Supramolecular Gating of Ion Transport in Nanochannels

Several covalent strategies towards surface charge‐reversal in nanochannels have been reported with the purpose of manipulating ion transport. However, covalent routes lack dynamism, modularity and post‐synthetic flexibility, and hence restrict their applicability in different environments. Here, we introduce a facile non‐covalent approach towards charge‐reversal in nanochannels (<10 nm) using strong charge‐transfer interactions between dicationic viologen (acceptor) and trianionic pyranine (donor). The polarity of ion transport was switched from anion selective to ambipolar to cation selective by controlling the extent of viologen bound to the pyranine. We could also regulate the ion transport with respect to pH by selecting a donor with pH‐responsive functional groups. The modularity of this approach further allows facile integration of various functional groups capable of responding to stimuli such as light and temperature to modulate the transport of ions as well as molecules.     

具有串/并联复合离子输运特性的仿生纳米通道的构筑与整流性能

人工构筑了基于分枝氧化铝纳米通道的串/并联复合的纳流体二极管体系, 其具有可调的离子整流性能. 在这种两级分枝结构的1-2-2, 1-2-3, 1-3-2和1-3-3型氧化铝纳米通道中, 若将每一个分枝节点等效为一个二极管, 那么其一级分枝节点相当于串联的1个二极管, 二级分枝节点相当于并联的多个二极管. 因此1-2-2和1-2-3型纳米通道的电路图可等效为并联的2个二极管与第3个二极管相串联, 1-3-2和1-3-3型纳米通道的电路图可等效为并联的3个二极管与第4个二极管相串联. 但由于1-2-2和1-2-3型以及1-3-2和1-3-3型的二级分枝的结构和数目不同, 可将这4种纳米通道等效为不同的串/并联复合特性的纳流体二极管体系, 并且表现出依次增大的离子整流. 即分枝氧化铝纳米通道内部一级分枝和二级分枝的结构或数目共同调控的表面电荷非对称性可以改变其离子整流性能. 进一步地, 具有代表性的1-2-2型分枝纳米通道的整流率随分枝通道长度的增加而增加, 这表明分枝部分对整个串/并联复合纳流体二极管的整流特性起到决定性的作用. 相比于以前的单个离子二极管体系, 这种具有串/并联复合特性的多级分枝氧化铝纳米通道将为构筑更复杂的仿生纳流体二极管的研究提供有价值的借鉴.     

Construction of biomimetic smart nanochannels with polymer membranes and application in energy conversion systems

Learning from nature has inspired the creation of intelligent devices to meet the increasing needs of the advanced community and also to better understand how to imitate biology. As one of biomimetic nanodevices, nanochannels or nanopores aroused particular interest because of their potential applications in nanofluidic devices, biosensing, filtration, and energy conversions. In this review we have summarized some recent results mainly focused on the design, construction and application in energy conversion systems. Like biological nanochannels, the prepared smart artificial nanochannels fabricated by ion track-etched polymer membranes and smart molecules show a great potential in the field of bioengineering and biotechnology. And these applications can not only help people to know and understand the living processes in nature, but can also inspire scientists to study and develop novel nanodevices with better performance for the mankind.     

The Combination of 2D Layered Graphene Oxide and 3D Porous Cellulose Heterogeneous Membranes for Nanofluidic Osmotic Power Generation

Salinity gradient energy, as a type of blue energy, is a promising sustainable energy source. Its energy conversion efficiency is significantly determined by the selective membranes. Recently, nanofluidic membrane made by two-dimensional (2D) nanomaterials (e.g., graphene) with densely packed nanochannels has been considered as a high-efficient membrane in the osmotic power generation research field. Herein, the graphene oxide-cellulose acetate (GO–CA) heterogeneous membrane was assembled by combining a porous CA membrane and a layered GO membrane; the combination of 2D nanochannels and 3D porous structures make it show high surface-charge-governed property and excellent ion transport stability, resulting in an efficient osmotic power harvesting. A power density of about 0.13 W/m² is achieved for the sea–river mimicking system and up to 0.55 W/m² at a 500-fold salinity gradient. With different functions, the CA and GO membranes served as ion storage layer and ion selection layer, respectively. The GO–CA heterogeneous membrane open a promising avenue for fabrication of porous and layered platform for wide potential applications, such as sustainable power generation, water purification, and seawater desalination.     

