Superhydrophobic Shape Memory Polymer Arrays with Switchable Isotropic/Anisotropic Wetting

Smart surfaces with tunable wettability have aroused much attention in the past few years. However, to obtain a surface that can reversibly transit between the lotus‐leaf‐like superhydrophobic isotropic and rice‐leaf‐like superhydrophobic anisotropic wettings is still a challenge. This paper, by mimicking microstructures on both lotus and rice leaves, reports such a surface that is prepared by creating micro/nanostructured arrays on the shape memory polymer. On the surface, the microstructure shapes can be reversibly changed between the lotus‐leaf‐like random state and the rice‐leaf‐like 1D ordered state. Accordingly, repeated switch between the superhydrophobic isotropic and anisotropic wettings can be displayed. Research results indicate that the smart controllability is ascribed to the excellent shape memory effect of the polymer, which endows the surface with special ability in memorizing different microstructure shapes and wetting properties. Meanwhile, based on the smart wetting performances, the surface is further used as a rewritable functional platform, on which various droplet transportation programmes are designed and demonstrated. This work reports a superhydrophobic surface with switchable isotropic/anisotropic wettings, which not only provides a novel functional material but also opens a new avenue for application in controlled droplet transportation.     

3D Porous Superhydrophobic CNT/EVA Composites for Recoverable Shape Reconfiguration and Underwater Vibration Detection

Functional superhydrophobic materials with shape memory and electrical conductivity play important roles in a wide variety of growing fields. Herein, a robust 3D porous superhydrophobic composite (PSC) with multiwalled carbon nanotube/poly(ethylene‐co‐vinyl acetate) (CNT/EVA) as its skeleton is proposed for recoverable shape reconfiguration and underwater vibration detection. Thanks to the capillary wicking of the interconnected porous structure and ethanol plasticization of the skeleton, this PSC achieves fast shape reconfiguration (<20 s) and recovery (<20 s), high shape fixity (>98%) and recovery ratio (>90%), and excellent shape‐memory repeatability (>10 times) even at 80% compressive strain. Additionally, induced by the wave‐sensitive air layer trapped on the superhydrophobic surface, the flexible CNT/EVA skeleton endures compressed/stretched deformation. Thus, the conductive PSC sensor presents high sensitivity in monitoring tiny underwater vibrations generated by stirring, objects falling, a ruler sliding, ultrasonic ation, and human activities. The findings conceivably stand out as a new methodology for the fabrication of functional superhydrophobic materials for innovative and broad applications.     

Wearable Superhydrophobic Elastomer Skin with Switchable Wettability

Flexible smart surfaces with tunable wettability are promising for emerging wearable uses. However, currently, wearable superhydrophobic surfaces with dynamic wetting behaviors are rarely reported. Here, a skin‐like superhydrophobic elastomer surface with switchable lotus leaf and rose petal states is reported. Direct laser writing technique is employed for one‐step, programmable, large‐scale fabrication of monolithic and hierarchical micro‐nanostructures on elastomer, leading to strong water repellence. The surface topography can be finely regulated in a rapid and reversible manner by simple stretching, providing the feasibility of controlling the surface wettability by simple body motions. The ability to switch wetting states enables the surface to capture and release multiple droplets in parallel. Furthermore, the active surface can be applied to the joints of fingers and operate as a droplet manipulator under finger motions without requiring energy supply or external appliance. In this work, dynamic tuning of wetting properties is integrated into the design of skin‐like wearable surfaces, revealing great potential in versatile applications such as wearable droplet manipulator, portable actuator, adaptive adhesion control, liquid repellent skin, and smart clothing.     

Simultaneous Detection and Repair of Wetting Defects in Superhydrophobic Coatings via Cassie–Wenzel Transitions of Liquid Marbles

Superhydrophobic materials that prevent unwanted liquid adhesion can easily lose this property because of limited mechanical durability despite topological/chemical control and/or robust material selection. Here, long‐lasting superhydrophobic coatings with a system to effectively detect and repair damaged areas with “liquid marble,” a droplet covered with hydrophobic nanoparticles, are reported. The particles prevent direct contact between the droplet and the substrate (Cassie state). However, they can adhere to the non‐superhydrophobic damaged area in response to the substrate wettability via an external force or an increase in liquid volume via penetration of the outer nanoparticle layer (Wenzel state). This Cassie–Wenzel transition thus induces self‐assembly of the nanoparticles onto the non‐superhydrophobic area in response to the wettability, restoring superhydrophobicity.     

