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Design elements extracted from biological ion channels guide the engineering of artificial nanofluidic membranes for efficient ionic transport and spawn biomimetic devices with great potential in many cutting-edge areas. In this context, polymeric nanofluidic membranes can be especially attractive because of their inherent flexibility and benign processability, which facilitate massive fabrication and facile device integration for large-scale applications. Herein, the state-of-the-art achievements of polymeric nanofluidic membranes are systematically summarized. Theoretical fundamentals underlying both biological and synthetic ion channels are introduced. The advances of engineering polymeric nanofluidic membranes are then detailed from aspects of structural design, material construction, and chemical functionalization, emphasizing their broad chemical and reticular/topological variety as well as considerable property tunability. After that, this Review expands on examples of evolving these polymeric membranes into macroscopic devices and their potentials in addressing compelling issues in energy conversion and storage systems where efficient ion transport is highly desirable. Finally, a brief outlook on possible future developments in this field is provided.

Macroporous structures can be developed within polyelectrolyte multilayer films for efficient drug loading, but these structures tend to collapse or fracture during conventional drying procedures. Herein, a facile dehydrating method for macroporous polyelectrolyte multilayer films is proposed using solvent exchange to ethanol and then spontaneous evaporation. During these processes, the collapse of the macroporous structures can be effectively avoided, which can be ascribed to a combined effect of two factors. On one hand, capillary pressure during ethanol evaporation is relatively small since the surface tension of ethanol is much lower than that of water. On the other hand, solvent exchange suppresses the interdiffusion of polyelectrolytes and substantially increases the mechanical strength of the macroporous films, more than three orders of magnitude, making the pore walls highly tolerant of the capillary pressure. The stability of macroporous polyelectrolyte films to ethanol enables the repeated wicking from the ethanol solution of drugs, leading to a higher loading beyond previous studies. Such a high loading is favorable for the long-term release of drugs from the surfaces of modified substrates and maintaining a local drug concentration above the minimum effective concentration.

Two-dimensional nanofluidic membranes offer great opportunities for developing efficient and robust devices for ionic/water-nexus energy harvesting. However, low counterion concentration and long pathway through limited ionic flux restrict their output performance. Herein, it is demonstrated that rapid diffusion kinetics can be realized in two-dimensional nanofluidic membranes by introducing in-plane holes across nanosheets, which not only increase counterion concentration but also shorten pathway length through the membranes. Thus, the holey membranes exhibited an enhanced performance relative to the pristine ones in terms of osmotic energy conversion. In particular, a biomimetic multilayered membrane sequentially assembled from pristine and holey sections offers an optimized combination of selectivity and permeability, therefore generating a power density up to 6.78 W m

Human skin can function steadily regardless of surrounding circumstances (dry or wet), while it is still a challenge for artificial ionic skins, which tend to release solvents in dry air and leach electrolytes in wetted state. Herein, a series of hierarchically crosslinked ionogels containing hydrophobic ionic liquids (ILs) is fabricated by combining a crystalline fluorinated copolymer with hydrophobic ILs. With a reasonable combination of nonvolatility, transparency, stretchablility, and sensitivity, such ionogels can work as reliable sensors for real-time monitoring human motions and operate steadily in complex environments as human skin does, which can contribute to the development of durable sensing devices with a simple design.

Surface-mediated gene delivery appears to be potential gene delivery modes for various applications. Still, controlled and smart delivery manners are required especially considering the need for gene therapy to deliver gene with selectivity. A surface that can effectively payload DNA, promote cell adhesion, and stimuli response is an important prerequisite. Here, we report a matrix metalloproteinase (MMP)-responsive surface-mediated gene delivery system by combining MMP-degradable hydrogel with a breath figure (BF) porous film. The MMP-degradable hydrogel containing plasmid DNA was loaded into the surface pores of the BF film as DNA reservoirs. The upper surface without hydrogel on the BF film served as footholds of integrin adhesions. MMP is one of the important endogenous signals in tumor-related pathologic changes, and MMP expressions in cancer cells are significantly higher than those in normal cells. Consequently, our surface-mediated gene delivery locally and rapidly released the payload DNA in response to cancer cells and transfected them. This work highlights the importance of the combination of stimuli-response and surface-mediated gene delivery to functional materials, showing good potential applications in the field of gene therapy.

