Positively K+‐Responsive Membranes with Functional Gates Driven by Host–Guest Molecular Recognition

A novel positively K⁺‐responsive membrane with functional gates driven by host‐guest molecular recognition is prepared by grafting poly(N‐isopropylacrylamide‐co‐acryloylamidobenzo‐15‐crown‐5) (poly(NIPAM‐co‐AAB₁₅C₅)) copolymer chains in the pores of porous nylon‐6 membranes with a two‐step method combining plasma‐induced pore‐filling grafting polymerization and chemical modification. Due to the cooperative interaction of host‐guest complexation and phase transition of the poly(NIPAM‐co‐AAB₁₅C₅), the grafted gates in the membrane pores could spontaneously switch from “closed” state to “open” state by recognizing K⁺ ions in the environment and vice versa; while other ions (e.g., Na⁺, Ca²⁺ or Mg²⁺) can not trigger such an ion‐responsive switching function. The positively K⁺‐responsive gating action of the membrane is rapid, reversible, and reproducible. The proposed K⁺‐responsive gating membrane provide a new mode of behavior for ion‐recognizable “smart” or “intelligent” membrane actuators, which is highly attractive for controlled release, chemical/biomedical separations, tissue engineering, sensors, etc.     

Organic Proton‐Conducting Molecules as Solid‐State Separator Materials for Fuel Cell Applications

Organic proton‐conducting molecules are presented as alternative materials to state‐of‐the‐art polymers used as electrolytes in proton‐exchanging membrane (PEM) fuel cells. Instead of influencing proton conductivity via the mobility offered by polymeric materials, the goal is to create organic molecules that control the proton‐transport mechanism through supramolecular order. Therefore, a series of phosphonic acid‐containing molecules possessing a carbon‐rich hydrophobic core and a hydrophilic periphery was synthesized and characterized. Proton conductivity measurements as well as water uptake and crystallinity studies (powder and single‐crystal X‐ray analysis) were performed under various conditions. These experiments reveal that proton mobility is closely connected to crystallinity and strongly dependent on the supramolecular ordering of the compound. This study provides insights into the proton‐conducting properties of this novel class of materials and the mechanisms responsible for proton transport.     

Droplet and Fluid Gating by Biomimetic Janus Membranes

The ability to gate (i.e., allow or block) droplet and fluid transport in a directional manner represents an important form of liquid manipulation and has tremendous application potential in fields involving intelligent liquid management. Inspired by passive transport across cell membranes which regulate permeability by transmembrane hydrophilic/hydrophobic interactions, macroscopic hydrophilic/hydrophobic Janus‐type membranes are prepared by facile vapor diffusion or plasma treatments for liquid gating. The resultant Janus membrane shows directional water droplet gating behavior in air‐water systems. Furthermore, membrane‐based directional gating of continuous water flow is demonstrated for the first time, enabling Janus membranes to act as facile fluid diodes for one‐way flow regulation. Additionally, in oil‐water systems, the Janus membranes show directional gating of droplets with integrated selectivity for either oil or water. The above remarkable gating properties of the Janus membranes could bring about novel applications in fluid rectifying, microchemical reaction manipulation, advanced separation, biomedical materials and smart textiles.     

Self‐Healing Actuating Adhesive Based on Polyelectrolyte Multilayers

Creating actuators capable of mechanical motion in response to external stimuli is a key for design and preparation of smart materials. The lifetime of such materials is limited by their eventual wear. Here, self‐healable and adhesive actuating materials are demonstrated by taking advantage of the solvent responsive of weak polyelectrolyte multilayers consisting of branched poly(ethylenimine)/poly(acrylic acid) (BPEI/PAA). BPEI/PAA multilayers are dehydrated and contract upon contact with organic solvent and become sticky when wetted with water. By constructing an asymmetric heterostructure consisting of a responsive BPEI/PAA multilayer block and a nonresponsive component through either layer‐by‐layer assembly or the paste‐to‐curl process, smart films that actuate upon exposure to alcohol are realized. The curl degree, defined as degrees from horizontal that the actuated material reaches, can be as high as ≈228.9°. With evaporation of the ethanol, the curled film returns to its initial state, and water triggers fast self‐healing extends the actuator's lifetime. Meanwhile, the adhesive nature of the wet material allows it to be attached to various substrates for possible combination with hydrophobic functional surfaces and/or applications in biological environments. This self‐healable adhesive for controlled fast actuation represents a considerable advance in polyelectrolyte multilayers for design and fabrication of robust smart advanced materials.     