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

A 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.     

Numerical investigation of the current transition regimes in nanochannels

The concentration polarization phenomena and its effects represent one of the main challenges for the optimal operation of many nanofluidic systems. A numerical investigation of the different electric current transition regimes observed during the concentration polarization phenomena in nanochannels is performed. This included a 2D‐axisymmetric simulation of the nanofluidic system (reservoir‐nanochannel‐reservoir). From these simulations, a novel mechanism is discovered that explains that different current transition regimes. This driving mechanism involves the applied electric field penetration while the convective flow mechanism is found to be negligible. This differs with the classical statement that the mixing process with less depleted areas initiated by an electrokinetic vortex instability starts the overlimiting regime. Additionally, the numerical approach allows us to identify new characteristics of the linear‐limiting transition such as source‐like and saddle‐like points of the electric field streamlines. The three voltage–current regimes (linear, limiting and overlimiting) are explained by observing and quantifying changes in electric field, potential, ion concentration and ion concentration gradients within the system.     

Highly-Efficient Ion Gating through Self-Assembled Two-Dimensional Photothermal Metal-Organic Framework Membrane

Biological ion channels regulate the ion flow across cell membrane via opening or closing of the pores in response to various external stimuli. Replicating the function of high ion gating effects with artificial porous materials has been challenging. Herein, we report that the self-assembled two-dimensional metal-organic framework (MOF) membrane can serve as an excellent nanofluidic platform for smart regulation of ion transport. The MOF membrane with good photothermal performance exhibits extremely high ion gating ratio (up to 10⁴), which is among the highest values in MOF membrane nanochannels for light-controlled ion gating reported so far. By repeatedly turning on and off the light, the nanofluidic device shows outstanding stability and reversibility that can be applied in the remote light-switching system. This work may spark promising applications of MOF membrane with variety of stimuli responsive properties in ion sieving, biosensing, and energy conversion.     

Nanoconfinement Effects: Glucose Oxidase Reaction Kinetics in Nanofluidics

Size‐tunable nanofluidic devices coupled to an electrochemical detector have been designed and then used to study glucose oxidase (GOx) reaction kinetics confined in nanospaces. The devices are fabricated via a photochemical decomposition reaction, which forms nanochannels covered with carboxyl groups. The generated carboxyl groups enable us to chemically pattern biological molecules on the polymer surfaces via covalent bonding. With this approach, the activity of the immobilized biological molecules confined in nanospaces with different sizes has been investigated. GOx species are chemically immobilized on the surface of the nanochannels, catalyzing the oxidation of substrate glucose as it flows through the channels. The enzyme reaction product, hydrogen peroxide, passing through the nanochannels, reaches an electrochemical detector, giving rise to an increase in anodic current. This steady‐state electrochemical current, which responds to various glucose concentrations, can be used to evaluate the GOx activity under confinement conditions. The results show significant nanoconfinement effects that are dependent on the channel size where the reaction occurs, demonstrating the importance of spatial confinement on the GOx reaction kinetics. The present approach provides an effective method for the study of enzyme activity and other bioassay systems, such as cell assays, drug discovery, and clinical diagnosis.     

