction of large-area membranes for nanofluidic applications, such as the separation of biomolecules.

Biomimetic Nanofluidic Diode Composed of Dual Amphoteric Channels Maintains Rectification Direction over a Wide pH Range

AbstractpH‐gated ion channels in cell membranes play important roles in the cell's physiological activities. Many artificial nanochannels have been fabricated to mimic the natural phenomenon of pH‐gated ion transport. However, these nanochannels show pH sensitivity only within certain pH ranges. Wide‐range pH sensitivity has not yet been achieved. Herein, for the first time, we provide a versatile strategy to increase the pH‐sensitive range by using dual amphoteric nanochannels. In particular, amphoteric polymeric nanochannels with carboxyl groups derived from a block copolymer (BCP) precursor and nanochannels with hydroxyl groups made from anodic alumina oxide (AAO) were used. Due to a synergistic effect, the hybrid nanochannels exhibit nanofluidic diode properties with single rectification direction over a wide pH range. The novel strategy presented here is a scalable, low‐cost, and robust alternative for the construction of large‐area membranes for nanofluidic applications, such as the separation of biomolecules.

A redox-sensitive nanofluidic diode based on nicotinamide-modified asymmetric nanopores

We demonstrate a redox-sensitive nanofluidic diode whose ion rectification is modulated by the oxidation and reduction of chemical moieties incorporated on its surface. To achieve this goal, we have first synthesized the chemical compounds 1-(4-aminobutyl)-3-carbamoylpyridin-1-ium (Nic-BuNH2) and 3-carbamoyl-1-(2,4-dinitrophenyl)pyridinium (Nic-DNP). Then, the surface of track-etched single asymmetric nanopores is decorated with the redox-sensitive Nic-BuNH2 and Nic-DNP molecules using carbodiimide coupling chemistry and Zincke reaction, respectively. The success of the modification reactions is monitored through the changes in the current–voltage (I–V) curves prior to and after pore functionalization. Upon exposing the modified pore to solutions of hydrogen peroxide (oxidizing agent) and sodium dithionite (reducing agent) the surface charge is reversibly modulated from positive to neutral, leading to measurable changes in the electronic readout of ion current passing through the nanopore. On oxidation, the quaternary nicotinamide units impart positive charge to the pore surface, resulting in the ion current rectification (anion-selective pore). On the contrary, the complementary reduced dihydronicotinamide moieties resulted in the loss of surface charge and ohmic behaviour (non-selective pore). The experimental results are further theoretically described by using Poisson-Nernst-Planck equations.

Geometrical control of ionic current rectification in a configurable nanofluidic diode.

Control of ionic current in a nanofluidic system and development of the elements analogous to electrical circuits have been the subject of theoretical and experimental investigations over the past decade. Here, we theoretically and experimentally explore a new technique for rectification of ionic current using asymmetric 2D nanochannels. These nanochannels have a rectangular cross section and a stepped structure consisting of a shallow and a deep side. Control of height and length of each side enables us to obtain optimum rectification at each ionic strength. A 1D model based on the Poisson-Nernst-Planck equation is derived and validated against the full 2D numerical solution, and a nondimensional concentration is presented as a function of nanochannel dimensions, surface charge, and the electrolyte concentration that summarizes the rectification behavior of such geometries. The rectification factor reaches a maximum at certain electrolyte concentration predicted by this nondimensional number and decays away from it. This method of fabrication and control of a nanofluidic diode does not require modification of the surface charge and facilitates the integration with lab-on-a-chip fluidic circuits. Experimental results obtained from the stepped nanochannels are in good agreement with the 1D theoretical model.

Passive nanofluidic diode using non-uniform nanochannels

In this work, we propose a nanofluidic diode for simple fluids using non-uniform nanochannels. Molecular dynamics simulations show that the fluidic diode allows water flows in the forward direction and blocks flows in the backward direction in a wide range of pressure drops. The unidirectional water flows are owing to the distinct activation pressures in different directions. In the forward (converging) direction, the activation pressure is small because of the relatively low capillary pressure and the water coalescence at the exit. In the backward direction, the activation pressure is high due to the high infiltration pressure. The pressure drop range for the fluidic diode can be varied by modifying the surface wettability, channel height, and/or the tilt angle of the channel. The fluidic diode can be used for flow control in integrated micro- and nanofluidic devices.

Anomalous Shrinking-Swelling of Nanoconfined End-Charged Polyelectrolyte Brushes: Interplay of Confinement and Electrostatic Effects.