Light‐Switchable Single‐Walled Carbon Nanotubes Based on Host–Guest Chemistry

A new type of light‐switchable “smart” single‐walled carbon nanotube (SWNTs) is developed by the reversible host–guest interaction between azobenzene‐terminal PEO (AzoPEO) and pyrene‐labeled host attached on the sidewalls of nanotubes via π–π stacking. The SWNTs hybrids not only are well dispersed in pure water, but also exhibit switchable dispersion/aggregation states upon the alternate irradiation of UV and visible light. Moreover, the SWNTs hybrids dispersion is preliminarily used as coating fluid to form transparent conductive films. The dispersant AzoPEO is removed by the contamination‐free UV treatment, decreasing the resistance of the films. This kind of light‐switchable SWNTs hybrids, possessing a ‘‘green’’ trigger and intact structure of the nanotube, may find potential applications in sensor of biomedicines, device fabrication, etc. Additionally, such a reversible host–guest interaction system may open up the possibility to control the dispersion state of SWNTs by other common polymers.     

pH‐Responsive Round‐Way Motions of a Smart Device through Integrating Two Types of Chemical Actuators in One Smart System

Smart motions of objects from the submicrometer to millimeter scale through chemical control with stimulus‐responsive way are significant to achieve various applications. However, the intelligence of the current devices with chemical responding system remains to be improved; especially, achieving a round‐way motion is still a challenge. Therefore, two types of actuators are simultaneously integrated into single smart device at the opposite ends to achieve cooperated functions in an orderly manner. One actuator is the pH‐responsive power supply of hydrogen bubbles produced from the reaction between magnesium and HCl. The smart device undergoes on–off–on locomotion through control over the solution pH values by using the pH‐responsive actuator of magnesium–HCl system. The other actuator is the hydrogen peroxide‐responsive system of oxygen bubbles generated through the decomposition of hydrogen peroxide catalyzed by platinum aggregates. When introducing hydrogen peroxide solution into the system, the generated oxygen bubbles at the opposite end of the device to push the device backward for round‐way motions. For the first time, two different types of actuators are simultaneously integrated into single smart device without disturbing each other, which realize pH‐responsive round‐way motions of the smart device and improve the system intelligence for further applications.     

Polymer‐Modified Mesoporous Silica Thin Films for Redox‐Mediated Selective Membrane Gating

Controlling structure and function to switch ionic transport through synthetic membranes is a major challenge in the fabrication of functional nanodevices. Here we describe the combination of mesoporous silica thin films as structural unit, functionalized with two different redox‐responsive ferrocene‐containing polymers, polyvinylferrocene (PVFc) and poly(2‐(methacryloyloxy)ethyl ferrocenecarboxylate) (PFcMA), by using either a grafting to, or a grafting from approach. Both mesoporous film functionalization strategies are investigated in terms of polymer effect on ionic permselectivity. A significantly different ionic permselective behavior can be observed. This is attributed to different polymer location within the mesoporous film, depending on the functionalization strategies used. Additionally, the influence of chemical oxidation on the ionic permselective behavior is studied by cyclic voltammetry showing a redox‐controlled membrane gating as function of polymer location and the pH value. This study is a first step of combining redox‐responsive ferrocene‐containing polymers and mesoporous membranes, and thus towards redox‐controlled ionic transport through nanopores.     

Dynamically Gas‐Phase Switchable Super(de)wetting States by Reversible Amphiphilic Functionalization: A Powerful Approach for Smart Fluid Gating Membranes

In nature, cellular membranes perform critical functions such as endocytosis and exocytosis through smart fluid gating processes mediated by nonspecific amphiphilic interactions. Despite considerable progress, artificial fluid gating membranes still rely on laborious stimuli‐responsive mechanisms and triggering systems. In this study, a room temperature gas‐phase approach is presented for dynamically switching a porous material from a superhydrophobic to a superhydrophilic wetting state and back. This is realized by the reversible attachment of bipolar amphiphiles, which promote surface wetting. Application of this reversible amphiphilic functionalization to an impermeable nanofibrous membrane induces a temporary state of superhydrophilicity resulting in its pressure‐less permeation. This mechanism allows for rapid smart fluid gating processes that can be triggered at room temperature by variations in the environment of the membrane. Owing to the universal adsorption of volatile amphiphiles on surfaces, this approach is applicable to a broad range of materials and geometries enabling facile fabrication of valve‐less flow systems, fluid‐erasable microfluidic arrays, and sophisticated microfluidic designs.     