Oppositely Charged Ti3C2Tx MXene Membranes with 2D Nanofluidic Channels for Osmotic Energy Harvesting

Membrane‐based reverse electrodialysis (RED) is considered as the most promising technique to harvest osmotic energy. However, the traditional membranes are limited by high internal resistance and low efficiency, resulting in undesirable power densities. Herein, we report the combination of oppositely charged Ti₃C₂T_x MXene membranes (MXMs) with confined 2D nanofluidic channels as high‐performance osmotic power generators. The negatively or positively charged 2D MXene nanochannels exhibit typical surface‐charge‐governed ion transport and show excellent cation or anion selectivity. By mixing the artificial sea water (0.5 m NaCl) and river water (0.01 m NaCl), we obtain a maximum power density of ca. 4.6 Wm^?2, higher than most of the state‐of‐the‐art membrane‐based osmotic power generators, and very close to the commercialization benchmark (5 Wm^?2). Through connecting ten tandem MXM‐RED stacks, the output voltage can reach up 1.66 V, which can directly power the electronic devices.     

Complete plastic nanofluidic devices for DNA analysis via direct imprinting with polymer stamps

Development of all polymer-based nanofluidic devices using replication technologies, which is a prerequisite for providing devices for a larger user base, is hampered by undesired substrate deformation associated with the replication of multi-scale structures. Therefore, most nanofluidic devices have been fabricated in glass-like substrates or in a polymer resist layer coated on a substrate. This letter presents a rapid, high fidelity direct imprinting process to build polymer nanofluidic devices in a single step. Undesired substrate deformation during imprinting was significantly reduced through the use of a polymer stamp made from a UV-curable resin. The integrity of the enclosed all polymer-based nanofluidic system was verified by a fluorescein filling experiment and translocation/stretching of λ-DNA molecules through the nanochannels. It was also found that the funnel-like design of the nanochannel inlet significantly improved the entrance of DNA molecules into nanochannels compared to an abrupt nanochannel/microfluidic network interface.     

pH gated glucose responsive biomimetic single nanochannels

The development of pH gated glucose (Glu) biosensor is of great significance to human health. Herein, we have designed a pH gated Glu responsive biomimetic nanochannel, modified with 3-aminobenzeneboronic acid. The Glu responsive property can be regulated by pH which can switch nanochannels from the "on" to "off" state.     

Engineering a NO-Regulated Nanofluidic Sensor through the Cyclization Reaction Strategy

Nitric oxide (NO) is known to be a secondary in vivo signaling agent, demonstrating various biological functions through regulating ion flux in channels. Considering the crucial role of NO in vivo, herein, a biomimetic NO-regulated nanofluidic sensor has been fabricated through a cyclization reaction strategy. This nanofluidic sensor exhibited a promising NO selectivity, sensitivity, and non-interference performance in complex matrices. Thus, such a NO-driven nanosensor will be meaningful for scientific researchers to grasp the in vivo functions of NO.     

Ion transport regulation through triblock copolymer/PET asymmetric nanochannel membrane:Model system establishment and rectification mapping

Controlling ions transport across the membrane at different pH environments is essential for the physiological process and artificial systems.Many efforts have been devoted to pH-responsive ion gating,while rarely systems can maintain the rectification in pH-changing environments.Here,a composite nanochannel system is fabricated,which shows unidirectional rectification with high performance in a wide pH range.In the system,block copolymer(BCP) and polyethylene te rephthalate(PET) are employed for the amphoteric nanochannels fabrication.Based on the composite system,a model is built for the theoretical simulation.Thereafter,rectification mapping is conducted on the system,which can provide abundant info rmation about the relations between charge distribution and ions transport prope rties.The proposed rectification mapping can definitely help to design new materials with special ion transport properties,such as high-performance membranes used in the salinity gradient power generation field.     

Design and Fabrication of a Biomimetic Nanochannel for Highly Sensitive Arginine Response in Serum Samples

Inspired from their biological counterparts, chemical modification of the interior surface of nanochannels with functional molecules may provide a highly efficient means to control ionic or molecular transport through nanochannels. Herein, we have designed and prepared a aldehyde calix[4]arene (C4AH), which was attached to the interior surface of a single nanochannel by using a click reaction, and that showed a high response for arginine (Arg). Furthermore, the nanofluidic sensing system has been challenged with complex matrices containing a high concentration of interfering sequences and serum. Based on this finding, we believe that the artificial nanochannel can be used for practical Arg‐sensing devices, and be applied in a biological environment.     