In this article, we model the structure and configuration of the end-charged polyelectrolyte (PE) brushes grafted on the inner walls of a nanochannel. When the confinement effect is weak, that is, d0 < h/2 (d0 is the PE brush height without electrostatic effects and h is the nanochannel half-height), d < d0 (d is the brush height with the electrostatic effects), that is, the brushes shrink due to the electrostatic effects. Furthermore, for this case, an increase in salt concentration increases d. On the contrary, for the case in which the confinement effect is strong (i.e., d0 > h/2), d > d0 (i.e., the electrostatic effects swell the brushes), and an increase in salt concentration decreases the brush height. These findings reveal that the behavior of the end-charged brushes shows three unique differences when compared to that of the standard PE brushes with charges along their entire backbone. These differences are (a) the presence of a distinct role of the confinement in dictating how the electrostatic effects mediated by the electric double layer govern the height of end-charged brushes, (b) electrostatic-effect-driven shrinking of end-charged brushes for d0 < h/2 (for backbone-charged brushes, the electrostatic effects always swell the brushes), and (c) swelling of end-charged brushes with an increase in salt concentration for d0 < h/2 (backbone-charged brushes always shrink with an increase in salt concentration). Such unique effects of confinement and electrostatics on PE brushes have not been reported previously, and we anticipate that these findings will shed new light on the structure and properties of PE-brush-functionalized nanochannels with implications in applications such as fabrication of functionalized-nanochannel-based nanofluidic diodes, valves, biosensors, current rectifiers, and so forth.

Multipore membranes with nanofluidic diodes allowing multifunctional rectification and logical responses

We have arranged two multipore membranes with conical nanopores in a three-compartment electrochemical cell. The membranes act as tunable nanofluidic diodes whose functionality is entirely based on the pH-reversed ion current rectification and does not require specific surface functionalizations. This electrochemical arrangement can display different electrical behaviors (quasi-linear ohmic response and inward/outward rectifications) as a function of the electrolyte concentration in the external solutions and the applied voltage at the pore tips. The multifunctional response permits to implement different logical responses including NOR and INHIBIT functions.

The Influence of Divalent Anions on the Rectification Properties of Nanofluidic Diodes: Insights from Experiments and Theoretical Simulations.

During the last decade, the possibility of generating synthetic nanoarchitectures with functionalities comparable to biological entities has sparked the interest of the scientific community related to diverse research fields. In this context, gaining fundamental understanding of the central features that determine the rectifying characteristics of the conical nanopores is of mandatory importance. In this work, we analyze the influence of mono- and divalent salts in the ionic current transported by asymmetric nanopores and focus on the delicate interplay between ion exclusion and charge screening effects that govern the functional response of the nanofluidic device. Experiments were performed using KCl and K2 SO4 as representative species of singly and doubly charged species. Results showed that higher currents and rectification efficiencies are achieved by doubly charged salts. In order to understand the physicochemical processes underlying these effects simulations using the Poisson-Nernst-Planck formalism were performed. We consider that our theoretical and experimental account of the effect of divalent anions in the functional response of nanofluidic diodes provides further insights into the critical role of electrostatic interactions (ion exclusion versus charge screening effects) in presetting the ionic selectivity to anions as well as the observed rectification properties of these chemical nanodevices.

Zn(2+) and EDTA Cooperative Switchable Nanofluidic Diode Based on Asymmetric Modification of Single Nanochannel.

Design and fabrication of smart switchable nanofluidic diodes remains a challenge in the life and materials sciences. Here, we present the first example of a novel Zn(2+)/EDTA switchable nanofluidic diode system based on the control of one-side of the modified hourglass-shaped nanochannel with salicylaldehyde Schiff base (SASB). The nanofluidic diode can be turned on in the response of Zn(2+) and turned off in response to EDTA solution with good reversibility and recyclability.

Voltage-controlled current loops with nanofluidic diodes electrically coupled to solid state capacitors

Nanofluidic diodes electrically coupled to solid state capacitors show electrical properties reminiscent of a resistor with memory.

Designing voltage multipliers with nanofluidic diodes immersed in aqueous salt solutions.

Membranes with nanofluidic diodes allow the selective control of molecules in physiological salt solutions at ambient temperature. The electrical coupling of the membranes with conventional electronic elements such as capacitors suggests opportunities for the external monitoring of sensors and actuators. We demonstrate experimentally and theoretically the voltage multiplier functionality of simple electrical networks composed of membranes with conical nanopores coupled to load capacitors. The robust operation of half and full wave voltage multipliers is achieved in a broad range of experimental conditions (single pore and multipore membranes, electrolyte concentrations, voltage amplitudes, and solid-state capacitances). The designed voltage multipliers operate in the liquid state and can be used in sensing devices because different electrical, optical, and chemical inputs are known to modulate the individual nanofluidic diode resistances in the electrical network.

Universal low-frequency asymptotes of dynamic conic nanopore rectification: An ionic nanofluidic inductor.

We report the first nanofluidic inductor (L) to complement the known nanofluidic capacitors (C), resistors (R), and diodes for ion currents. Under negative bias, the nanopore behaves like a parallel RC circuit at low frequencies; however, under positive bias, the asymptotic dynamics is that of a serial RL circuit. This new ionic circuit element can lead to nanofluidic RLC or diode-inductor oscillator circuits and new intrapore biosensing/rapid sequencing strategies. A universal theory, with explicit estimates for the capacitance and inductance at opposite biases, is derived to collapse the rectified dynamics of all conic nanopores to facilitate design of this new nanofluidic circuit.