High‐Efficiency Water‐Transport Channels using the Synergistic Effect of a Hydrophilic Polymer and Graphene Oxide Laminates

Graphene oxide (GO) laminates possess unprecedented fast water‐transport channels. However, how to fully utilize these unique channels in order to maximize the separation properties of GO laminates remains a challenge. Here, a bio‐inspired membrane that couples an ultrathin surface water‐capturing polymeric layer (<10 nm) and GO laminates is designed. The proposed synergistic effect of highly enhanced water sorption from the polymeric layer and molecular channels from the GO laminates realizes fast and selective water transport through the integrated membrane. The prepared membrane exhibits highly selective water permeation with an excellent water flux of over 10 000 g m^?2 h^?1, which exceeds the performance upper bound of state‐of‐the‐art membranes for butanol dehydration. This bio‐inspired strategy demonstrated here opens the door to explore fast and selective channels derived from 2D or 3D materials for highly efficient molecular separation.     

2D Laminar Membranes for Selective Water and Ion Transport

Selective water and ion transport are essential in fields related to the environment, resources, energy, and more. Membranes, especially those constituted by 2D materials, are promising to control mass transport within nano‐ and sub‐nanoscales. When stacked together, the ultrathin nanosheets of these materials can build up laminar membranes with an ordered layer‐like structure. Numerous channels are thereby created among layers for fast and selective mass transport, which arouses huge research and application interests. This Review aims to present the latest theoretical and experimental advances of 2D laminar membranes for selective water and ion transport, covering three fundamental aspects. Starting with a concise introduction to the materials and assembly for laminar membranes, it then mainly focuses on systematically discussing the transport‐controlling effects caused by intrinsic membrane structure and extrinsic influences. The relation between these effects and current membrane selective performance as well as future membrane designs is then elucidated. The most urgent challenges and corresponding opportunities that emerge around 2D laminar membranes are highlighted thereafter.     

Ultra‐Thin Self‐Assembled Protein‐Polymer Membranes: A New Pore Forming Strategy

Self‐assembled membranes offer a promising alternative for conventional membrane fabrication, especially in the field of ultrafiltration. Here, a new pore‐making strategy is introduced involving stimuli responsive protein‐polymer conjugates self‐assembled across a large surface area using drying‐mediated interfacial self‐assembly. The membrane is flexible and assembled on porous supports. The protein used is the cage protein ferritin and resides within the polymer matrix. Upon denaturation of ferritin, a pore is formed which intrinsically is determined by the size of the protein and how it resides in the matrix. Due to the self‐assembly at interfaces, the membrane constitutes of only one layer resulting in a membrane thickness of 7 nm on average in the dry state. The membrane is stable up to at least 50 mbar transmembrane pressure, operating at a flux of about 21 000–25 000 L m^?2 h^?1 bar^?1 and displayed a preferred size selectivity of particles below 20 nm. This approach diversifies membrane technology generating a platform for “smart” self‐assembled membranes.     

Preprogrammed Dynamic Microstructured Polymer Interfaces

The advancement of new‐generation complex integrated responsive systems depends on the progress in the development of functional stimuli‐responsive polymer components that could be put together and engineered to perform in concert as an ensemble. This progress report highlights recent substantial progress in the development of such soft‐matter components capable of changes according to preprogrammed scenarios. The components interact via interfaces that play a key role in the performance of the microstructured materials. The list of the most important properties that can be changed by altering the interfaces upon external stimuli includes gating, transport, release, wetting, adhesion, and self‐regeneration (healing) realized in different architectures of soft stimuli‐responsive materials.     

Layer‐by‐Layer Assembly of Light‐Responsive Polymeric Multilayer Systems

Layer‐by‐Layer (LbL) assembly is a simple and highly versatile method to modify surfaces and fabricate robust and highly‐ordered nanostructured coatings over almost any type of substrate. Such versatility enables the incorporation of a plethora of building blocks, including materials exhibiting switchable properties, in a single device through a multitude of complementary intermolecular interactions. Switchable materials may undergo reversible physicochemical changes in response to a variety of external triggers. Although most of the works in the literature have been focusing on stimuli‐responsive materials that are sensitive to common triggers such as pH, ionic strength, or temperature, much less has been discussed on LbL systems which are sensitive to non‐invasive and easily controlled light stimulus, despite its unique potential. This review provides a deep overview of the recent progresses achieved in the design and fabrication of light‐responsive LbL polymeric multilayer systems, their potential future challenges and opportunities, and possible applications. Many examples are given on light‐responsive polymeric multilayer assemblies built from metal nanoparticles, functional dyes, and metal oxides. Such stimuli‐responsive functional materials, and combinations among them, may lead to novel and highly promising nanostructured smart functional systems well‐suited for a wide range of research fields, including biomedicine and biotechnology.     