Efficient Gating of Ion Transport in Three‐Dimensional Metal–Organic Framework Sub‐Nanochannels with Confined Light‐Responsive Azobenzene Molecules

1D nanochannels modified with responsive molecules are fabricated to replicate gating functionalities of biological ion channels, but gating effects are usually weak because small molecular gates cannot efficiently block the large channels in the closed states. Now, 3D metal–organic framework (MOF) sub‐nanochannels (SNCs) confined with azobenzene (AZO) molecules achieve efficient light‐gating functionalities. The 3D MOFSNCs consisting of a MOF UiO66 with ca. 9–12 Å cavities connected by ca. 6 Å triangular windows work as angstrom‐scale ion channels, while confined AZO within the MOF cavities function as light‐driven molecular gates to efficiently regulate the ion flux. The AZO‐MOFSNCs show good cyclic gating performance and high on–off ratios up to 17.8, an order of magnitude higher than ratios observed in conventional 1D AZO‐modified nanochannels (1.3–1.5). This work provides a strategy to develop highly efficient switchable ion channels based on 3D porous MOFs and small responsive molecules.     

Biomimetic Ion Nanochannels as a Highly Selective Sequential Sensor for Zinc Ions Followed by Phosphate Anions

A novel biomimetic ion‐responsive multi‐nanochannel system is constructed by covalently immobilizing a metal‐chelating ligand, 2,2′‐dipicolylamine (DPA), in polyporous nanochannels prepared in a polymeric membrane. The DPA‐modified multi‐nanochannels show specific recognition of zinc ions over other common metal ions, and the zinc‐ion‐chelated nanochannels can be used as secondary sensors for HPO₄^2? anions. The immobilized DPA molecules act as specific‐receptor binding sites for zinc ions, which leads to the highly selective zinc‐ion response through monitoring of ionic current signatures. The chelated zinc ions can be used as secondary recognition elements for the capture of HPO₄^2? anions, thereby fabricating a sensing nanodevice for HPO₄^2? anions. The success of the DPA immobilization and ion‐responsive events is confirmed by measurement of the X‐ray photoelectron spectroscopy (XPS), contact angle (CA), and current–voltage (I–V) characteristics of the systems. The proposed nanochannel sensing devices display remarkable specificity, high sensitivity, and wide dynamic range. In addition, control experiments performed in complex matrices suggest that this sensing system has great potential applications in chemical sensing, biotechnology, and many other fields.     

Effect of solution chemistry on the surface charge of polymeric reverse osmosis and nanofiltration membranes

A streaming potential analyzer has been used to investigate the effect of solution chemistry on the surface charge of four commercial reverse osmosis and nanofiltration membranes. Zeta potentials of these membranes were analyzed for aqueous solutions of various chemical compositions over a pH range of 2 to 9. In the presence of an indifferent electrolyte (NaCl), the isoelectric points of these membranes range from 3.0 to 5.2. The curves of zeta potential versus solution pH for all membranes display a shape characteristic of amphoteric surfaces with acidic and basic functional groups. Results with salts containing divalent ions (CaCl₂, Na₂SO₄, and MgSO₄) indicate that divalent cations more readily adsorb to the membrane surface than divalent anions, especially in the higher pH range. Three sources of humic acid, Suwannee River humic acid, peat humic acid, and Aldrich humic acid, were used to investigate the effect of dissolved natural organic matter on membrane surface charge. Other solution chemistries involved in this investigation include an anionic surfactant (sodium dodecyl sulfate) and a cationic surfactant (dodecyltrimethylammonium bromide). Results show that humic substances and surfactants readily adsorb to the membrane surface and markedly influence the membrane surface charge.     