Inspired by nature, many functional surfaces have been developed with special structures in biology, chemistry, and materials. Many research studies have been focused on the preparation of surfaces with static structure. Achieving dynamical manipulation of surface structure is desired but still a great challenge. Herein, a polyelectrolyte film capable of regional and reversible changes in the microporous structure is presented. Our proposal is based on the combination of azobenzene (Azo) π-π stacking and electrostatic interaction, which could be affected respectively by ultraviolet (UV) irradiation and water plasticization, to tune the mobility of polyelectrolyte chains. The porous patterns can be obtained after regional ultraviolet irradiation and acid treatment. Owing to the reversibility of Azo π-π stacking and electrostatic interaction, the patterns can be repeatedly created and erased in the polyelectrolyte film made by layer-by-layer (LbL) self-assembly of poly(ethyleneimine)-azo and poly(acrylic acid). Furthermore, through two rounds of porous pattern formation and erasure, different functional species can be loaded separately and confined regionally within the film, showing potential applications in the functional surface. This work highlights the coordination of two noncovalent interactions in thin films for regional and reversible controlling its structure, opening a window for more in-depth development of functional surfaces.

Patterned slippery surfaces based on the technique of slippery liquid-infused porous surface (SLIPS) have broad technological applications in biofouling, liquid handling, biomolecule collection, and droplet microarrays. However, methods to generate patterned SLIPS with flexibility and practical potential remain a technical roadblock. Here, we report an approach for generating patterned SLIPS, and by utilizing which, as a proof-of-technique application, the droplet microarrays have been presented. Our approach is based on a photocross-linkable polyelectrolyte poly(ethyleneimine)/azide-poly(acrylic acid) (PEI/PAA-N3) film, whose surface structures can be dynamically controlled. We have prepared the surface-patterned PEI/PAA-N3 film containing microstructured and flat regions. We then demonstrate that, because of much higher lubricant retaining capability of the microstructured regions, a patterned SLIPS can be simply generated through infusing the lubricant onto the surface and applying a shear spinning pro...

A constant increase of nosocomial infections that are caused by adhesion and colonization of pathogenic microorganisms, especially drug-resistant bacteria, on the surfaces of healthcare devices has received considerable attention worldwide. In this study, bioinspired by antimicrobial skins of natural living beings, we developed a self-healing bactericidal coating through the immobilization of hydrophobic antimicrobial peptides (AMPs) into a multilayer film, which was constructed through the enhanced exponential layer-by-layer assembly of polyethylenimine (PEI) and poly(acrylic acid) (PAA). The (PEI/PAA) film shows particular dynamic properties from the as-prepared thin solid film to a spongy microporous structure via acid solution treatment, and then back to the thin solid film by eliminating micropores via the treatment of saturated humidity. Consequently, the loading and integration of hydrophobic AMPs such as gramicidin A (GA) into the (PEI/PAA) film were achieved via simple wicking action with GA solution and subsequent humidity treatment, respectively. The GA loading densities can be precisely controlled by using different concentrations of GA solution. We demonstrated that the GA immobilized (PEI/PAA) film has rapid self-healing properties, and that Gram-positive bacteria S. aureus including the methicillin-resistant type were efficiently killed through the contact-killing mode. Collectively, this self-healing bactericidal coating shows practical potential in a variety of healthcare applications.

Generating a biofunctional film that can mimic the extracellular matrix (ECM) in an efficient and robust technique that may have great potential for medical devices, tissue engineering, and regenerative medicines. Herein, a facile approach to generate ECM biomimetic films based on the humidity-triggered relaxation of polyelectrolyte complex (PEC) nanoparticles is reported. The poly(l-lysine) and hyaluronan are precomplexed and sprayed onto a substrate, which, via a trigger of vaporous water, can be transformed into an even and stable film. The spontaneous polymer chain interfusion (diffusion coefficient ≈1.01 × 10-9 cm2 s-1 ) under saturated humidity, allowing for the rapid reorganization (within 30 min) of film morphology and structure is demonstrated. A controllable and scalable way for the loading of diversified bioactive agents, as well as on-demand modulation of stiffness is further presented. Moreover, the high-throughput arrays and programmed patterns can be easily completed, suggesting huge potentials that surpass those of state-of-the-art methods. Combined with high efficiency and flexible functionalization, it is believed that this approach should be beneficial for extending the practical applications of PEC films, such as medical implants, chip detectors, and so on.

Spatially controlling the evolution of surface structures may provide an effective strategy for patterning surface roughness and facilitating the construction of various functional surfaces. In this study, we report a photo-cross-linkable polymeric film with dynamic surface micro/nanostructures. The surface structures of the un-cross-linked regions can be eliminated under saturated humidity, which can be utilized to create patterned roughness on the film. One potential application of this patternable platform is as a "smart" label material for graphical symbols. Various graphical symbols can be programmed onto this film by partially erasing its surface roughness, enabling visibility due to the difference in light scattering between different areas of the film. When a thus-prepared label was blurred by mechanical scratches, it could be healed under saturated humidity, and its original readability could be fully restored. Furthermore, the patterned rough surface created using our approach can also be very useful in many other research fields, such as surface wettability and cell behavior manipulation.