Biomimetic Supertough and Strong Biodegradable Polymeric Materials with Improved Thermal Properties and Excellent UV‐Blocking Performance

The preparation of biodegradable polymeric materials with both great strength and toughness remains a huge challenge. The natural spider silk exhibits a combined super high tensile strength and high fracture toughness (150–190 J g^?1), attributing to the hierarchically assembled nanophase separation and the densely organized sacrificial hydrogen bonds confined in the nanoscale granules. Herein, inspired by natural spider silk, a facile strategy is reported for the preparation of nanostructured biomimetic polymeric material by incorporating biomass‐derived lignosulfonic acid (LA) as interspersed nanoparticles into a biodegradable poly(vinyl alcohol) (PVA) matrix. The fabricated PVA/LA nanocomposite film exhibits the world's highest toughness of 172 (±5) J g^?1 among the PVA materials, as well as a powerful tensile strength of 98.2 MPa and a large breaking strain of 282%. The outstanding performance is attributed to the strain‐induced scattering of LA nanoparticles in the PVA matrix and the strong intermolecular sacrificial hydrogen bonds confined in the interphase. Moreover, after introducing the easily available green biomass LA, the prepared biomimetic polymer films show excellent ultraviolet‐blocking performance and good thermal stability. As both PVA and LA are biodegradable, this work presents an innovative design strategy for fully biodegradable robust polymeric materials with integrated strength and toughness.     

Chameleon Nonwovens by Green Electrospinning

Electrospun ionic nonwovens are obtained by green electrospinning of aqueous dispersions. The resulting nonwovens are termed as chameleon nonwovens since their surface properties can be tailored in a large variety by coating of different functionalities following the protocol of the layer‐by‐layer process (LBL). The dimensional stability of the electrospun fibers in the chameleon nonwovens is achieved by photo‐cross‐linking after electrospinning and thereby overcoming the repulsive forces of the ionic moieties in the fibers. Depending on the nature of the ionic moieties different materials are coated by LBL including dyes, antibacterial materials, silver, and gold nanoparticles. Enhanced coating efficiency for coating of metal nanoparticles is observed when the chameleon nonwovens were precoated by a polyelectrolyte.     

A Mechanistic Study of Wetting Superhydrophobic Porous 3D Meshes

Superhydrophobic, porous, 3D materials composed of poly(?‐caprolactone) (PCL) and the hydrophobic polymer dopant poly(glycerol monostearate‐co‐?‐caprolactone) (PGC‐C18) are fabricated using the electrospinning technique. These 3D materials are distinct from 2D superhydrophobic surfaces, with maintenance of air at the surface as well as within the bulk of the material. These superhydrophobic materials float in water, and when held underwater and pressed, an air bubble is released and will rise to the surface. By changing the PGC‐C18 doping concentration in the meshes and/or the fiber size from the micro‐ to nanoscale, the long‐term stability of the entrapped air layer is controlled. The rate of water infiltration into the meshes, and the resulting displacement of the entrapped air, is quantitatively measured using X‐ray computed tomography. The properties of the meshes are further probed using surfactants and solvents of different surface tensions. Finally, the application of hydraulic pressure is used to quantify the breakthrough pressure to wet the meshes. The tools for fabrication and analysis of these superhydrophobic materials as well as the ability to control the robustness of the entrapped air layer are highly desirable for a number of existing and emerging applications.     

Tailorable Thermal Properties Through Reactive Blending Using Orthogonal Chemistries and Layer‐by‐Layer Deposition of Poly(1,3,5‐hexahydro‐1,3,5‐triazine) Networks

The ability to tune both the thermal and mechanical properties of poly(1,3,5‐hexahydro‐1,3,5‐triazine)s (PHTs) is critical to meet the increasingly stringent demands of structural materials. To this end, PHTs are modified during the process of vitrification using a reactive blending technique. Two strategies are employed: (i) the incorporation of a monomer or oligomer that contains amino end groups that are integrated into the network via hemiaminal chemistry and (ii) the incorporation of functional monomers bearing reactive end groups capable of self‐polymerization, as well as insertion by copolymerization with the PHT‐forming reagents to form mixed networks. Both strategies produce homogeneous materials, mitigating any adverse thermal properties of the parent PHT material. Here, a deposition method bringing the PHT technology platform to more diverse, economical and large‐scale applications is also introduced. A unique layer‐by‐layer spray‐coating approach of solutions containing 4,4′‐oxydianiline (ODA) and multifunctional amines obtained by conjugate addition to acrylates is developed, allowing for the preparation of large‐scale PHT‐polymer blend films. The ODA–PHT enables high strength and modulus of the final material, while incorporation of acrylates provide an economical approach to polymer blends with tremendous functional group diversity and will allow for recyclability under mild conditions.     