Stability Enhancement of All‐Solid‐State H+ ISEs with Cross‐Linked Silicon‐Urethane Matrices

An all‐solid‐state hydrogen‐ion‐selective electrode (ASHISE) was fabricated using the polymer hybrid membrane. Polymer membranes composed of Tecoflex polyurethane (TPU), polyvinyl chloride (PVC), silicon rubber (SR), and additives (KTpClPB, DOA, and TDDA) were cast on a carbon rod. The TPU/SR hybrid membrane exhibited a longer lifetime and a higher sensitivity in the sensing of the H⁺ ion compared to conventional TPU/PVC and PVC/SR hybrid membranes. Moreover, the addition of SiCl₄ to TPU‐based matrices enhanced the potentiometric response and ISE stability, due to the chemical bonding between Si and C?O in urethane, in which the cross‐linking configuration was confirmed by DSC, FT‐IR, and XPS experiments. TPU/SR membranes containing SiCl₄ were rendered more stable and showed a pH response over a wide range (i.e., pH 2–11.5) with the slope of 60±2 mV/pH for more than four months. The ASHISE exhibited a small interfering potential variation in the wide range of the salt concentration (from 1.0×10^?6 M up to 0.1 M). The ASHISE showed a result comparable to a commercial clinical blood analyzer.     

Synthesis and properties of amphoteric copolymer of 5‐vinyltetrazole and vinylbenzyl phosphonic acid

Amphoteric polymers have been studied for various applications such as separation of low molecular weight organic molecules from inorganic salt mixtures, selective ion transport, drug delivery through membranes of biological interest, separation of ionic drugs and proteins, and separation of alcohol and water. Typical amphoteric polymers consist of weak base and weak acid groups. In present study, the copolymerization of 5‐vinyltetrazole (VT) and diisopropyl‐p‐vinylbenzyl phosphate (DIPVBP) via free radical polymerization is studied. The reactivity ratio of VT and DIPVBP, which is calculated from Kelen‐Tudos plot, is 0.251 and 0.345, respectively. The amphoteric copolymer of VT and diisopropyl‐p‐vinylbenzyl phosphonic acid (poly(VT‐co‐VBPA)) is obtained from hydrolysis of the copolymer of VT and DIPVBP (poly(VT‐co‐DIPVBP)). Poly(VT‐co‐VBPA) is thermally stable under 190 °C. The anhydrous proton conductivity of amphoteric poly(VT‐co‐VBPA) can reach 1.54 × 10^‐4 S cm^?1 at 170 °C with an activation energy of 114.7 kJ mol^?1. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3486–3493     

Ionic conductance of nanopores in microscale analysis systems: where microfluidics meets nanofluidics

In this tutorial review we illustrate the origin and dependence on various system parameters of the ionic conductance that exists in discrete nanochannels as well as in nanoporous separation and preconcentration units contained as hybrid configurations, membranes, packed beds, or monoliths in microscale liquid phase analysis systems. A particular complexity arises as external electrical fields are superimposed on internal chemical and electrical potential gradients for tailoring molecular transport. It is demonstrated that the variety of geometries in which the microfluidic/nanofluidic interfaces are realized share common, fundamental features of coupled mass and charge transport, but that phenomena behind the key steps in a particular application can be significantly tuned, depending on the morphology of a material. Thus, the understanding of morphology-related transport in internal and external electrical potential gradients is critical to the performance of a device. This addresses a variety of geometries (slits, channels, filters, membranes, random or regular networks of pores, etc.) and applications, e. g., the gating, sensing, preconcentration, and separation in multifunctional miniaturized devices. Inherently coupled mass and charge transport through ion-permselective (charge-selective) microfluidic/nanofluidic interfaces is analyzed with a stepwise-added complexity and discussed with respect to the morphology of the charge-selective spatial domains. Within this scenario, the electrostatics and electrokinetics in microfluidic and nanofluidic channels, as well as the electrohydrodynamics evolving at microfluidic/nanofluidic interfaces, where microfluidics meets nanofluidics, define the platform of central phenomena.