Cationic antibacterial coating based on quaternary ammonium compounds, with an efficient and broad spectrum bactericidal property, has been widely used in various fields. However, the high density of positive charges tends to induce weak hemocompatibility, which hinders the application of the cationic antibacterial coating in blood-contacting devices and implants. It has been reported that a negatively charged surface can reduce blood coagulation, showing improved hemocompatibility. Here, we describe a strategy to combine the cationic and anionic groups by using mixed-charged copolymers. The copolymers of poly (quaternized vinyl pyridine- co- n-butyl methacrylate- co-methacrylate acid) [P(QVP- co- nBMA- co-MAA)] were synthesized through free radical copolymerization. The cationic group of QVP, the anionic group of MAA, and the hydrophobic group of nBMA were designed to provide bactericidal capability, hemocompatibility, and coating stability, respectively. Our findings show that the hydrophilicity of the copolymer coating increased, and its zeta potential decreased from positive charge to negative charge with the increase of the anionic/cationic ratio. Meanwhile, the bactericidal property of the copolymer coating was kept around a similar level compared with the pure quaternary ammonium copolymer coating. Furthermore, the coagulation time, platelet adhesion, and hemolysis tests revealed that the hemocompatibility of the copolymer coating improved with the addition of the anionic group. The mixed-charged copolymer combined both bactericidal property and hemocompatibility and has a promising potential in blood-contacting antibacterial devices and implants.

Polyelectrolyte multilayers have received broad interests in the fields of functional coatings due to their easy deposition procedure, environmentally friendly nature and wide sensitivities to manifold external stimuli. Stimuli-triggered generation of nanoscopic structures on polyelectrolyte multilayers can be reversible generally when their structural size is less than dozens of nanometers. Transforming larger structures reversibly would represent a breakthrough of these materials for novel applications. Herein, we report that surface structures up to hundreds of nanometers can be developed on exponentially growing polyelectrolyte multilayers reversibly, which feature the diffusion of polyelectrolytes throughout the whole assemblies. These multilayers are prepared utilizing pH-amplified layer-by-layer assembly of branched polyethylenimine and photo-reactive poly(acrylic acid) azido derivative. Other than applying a single stimulus on the mobility of polymeric chains, the surface structures were developed by inducing electrostatic repulsion between chains in aqueous phases while subsequently erased by shielding supramolecular electrostatic interactions in gaseous phases. These processes are completely reversible and one potential application of this dynamic platform is to be a “smart” material for reversible visualization of various high-definition patterns with fine brightness contrast, which can be especially significant in some cutting-edge fields like the Internet of Things, information encryption/decryption and anti-counterfeiting. Beyond that, such dynamic platform can be very useful in many other research fields, such as surface wettability and smart homes.

Introducing a lubricant layer onto surfaces has emerged as a novel strategy to address a wide range of interface-related challenges. Recent studies of lubricant-infused surfaces have extended beyond repelling liquids to manipulating the mobility of fluids. In this study, we report a design of slippery surfaces based on infusing lubricant onto a polyelectrolyte multilayer film whose surface microstructures can be erased rapidly under mild condition. Unlike other lubricant-infused surfaces, the liquid movements (e.g., moving resistance and direction) on such surfaces can be manipulated via programming the surface microstructures beforehand. The work reported here offers a versatile design concept of lubricant-infused surfaces and may turn on new applications of this emerging class of bioinspired materials.

Optimized ratio in the codelivery of therapeutics is of crucial importance to promote the synergism rather than the antagonistic effects. In this study, a self-healing spongy coating was described to facilitate the surface-mediated delivery of drug "cocktails" proportionally. The formation of spongy structures within the coating was achieved by acidic treatment and freeze-drying. Various drug combinations can be readily integrated through wicking method and subsequent micropore self-healing. The ratio of drug loading can be precisely regulated by the composition of loading solution and the embedded drugs were released in proportion according to the initial ratio of drug combination.