Continuous Synthesis of Device‐Grade Semiconducting Polymers in Droplet‐Based Microreactors

A method is reported for the controlled synthesis of device‐grade semiconducting polymers, utilizing a droplet‐based microfluidic reactor. Using poly(3‐hexylthiophene) (P3HT) as a test material, the reactor is shown to provide a controlled and stable environment for polymer synthesis, enabling control of molecular weight via tuning of flow conditions, reagent composition or temperature. Molecular weights of up to 92 000 Da are readily attainable, without leakage or reactor fouling. The method avoids the usual deterioration in materials quality that occurs when conventional batch syntheses are scaled from the sub‐gram level to higher quantities, with a prototype five‐channel reactor producing material of consistent molecular weight distribution and high regioregularity (>98%) at a rate of ≈60 g/day. The droplet‐synthesized P3HT compares favorably with commercial material in terms of absorption spectrum, polydispersity, regioregularity, and crystallinity, yielding power conversion efficiencies of up to 4% in bulk heterojunction solar cells with [6,6]‐phenyl‐C61‐butyric acid methyl ester.     

Fermi Level Engineering of Passivation and Electron Transport Materials for p‐Type CuBi2O4 Employing a High‐Throughput Methodology

Metal oxide semiconductors are promising for solar photochemistry if the issues of excessive charge carrier recombination and material degradation can be resolved, which are both influenced by surface quality and interface chemistry. Coating the semiconductor with an overlayer to passivate surface states is a common remedial strategy but is less desirable than application of a functional coating that can improve carrier extraction and reduce recombination while mitigating corrosion. In this work, a data‐driven materials science approach utilizing high‐throughput methodologies, including inkjet printing and scanning droplet electrochemical cell measurements, is used to create and evaluate multi‐element coating libraries to discover new classes of candidate passivation and electron‐selective contact materials for p‐type CuBi₂O₄. The optimized overlayer (Cu_1.5TiO_z) improves the onset potential by 110 mV, the photocurrent by 2.8×, and the absorbed photon‐to‐current efficiency by 15.5% compared to non‐coated photoelectrodes. It is shown that these enhancements are related to reduced surface recombination through passivation of surface defect states as well as improved carrier extraction efficiency through Fermi level engineering. This work presents a generalizable, high‐throughput method to design and optimize passivation materials for a variety of semiconductors, providing a powerful platform for development of high‐performance photoelectrodes for incorporation into solar‐fuel generation systems.     

Inside Front Cover: Fine Control of the Wettability Transition Temperature of Colloidal‐Crystal Films: From Superhydrophilic to Superhydrophobic (Adv. Funct. Mater. 2/2007)

A facile strategy for finely controlling the wettability transition temperature of colloidal‐crystal films from superhydrophilic to superhydrophobic is demonstrated by Song and co‐workers on p. 219. The films are assembled from poly(styrene‐n‐butyl acrylate–acrylic acid) latex spheres. The wettability transition temperature of the films is tuned by adjusting the n‐butyl acrylate/styrene balance. This approach offers flexibile fabrication of colloidal crystals with tunable wettability, and can be further extended to general materials. A facile strategy for finely controlling the wettability transition temperature of colloidal‐crystal films from superhydrophilic (water contact angle, CA, 0°) to superhydrophobic (water CA, 150.5°) is demonstrated. The colloidal‐crystal films are assembled from poly(styrene‐n‐butyl acrylate–acrylic acid) amphiphilic latex spheres. The wettability transition temperature of the films can be well tuned by adjusting the n‐butyl acrylate/styrene balance of the latex spheres. Superhydrophobic films are achieved when assembled at 90, 80, 70, 60, 40, or even 20 °C. This approach offers the flexibility of fabricating colloidal crystals with desired and tunable wettability, and can be further extended to general materials, opening up new perspectives in controlling the wettability behavior by chemical composition.     

Smart Anisotropic Wetting Surfaces with Reversed pH‐Responsive Wetting Directions

Smart pH‐responsive surfaces that could autonomously induce unidirectional wetting of acid and base with reversed directions are fabricated. The smart surfaces, consisting of chemistry‐asymmetric “Janus” silicon cylinder arrays (Si‐CAs), are prepared by precise modification of functional groups on each cylinder unit. Herein, amino and carboxyl groups are chosen as typical pH‐responsive groups, owing to their protonation/deprotonation effect in response to pH of the contacted aqueous solution. One side of the Si‐CAs is modified by poly(2‐(dimethylamino)ethyl methacrylate), while the other side is modified by mixed self‐assembled monolayers of 1‐dodecanethiol and 11‐mercaptoundecanoic acid. On such surfaces, it is observed that acid and base wet in a unidirectional manner toward corresponding directions that are modified by amino or carboxyl groups, which is caused by asynchronous change of wetting property on two sides of the asymmetric structures. The as‐prepared Janus surfaces could regulate the wetting behavior of acid and base and could direct unidirectional wetting of water with reversed directions when the surfaces are treated by strong acid or base. Due to the excellent response capability, the smart surfaces are potential candidates to be applied in sensors, microfluidics, oil/water separation, and smart interfacial design.     

