Biomimetic smart nanopores and nanochannels

Nature provides a huge range of biological materials, just as ion channels, with various smart functions over millions of years of evolution, and which serve as a big source of bio-inspiration for biomimetic materials. In this critical review, a strategy for the design and synthesis of biomimetic smart nanopores and nanochannels is presented and put into context with recent progress in this rapidly growing field from biological, inorganic, organic to composite nanopore and nanochannel materials, which can respond to single/multiple external stimuli, e.g., pH, temperature, light, and so on. This review is intended to utilize a specific responsive behavior for regulating ionic transport properties inside the single nanopore or nanochannel as an example to demonstrate the feasibility of the design strategy, and provide an overview of this fascinating research field (109 references).     

Building bio-inspired artificial functional nanochannels: from symmetric to asymmetric modification

Over millions of years, complex processes of intelligent control have evolved in nature. Learning from nature is a continuing theme in the development of smart materials and intelligent systems. For example, biological nanochannels, which are typically ion channels, play a very important role in basic biochemical processes in cells. Inspired by ion channels, in which the components are asymmetrically distributed between the membrane surfaces, the generation of biomimetic smart nanochannels is a broad and varied scientific research field. The design and development of new biomimetic channels includes the use of different shapes of channels, different stimuli-responsive molecules, and different symmetric/asymmetric modification methods. In this Minireview, we summarize recent developments in building functional nanochannels by applying various symmetric and asymmetric modifications.     

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.     

异质膜纳米通道的构建及其应用研究

从生物体离子通道中得到启发,研究人员开发了一系列仿生纳米通道,通过对内外表面的化学修饰,实现了在仿生纳米通道受限空间内离子转运的智能调控.目前的研究主要集中在均质膜方向,均质膜单一的结构和功能限制了其进一步发展,研发制备过程简单、稳定性好和功能多样的异质膜逐渐成为研究热点.与均质膜相比,异质膜被赋予单独使用均质膜时无法...     

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.     

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.     

Construction and application of bioinspired nanochannels based on two-dimensional materials

With the development of nanotechnology and materials science, bioinspired nanochannels appeared by mimicking the intelligent functions of biological ion channels. They have attracted a great deal of attention in recent years due to their controllable structure and tunable chemical properties. Inspired by the layered microstructure of nacre, 2D layered materials as excellent matrix material of nanochannel come into our field of vision. Bionic nanochannels based on 2D materials have the advantages...     

Stimulus‐Responsive Metal–Organic Frameworks

Materials that can recognize the changes in their local environment and respond by altering their inherent physical and/or chemical properties are strong candidates for future “smart” technology materials. Metal–organic frameworks (MOFs) have attracted a great deal of attention in recent years owing to their designable architecture, host–guest chemistry, and softness as porous materials. Despite this fact, studies on the tuning of the properties of MOFs by external stimuli are still rare. This review highlights the recent developments in the field of stimulus‐responsive MOFs or so‐called smart MOFs. In particular, the various stimuli used and the utility of stimulus‐responsive smart MOFs for various applications such as gas storage and separation, sensing, clean energy, catalysis, molecular motors, and biomedical applications are highlighted by using representative examples. Future directions in the developments of stimulus‐responsive smart MOFs and their applications are proposed from a personal perspective.     

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.     

Metal–Organic Framework Membrane Nanopores as Biomimetic Photoresponsive Ion Channels and Photodriven Ion Pumps

Biological ion channels and ion pumps with sub‐nanometer sizes modulate ion transport in response to external stimuli. Realizing such functions with sub‐nanometer solid‐state nanopores has been an important topic with wide practical applications. Herein, we demonstrate a biomimetic photoresponsive ion channel and photodriven ion pump using a porphyrin‐based metal–organic framework membrane with pore sizes comparable to hydrated ions. We show that the molecular‐size pores enable precise and robust optoelectronic ion transport modulation in a broad range of concentrations, unparalleled with conventional solid‐state nanopores. Upon decoration with platinum nanoparticles to form a Schottky barrier photodiode, photovoltage across the membrane is generated with “uphill” ion transport from low concentration to high concentration. These results may spark applications in energy conversion, ion sieving, and artificial photosynthesis.     

Multi‐Stimuli‐Responsive Polymeric Materials

Stimuli‐responsive materials are of immense importance because of their ability to undergo alteration of their properties in response to their environment. The properties of such materials can be tuned by subtle adjustments in temperature, pH, light, and so forth. Among such smart materials, multi‐stimuli‐responsive polymeric materials are of pronounced significance as they offer a wide range of applications and their properties can be tuned through several mechanisms. Here, we aim to highlight some recent studies showcasing the multi‐stimuli‐responsive character of these polymers, which are still relatively little known compared to their single‐stimuli‐responsive counterpart.     