Nanofluidic Diodes with Dynamic Rectification Properties Stemming from Reversible Electrochemical Conversions in Conducting Polymers.

The use of solid state nanochannels as nanofluidic diodes is currently a topic of large interest in nanotechnology. Particularly, there is a focus in the development of nanochannels with surface functionalities that make them responsive to multiple environmental variables. Here, we present for the first time the construction of electrochemical potential- and pH-responsive nanofluidic diodes using a novel approach based on a controlled electrochemical polymerization of aniline on gold-coated polycarbonate asymmetric nanochannels. The polyaniline-modified nanochannels showed three different levels of reversible ionic rectification corresponding to the degrees of oxidation of the conducting polymer. Our results demonstrate that this strategy enables an accurate and reversible control of the rectification properties due to the well-defined and predictable electrochemical conversion of charged species generated on the pore walls. We envision that these results will create novel avenues to fabricate electrochemically modulated nanofluidic diodes using conducting polymers integrated into single conical nanopores.

Electrical network of nanofluidic diodes in electrolyte solutions: Connectivity and coupling to electronic elements

We consider a nanopore network with simple connectivity, demonstrating a two-dimensional circuit (full-wave rectifier) with ensembles of conical pores acting as nanofluidic diodes. When the bridge nanopore network is fed with an input potential signal of fluctuating polarity, a fixed output polarity is obtained. The full-wave rectification characteristics are demonstrated with square, sinusoidal, and white noise input waveforms. The charging of a load capacitor located between the two legs of the bridge demonstrates that the nanofluidic network is effectively coupled to this electronic element. These results can be relevant for energy transduction and storage procedures with nanopores immersed in electrolyte solutions. Because the individual nanofluidic resistances can be modulated by chemical, electrical, and optical signals, the balanced bridge circuit can also be useful to miniaturize nanopore-based sensing devices.

Modeling and Simulation of Thermo-Fluid-Electrochemical Ion Flow in Biological Channels

Abstract In this articlewe address the study of ion charge transport in the biological channels separating the intra and extracellular regions of a cell. The focus of the investigation is devoted to including thermal driving forces in the well-known velocity-extended Poisson-Nernst-Planck (vPNP) electrodiffusion model. Two extensions of the vPNP system are proposed: the velocity-extended Thermo-Hydrodynamic model (vTHD) and the velocity-extended Electro-Thermal model (vET). Both formulations are based on the principles of conservation of mass, momentum and energy, and collapse into the vPNP model under thermodynamical equilibrium conditions. Upon introducing a suitable one-dimensional geometrical representation of the channel,we discuss appropriate boundary conditions that depend only on effectively accessible measurable quantities. Then, we describe the novel models, the solution map used to iteratively solve them, and the mixed-hybrid flux-conservative stabilized finite element scheme used to discretize the linearized equations. Finally,we successfully apply our computational algorithms to the simulation of two different realistic biological channels: 1) the Gramicidin-A channel considered in [12]; and 2) the bipolar nanofluidic diode considered in [45].

Nanofluidic Diode for Simple Fluids without Moving Parts.

The fabrication of small scale, fixed structure fluidic diodes for simple fluids is quite challenging and has not yet been achieved. Here, we fabricate a moving part-free nanofluidic diode for simple fluids using heterogeneous nanochannels, half of which is hydrophilic and the other half is hydrophobic. It accepts water flows in the forward (from hydrophilic to hydrophobic) direction, while the flows in the backward direction are blocked for pressure drop range 0<ΔP<0.63 MPa. The diode is ensured by a potential energy barrier at the channel entrance on the hydrophobic side due to the molecular interactions between the water and channel surface. As the upstream pressure becomes higher than 0.63 MPa, the fluidic diode turns to be a rectifier, which allows flows in both the forward and backward directions but with different flow rates. At sufficiently high driving pressures, the fluidic system fails in flow rectification, analogous to the breakdown of electronic diodes. The three different flow modes (diode, rectifier, and breakdown) of the fluidic chip and the underlying rectification mechanisms are confirmed by molecular dynamics simulations.

A Bioinspired Switchable and Tunable Carbonate‐Activated Nanofluidic Diode Based on a Single Nanochannel

AbstractA smart nanofluidic diode that exhibits both ion gating and ion current rectification has been developed using a 1‐(4‐amino‐phenyl)‐2,2,2‐trifluoro‐ethanone‐functionalized, conical nanochannel in a polyimide (PI) membrane. The switch‐like property can be tuned by controlling the wettability and charge distribution with carbonate ions. Such a nanodevice is advantageous for precisely controlling conductive states with an ultrahigh gating ratio of up to 5000, and a high rectification ratio of 27. By virtue of the high selectivity and sensitivity for carbonate ions, this nanofluidic diode may find applications in carbonate or carbon dioxide detection.