Biomimetic Miniaturized Platform Able to Sustain Arrays of Liquid Droplets for High‐Throughput Combinatorial Tests

The development of high‐throughput and combinatorial technologies is helping to speed up research that is applicable in many areas of chemistry, engineering, and biology. A new model is proposed for flat devices for the high‐throughput screening of accelerated evaluations of multiplexed processes and reactions taking place in aqueous‐based environments. Superhydrophobic (SH) biomimetic surfaces based on the so‐called lotus effect are produced, onto which arrays of micro‐indentations allow the fixing of liquid droplets, based on the rose‐petal effect. The developed platforms are able to sustain arrays of quasi‐spherical microdroplets, allowing the isolation and confinement of different combinations of substances and living cells. Distinct compartmentalized physical, chemical, and biological processes may take place and be monitored in each droplet. The devices permit the addition/removal of liquid and mechanical stirring by adding magnetic microparticles into each droplet. By facing the chip downward, it is possible to produce arrays of cell spheroids developed by gravity in the suspended droplets, with the potential to be used as microtissues in drug screening tests.     

Dielectric Properties of Sustainable Nanocomposites Based on Zein Protein and Lignin for Biodegradable Insulators

Two types of lignin, alkali lignin and lignosulfonic acid sodium salt, are blended into thermoplastic zein through melt mixing in order to develop biodegradable insulator materials for multifunctional applications in electronics. The effects of lignin type and content on the dielectric properties of the resulting bio‐nanocomposites are investigated. The results indicate that, by modifying the structural arrangement of the zein with the use of lignin, it is possible to obtain bio‐nanocomposites characterized by tunable dielectric properties. The bio‐nanocomposites containing low amounts of lignin derivatives exhibit extensive protein structural changes together with a modification of the dielectric properties compared to the pristine thermoplastic zein. Changes in the dielectric properties of these systems are also observed to change over time, indicating a loss of plasticizer, as is evident by a decrease in the glass‐transition temperature. At high frequencies, the resulting values of the dielectric permittivity and of the loss tangent demonstrate that the bio‐nanocomposite can be used as biodegradable dielectric material for transient (temporary) electronics.     

Porous Polymer Coatings: a Versatile Approach to Superhydrophobic Surfaces

Here, a facile and inexpensive approach to superhydrophobic polymer coatings is presented. The method involves the in situ polymerization of common monomers in the presence of a porogenic solvent to afford superhydrophobic surfaces with the desired combination of micro‐ and nanoscale roughness. The method is applicable to a variety of substrates and is not limited to small areas or flat surfaces. The polymerized material can be ground into a superhydrophobic powder, which, once applied to a surface, renders it superhydrophobic. The morphology of the porous polymer structure can be efficiently controlled by composition of the polymerization mixture, while surface chemistry can be adjusted by photografting. Morphology control is used to reduce the globule size of the porous architecture from micro down to nanoscale thereby affording a transparent material. The influence of both surface chemistry as well as the length scale of surface roughness on the superhydrophobicity is discussed.     

Hierarchical Assembly of Complex Block Copolymer Nanoparticles into Multicompartment Superstructures through Tunable Interparticle Associations

A challenging aim in both materials physics and chemistry is the construction of complex and functional superstructures from designed nanoscale building units. Block copolymer nanoparticles with morphological variety and compositional complexity have been made with solution‐based assembly. However, routine ability to build hierarchical superstructures by inter‐nanoparticle association is not yet possible. A hierarchical assembly strategy of organizing pre‐formed spherical block copolymer nanoparticles into superstructures, including linear, circular, and close‐packed arrays, via tunable interparticle interactions is presented. Solution‐state mixtures are made of two amphiphilic diblock copolymers, poly(acrylic acid)‐block‐poly(methyl methacrylate) (PAA‐b‐PMMA) and poly(acrylic acid)‐block‐polybutadiene (PAA‐b‐PB) with additional crown ether functionalities grafted onto 40 mol% of the AA repeat units on the PAA‐b‐PMMA diblock copolymer. Through kinetic control of the solution assembly process in aqueous/N,N‐dimethylformamide (DMF) mixtures (4:1 water:DMF), spherical nanoparticles with compositional complexity confined in both the core and shell are obtained. Benefiting from host‐guest chemistry, interparticle association is triggered and tuned by the addition of di‐functional organoamines due to amine‐crown ether complexation. The resultant multiparticle superstructures contain well‐defined multicompartments within individual, constituent nanoparticles due to the local separation of unlike PB and PMMA hydrophobic blocks within the cores of the individual particles. Through competitive complexation with potassium ions, the superstructures are disassembled into individual multicomparment nanoparticles.     