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.     

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.     

Stimuli‐Responsive Supramolecular Hydrogels and Their Applications in Regenerative Medicine

Supramolecular hydrogels are a class of self‐assembled network structures formed via non‐covalent interactions of the hydrogelators. These hydrogels capable of responding to external stimuli are considered to be smart materials due to their ability to undergo sol–gel and/or gel–sol transition upon subtle changes in their surroundings. Such stimuli‐responsive hydrogels are intriguing biomaterials with applications in tissue engineering, delivery of cells and drugs, modulating tissue environment to promote innate tissue repair, and imaging for medical diagnostics among others. This review summarizes the recent developments in stimuli‐responsive supramolecular hydrogels and their potential applications in regenerative medicine. Specifically, various structural aspects of supramolecular hydrogelators involved in self‐assembly, the role of external stimuli in tuning/controlling their phase transitions, and how these functions could be harnessed to advance applications in regenerative medicine are focused on. Finally, the key challenges and future prospects for these versatile materials are briefly described.     

Multi‐Stimuli‐Responsive Polymer Materials: Particles,Films, and Bulk Gels

Stimuli‐responsive polymers have received tremendous attention from scientists and engineers for several decades due to the wide applications of these smart materials in biotechnology and nanotechnology. Driven by the complex functions of living systems, multi‐stimuli‐responsive polymer materials have been designed and developed in recent years. Compared with conventional single‐ or dual‐stimuli‐based polymer materials, multi‐stimuli‐responsive polymer materials would be more intriguing since more functions and finer modulations can be achieved through more parameters. This critical review highlights the recent advances in this area and focuses on three types of multi‐stimuli‐responsive polymer materials, namely, multi‐stimuli‐responsive particles (micelles, micro/nanogels, vesicles, and hybrid particles), multi‐stimuli‐responsive films (polymer brushes, layer‐by‐layer polymer films, and porous membranes), and multi‐stimuli‐responsive bulk gels (hydrogels, organogels, and metallogels) from recent publications. Various stimuli, such as light, temperature, pH, reduction/oxidation, enzymes, ions, glucose, ultrasound, magnetic fields, mechanical stress, solvent, voltage, and electrochemistry, have been combined to switch the functions of polymers. The polymer design, preparation, and function of multi‐stimuli‐responsive particles, films, and bulk gels are comprehensively discussed here.     

Stimuli‐Responsive Water‐Soluble Fullerene (C60) Polymeric Systems

This review documents the advances in stimuli‐responsive water‐soluble fullerene (C₆₀) polymeric systems. Stimuli‐responsive polymers, when grafted onto C₆₀ impart “smart” and “responsive” characteristics, and these novel materials adopt various morphologies when subjected to external stimuli, such as pH, temperature, and salt. Various synthetic approaches for producing C₆₀‐polymers are outlined and discussed. The responsive behavior, water solubility, and self‐assembly characteristics of these C₆₀‐polymers make them attractive for applications such as drug delivery, temperature sensors, and personal care.     

Supramolecular Vesicles Coassembled from Disulfide‐Linked Benzimidazolium Amphiphiles and Carboxylate‐Substituted Pillar[6]arenes that Are Responsive to Five Stimuli

Novel supramolecular vesicles based on host–guest systems were coassembled from carboxylate‐substituted pillar[6]arene (CPA[6]) and disulfide‐linked benzimidazolium amphiphiles, and the microstructures of the CPA‐based supramolecular vesicles were clearly elaborated. The supramolecular vesicles showed controlled drug release in response to five stimuli, with glutathione, pH, CO₂, Zn²⁺ ions, and hexanediamine, leading to cleavage of the disulfide bonds, protonation of the carboxylate groups, metal chelation, and competitive binding. This is the first case of a smart pillararene‐based supramolecular vesicle being integrated with five stimuli‐responsive functions to meet the diverse requirements of controlled drug release. Importantly, each of the five stimuli is closely related to microenvironments of tumors and diseases of the human body. The smart stimuli‐responsive supramolecular vesicles have promising applications in drug therapy of tumors and relevant diseases.     

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.     

A Tunable Ionic Diode Based on a Biomimetic Structure‐Tailorable Nanochannel

A tunable ionic diode is presented that is based on biomimetic structure‐tailorable nanochannels, with precise ion‐transport characteristics from ohmic behavior to bidirectional rectification as well as gating properties. The forward/reverse directions of the ionic diode and the degree of rectification can be well‐regulated by combining the patterned surface charge and the sophisticated structure. This system creates an ideal platform for precise transportation of ions and molecules, and potential applications in analytical sciences are anticipated.