Carbon Fiber–Bismaleimide Composites Filled with Nickel‐Coated Single‐Walled Carbon Nanotubes for Lightning‐Strike Protection

Multifunctional carbon fiber composites are imperative for next‐generation lightweight aircraft structures. However, lightning‐strike protection is a feature that is lacking in many modern carbon fiber high‐temperature polymer systems, due to their high electrical resistivity. This work presents a study on processing, materials optimization, and property development of high‐temperature bismaleimide (BMI)–carbon fiber composites filled with nickel‐coated single‐walled carbon nanotubes (Ni‐SWNTs) based on three key factors: i) dispersion of Ni‐SWNTs, ii) their surface coverage on the carbon plies and, iii) the composite surface resistivity. Atomic force microscopy analysis revealed that coating purified SWNTs with nickel enabled improved dispersion which resulted in uniform surface coverage on the carbon plies. The electrical resistivity of the baseline composite system was reduced by ten orders of magnitude by the addition of 4 wt% Ni‐SWNTs (calculated with respect to the weight of a single carbon ply). Ni‐SWNT–filled composites showed a reduced amount of damage to simulated lightning strike compared to their unfilled counterparts, as indicated by the minimal carbon fiber pull‐out.     

Temperature‐ and Light‐Regulated Gas Transport in a Liquid Crystal Polymer Network

Azobenzene‐containing liquid crystal polymer networks (LCNs) are developed for temperature‐ and light‐regulated gas permeation. The order in a chiral‐nematic LCN (LCN*) is found to be essential to couple the unique structure of the membrane and its gas permeation responses to external stimuli such as temperature and varying irradiation conditions. An LCN membrane polymerized in the isotropic phase exhibits enhanced N₂ permeation with increasing temperature, like most traditional polymers, but barely responds to exposure with 455 and 365 nm light. In sharp contrast, a reversible decrease of N₂ transport is observed for the LCN* membrane of exactly the same chemical composition, but molecularly ordered, when submitted to an elevated temperature. More importantly, alternating in situ illumination with 455 and 365 nm light modulates reversibly N₂ permeation performance of the LCN* membrane, through the trans–cis isomerization of azo moieties. The authors postulate that, besides the anisotropic deformation of LCN*, the decreased order in LCN* membrane caused by external stimuli (i.e., increasing temperature or UV light illumination) is responsible for an inhibition of gas permeation. These results show potential applications of liquid crystal polymers in the gas transport and separation, and also contribute to the development of “smart” membranes.     

Thermoresponsive Graphene Membranes with Reversible Gating Regularity for Smart Fluid Control

Precisely regulating water and molecule permeation through membranes is of crucial significance in broad domains such as water filtration and smart reactors. Comparing with routine stiff membranes, stimuli‐response polymers endow porous membranes with various gating properties, but most of these membranes have only one‐way gating performance, that is, either positive or negative. Here poly(N‐isopropylacrylamide) (PNIPAM) grafted graphene oxide (GO) membranes with reversible positive/negative gating regularity are constructed by simply tuning the molecule grafting density. The water and small molecule permeance of the membranes can be regulated by adjusting environment temperature. Based on this tunable thermoresponsive gating regularity, a bidirectional fluidic controlling system is designed by integrating a positive membrane and a negative membrane, which can be employed as a self‐adaptive gating reactor. This strategy provides an insight into constructing smart gating membranes with extraordinary properties, showing promising applications in micro/nanofluidic valves and temperature sensitive biochemical reactors.     