Superoleophilic and Superhydrophobic Inverse Opals for Oil Sensors

An inverse opal with both superoleophilic (oil contact angle (CA), 5.1° ± 1.2°) and superhydrophobic (water CA, 153.8° ± 1.2°) properties is fabricated using a phenolic resin (PR) as precursor and poly(styrene‐methyl methacrylate‐acrylic acid) (poly(St‐MMA‐AA)) colloidal crystals as templates. The stopband of the inverse opal can shift reversibly upon sorption of oils, whereby the peak position is a linear function of the refractive index of the adsorbed oil, e.g., a variation in refractive index of 0.02 will result in a stopband shift of 26 nm. Therefore, the inverse opals show a high sensitivity and selectivity for different petroleum oils. Moreover, as‐prepared PR inverse opals show excellent oil‐sensing stability in cyclic sorption experiments, which suggests a promising and economical alternative to traditional oil‐sensing materials, and will provide a new approach to in situ petroleum monitoring and detection.     

Electrically Adjustable,Super Adhesive Force of a Superhydrophobic Aligned MnO2 Nanotube Membrane

A superhydrophobic membrane of MnO₂ nanotube arrays on which a water droplet can be immobilized by application of a small DC bias, despite a large contact angle, is reported. For a 3 μL water droplet, the measured adhesive force increases monotonically with increasing negative voltage, reaching a maximum of 130 μN at 22 V, 25 times the original value. It follows that the nearly spherical water droplet can be controllably pinned on the substrate, even if the substrate is turned upside down. Moreover, the electrically adjustable adhesion is strongly polarity‐dependent: only a five‐fold increase is found when a positive bias of 22 V is applied. This remarkable electrically‐controlled adhesive property is ascribed to the change in contact geometry between the water droplet and MnO₂ nanotube array, on which water droplets exhibit the different continuities of three‐phase contact line. As the modulation in this manner is in situ, fast, efficient and environmentally‐friendly, this kind of smart material with electrically adjustable adhesive properties has a wide variety of applications in biotechnology and in lab‐on‐chip devices.     

Spatial Analysis of Metal–PLGA Hybrid Microstructures Using 3D SERS Imaging

The incorporation of gold nanoparticles in biodegradable polymeric nanostructures with controlled shape and size is of interest toward different applications in nanomedicine. Properties of the polymer such as drug loading and antibody functionalization can be combined with the plasmonic properties of gold nanoparticles, to yield advanced hybrid materials. This study presents a new way to synthesize multicompartmental microgels, fibers, or cylinders, with embedded anisotropic gold nanoparticles. Gold nanoparticles dispersed in an organic solvent can be embedded within the poly(lactic‐co‐glycolic acid) (PLGA) matrix of polymeric microstructures, when prepared via electrohydrodynamic co‐jetting. Prior functionalization of the plasmonic nanoparticles with Raman active molecules allows for imaging of the nanocomposites by surface‐enhanced Raman scattering (SERS) microscopy, thereby revealing nanoparticle distribution and photostability. These exceptionally stable hybrid materials, when used in combination with 3D SERS microscopy, offer new opportunities for bioimaging, in particular when long‐term monitoring is required.     

Synthesis of Microscale Raft‐shaped Zinc(II)–Phenylalanine Complexes and Zinc(II)–Phenylalanine/dye Hybrid Bundles with New Optical Properties

Novel raft‐like zinc(II)–phenylalanine complexes and zinc(II)–phenylalanine/acid green 27 (AG27) hybrid radial bundles have been successfully synthesized by a simple refluxing reaction. The formation processes of the morphologies and the superstructures of the hybrid bundles were proposed based on the time‐dependent evolution process. The AG27 molecules act as both the inclusion compound and the controller of the morphologies and the superstructures of the final hybrid. The combination of the zinc(II)–phenylalanine complex and AG27 leads to distinct optical properties compared with the individual component materials. This approach opens a new and effective way for the fabrication of amino acid/dye hybrid materials with unique optical properties and is expected to allow access to other organic/organic hybrid materials with structural specificity and functional novelty.