Medical coatings cooperated with biomacromolecules can regulate biological events and tissue responses, thus increasing medical implant longevity and providing improved and/or new therapeutic functions. In particular, medical coatings, which can load the correct species and doses of biomacromolecules according to individual diagnoses, will significantly optimize treatment effects and satisfy the rising clinical need of “precision medicine”. Herein, we report on a dynamic microporous coating with an ultrafast self-healing property to fulfill the “load-and-play” concept for “precision medicine”. A structure-switchable coating based on poly(e-caprolactone)-poly(ethylene glycol)-poly(e-caprolactone) triblock copolymer network is constructed. The coating can be switched to microporous morphology via a water swelling and freeze-drying process. Then, through a mild thermo-trigger as low as 40 °C, this spongy coating can undergo self-healing to switch back to a pore-free structure within minutes to even 5 s. Based on this dynamic coating, we suggest a simple and versatile method to encapsulate biomacromolecules for surface-mediated delivery. The ultrafast self-healing of the microporous structure enables uniform incorporation of biomacromolecules with an easily achieved high loading of albumin of 16.3 μg/cm2 within 1 min. More importantly, controllable encapsulation can be realized by simple control of the concentration of the loading solution. We further demonstrate that the encapsulated biomacromolecules retained their bioactivity. This work may benefit clinicians with flexibility to provide personalized medical coatings for individual patients during treatment.

Introducing wrinkling or rough features into substrates is of great practical significance to construct various functional surfaces. Due to the sensitivity of assembled units towards environmental stimuli, the internals of layer-by-layer films can be readily adjusted to generate various micro- and nanostructures. We previously described a self-roughening polyelectrolyte multilayer (PEM) to facilitate the introduction of surface microstructures. In the present work, the growth process of PEI/PAA multilayer films was investigated and the mean size of the surface microstructures was found to increase linearly with the film thickness. The spontaneous formation of these surface features can be attributed to swelling-induced film deformation during the assembling process, which is similar to the surface wrinkling of hydrogels undergoing a volume phase transition. When exposed to saturated humidity, the internal stress as well as the surface microstructures can be diminished spontaneously, leading to a flat surface over the substrates. Given the effect of the underlying film thickness on the characteristic wavelength of the surface wrinkles, multiscale surface microstructures can be readily realized by means of spatially presetting the distribution of the film thickness.

Layer-by-layer (LbL) self-assemblies have inherent potential as dynamic coatings because of the sensitivity of their building blocks to external stimuli. Here, humidity serves as a feasible trigger to activate the self-healing of a microporous polyethylenimine/poly(acrylic acid) multilayer film. Microporous structures within the polyelectrolyte multilayer (PEM) film are created by acid treatment, followed by freeze-drying to remove water. The self-healing of these micropores can be triggered at 100% relative humidity, under which condition the mobility of the polyelectrolytes is activated. Based on this, a facile and versatile method is suggested for directly integrating hydrophobic drugs into PEM films for surface-mediated drug delivery. The high porosity of microporous film enables the highest loading (≈303.5 μg cm−2 for a 15-bilayered film) of triclosan to be a one-shot process via wicking action and subsequent solvent removal, thus dramatically streamlining the processes and reducing complexities compared to the existing LbL strategies. The self-healing of a drug-loaded microporous PEM film significantly reduces the diffusion coefficient of triclosan, which is favorable for the long-term sustained release of the drug. The dynamic properties of this polymeric coating provide great potential for its use as a delivery platform for hydrophobic drugs in a wide variety of biomedical applications.

In-stent restenosis and thrombosis are the main severe problems that occur after the percutaneous vascular intervention. The competition between endothelial cells (ECs) and smooth muscle cells (SMCs) plays a key role during these pathological changes. The regulation of this competition offers new opportunities to design biomaterials in the cardiovascular fields. Bioactive molecules have been typically employed to increase EC adhesion and thereafter to enhance EC competitiveness; however, this method is associated with limitations from the point of view of practical and industrial applications. Herein, we present an approach to enhance EC competitiveness over that of SMC through the selective EC adhesion, which is achieved by modulating a complex surface stiffness based on the technique of layer-by-layer (LbL) assembly. This complex stiffness can be achieved by regulating the thickness of multilayer films coordinating with a rigid underlying substrate. The selective cell adhesion is attributed to changes in the complex surface stiffness and a different intrinsic property between ECs and SMCs. This study provides a facile and broadly applicable approach for the purpose of the enhancement of EC competitiveness over that of SMC, which has great potential for the development of cell-based functional biomaterials in the cardiovascular field.

A pseudo-polycation was prepared based on the supramolecular cucurbit[8]uril ternary complex. It was then layer-by-layer assembled with poly(acrylic acid) to fabricate a stimuli-responsive film, which exhibited disassembly properties in response to stimuli, providing a supramolecular route for the fabrication of free-standing thin films.