A pH‐Responsive Gating Membrane System with Pumping Effects for Improved Controlled Release

In this study, we report on a novel composite membrane system for pH‐responsive controlled release, which is composed of a porous membrane with linear grafted, positively pH‐responsive polymeric gates acting as functional valves, and a crosslinked, negatively pH‐responsive hydrogel inside the reservoir working as a functional pumping element. The proposed system features a large responsive release rate that goes effectively beyond the limit of concentration‐driven diffusion due to the pumping effects of the negatively pH‐responsive hydrogel inside the reservoir. The pH‐responsive gating membranes were prepared by grafting poly(methacrylic acid) (PMAA) linear chains onto porous polyvinylidene fluoride (PVDF) membrane substrates using a plasma‐graft pore‐filling polymerization, and the crosslinked poly(N,N‐dimethylaminoethyl methacrylate) (PDM) hydrogels were synthesized by free radical polymerization. The volume phase‐transition characteristics of PMAA and PDM were opposite. The proposed system opens new doors for pH‐responsive “smart” or “intelligent” controlled‐release systems, which are highly attractive for drug‐delivery systems, chemical carriers, sensors, and so on.     

Stimuli‐Responsive Bioinspired Materials for Controllable Liquid Manipulation: Principles,Fabrication, and Applications

Many emerging interfacial technologies, such as self‐cleaning surfaces, oil/water separation, water collection, and microfluidics, are essentially liquid manipulation processes. In this regard, micro‐nanostructures of the living organisms are highly preferable, by virtue of the evolutionary pressure and the adaptation to the specific environments, to inspire the optimization of man‐made interfaces. With the increasing demands of modern life, research, and industry, intelligent materials with stimuli‐responsive liquid manipulation functions have gained substantial attention from interfacial scientists. This review introduces the recent progress in the development of stimuli‐responsive liquid‐manipulating materials with bioinspired structures and surface chemistry according to two classified manipulation modes: (i) smart manipulation of liquid wetting behaviors, including lyophobic/lyophilic and superlyophobic/superlyophilic, and (ii) smart manipulation of liquid motion behaviors, including coalescence, transportation, rolling/adhesion, and sliding/pinning. At the beginning of the presentation of each classification, the theoretical basis and the sources of inspiration are introduced comprehensively to ensure a better understanding. This review mainly focuses on the mechanisms, fabrication, and applications of the state‐of‐the‐art works related to smart and biomimetic liquid‐manipulating materials. Finally, conclusions and future prospects are provided, and the remaining problems and promising breakthroughs in fabricating large‐scale, cost‐effective, and efficient smart liquid‐manipulating materials are outlined.     

Hydroactuated Configuration Alteration of Fibrous Dandelion Pappi: Toward Self‐Controllable Transport Behavior

Stimuli‐responsive materials, especially those inspired by natural organism, have been extensively studied because of their versatile applications. Here, this study demonstrates that the unique hydroactuated reversible configuration alternation of the dandelion pappus, featured by the responsive spatial closing and opening the umbrella‐like pappus depending on the environmental humidity, is a determining factor that allows the pappus to regulate its transport behavior. It is proposed that the anisotropic hydroactuated swelling of tracheids, which are typically arranged with an oblique crossing orientation, helps to generate the directional stress on the pappus. By this strategy, the pappus control its transport behavior in response to the environmental moisture, which allows long‐distance and effective seeds dispersal selectively to local sites for optimal reproduction. Inspired by this, this study develops a hydroresponsive fiber array by integrating the hydrogel, whose configuration can be altered reversibly between the opening and closing state depending on the environmental humidity. This study believes the research can offer inspirations for designing and developing adaptive devices by using fibers array, as smart aerocraft.     

Dopamine: Just the Right Medicine for Membranes

Mussel‐inspired chemistry has attracted widespread interest in membrane science and technology. Demonstrating the rapid growth of this field over the past several years, substantial progress has been achieved in both mussel‐inspired chemistry and membrane surface engineering based on mussel‐inspired coatings. At this stage, it is valuable to summarize the most recent and distinctive developments, as well as to frame the challenges and opportunities remaining in this field. In this review, recent advances in rapid and controllable deposition of mussel‐inspired coatings, dopamine‐assisted codeposition technology, and photoinitiated grafting directly on mussel‐inspired coatings are presented. Some of these technologies have not yet been employed directly in membrane science. Beyond discussing advances in conventional membrane processes, emerging applications of mussel‐inspired coatings in membranes are discussed, including as a skin layer in nanofiltration, interlayer in metal‐organic framework based membranes, hydrophilic layer in Janus membranes, and protective layer in catalytic membranes. Finally, some critical unsolved challenges are raised in this field and some potential pathways are proposed to address them.