Polyhedral Liquid Marbles

A new type of armored droplet, a so‐called polyhedral liquid marble, is introduced in this work. These armored liquid marbles consist of liquid droplets stabilized by hydrophobic hexagonal plates made of poly(ethylene terephthalate), which adsorb to the liquid–air interface. Depending on the specific combination of plate size and droplet diameter, the plates self‐assemble into highly ordered hexagonally arranged domains. Even tetrahedral‐, pentahedral‐, and cube‐shaped liquid marbles composed of only 4 to 6 plates are demonstrated. During evaporation of the internal liquid, due to the high adsorption energy of the plates at the liquid–air interface, the overall surface area stays constant, resulting in strongly deformed polyhedral liquid marbles. In line with this, highly asymmetric polyhedral liquid marbles and letters are obtained due to the strong interfacial jamming exerted by the rigid hexagonal plates. This is particularly pronounced for larger plate sizes, leading to liquid marbles with unusually sharp edges (for example, rectangular edges). The polyhedral liquid marbles exhibit various stimuli‐responsive behaviors simultaneously being exposed to water, ammonia, or tetrahydrofuran vapors. Air‐driven polyhedral liquid marbles floating on water can reach velocities of several centimeters per second.     

Light‐Driven Delivery and Release of Materials Using Liquid Marbles

Remote control of the locomotion of small objects is a challenge in itself and may also allow for the stimuli control of entire systems. Here, it is described how encapsulated liquids, referred to as liquid marbles, can be moved on a water surface with a simple near‐infrared laser or sunlight. Using light rather than pH or temperature as an external stimulus allows for the control of the position, area, timing, direction, and velocity of delivery. This approach makes it possible to not only transport the materials encapsulated within the liquid marble but also to release them at a specific place and time, as controlled by external stimuli. Furthermore, it is shown that liquid marbles can work as light‐driven towing engines to push or pull objects. Being able to remotely transport and push/pull the small objects by light and control the release of active substances on demand should open up a wide field of conceivable applications.     

Magnetocontrollable Droplet and Bubble Manipulation on a Stable Amphibious Slippery Gel Surface

Smart manipulation of liquid/bubble transport has garnered widespread attention due to its potential applications in many fields. Designing a responsive surface has emerged as an effective strategy for achieving controllable transport of liquids/bubbles. However, it is still challenging to fabricate stable amphibious responsive surfaces that can be used for the smart manipulation of liquid in air and bubbles underwater. Here, amphibious slippery surfaces are fabricated using magnetically responsive soft poly(dimethylsiloxane) doped with iron powder and silicone oil. The slippery gel surface retains its magnetic responsiveness and demonstrates strong affinity for bubbles underwater but shows small and switching resistance forces with the water droplets in air and bubbles underwater, which is the key factor for achieving the controllable transport of liquids/bubbles. On the slippery gel surface, the sliding behaviors of water droplets and bubbles can be reversibly controlled by alternately applying/removing an external magnetic field. Notably, compared with slippery liquid‐infused porous surfaces, the slippery gel surface demonstrates outstanding stability, whether in air or underwater, even after 100 cycles of alternately applying/removing the magnetic field. This surface shows potential applications in gas/liquid microreactors, gas–liquid mixed fluid transportation, bubble/droplet manipulation, etc.     

Novel,Robust, and Versatile Bijels of Nitromethane,Ethanediol, and Colloidal Silica: Capsules,Sub‐Ten‐Micrometer Domains,and Mechanical Properties

Bicontinuous, interfacially jammed emulsion gels (bijels) are a class of soft solid materials in which interpenetrating domains of two immiscible fluids are stabilized by an interfacial colloidal monolayer. Such structures form through the arrest of the spinodal decomposition of an initially single‐phase liquid mixture containing a colloidal suspension. With the use of hexalmethyldisilazane, the wetting character of silica colloids, ranging in size and dye content, can be modified for fabricating a novel bijel system comprising the binary liquid ethanediol–nitromethane. Unlike the preceding water‐lutidine based system, this bijel is stable at room temperature and its fabrication and resultant manipulation are comparatively straightforward. The new system has facilitated three advancements: firstly, we use sub 100 nm silica particles to stabilize the first bijel made from low molecular weight liquids that has domains smaller than ten micrometers. Secondly, our new and robust bijel permits qualitative rheological work which reveals the bijel to be significantly elastic and self healing whilst its domains are able to break, reform and locally rearrange. Thirdly, we encapsulate the ethanediol–nitromethane bijel in Pickering drops to form novel particle‐stabilized bicontinuous multiple emulsions that we christen bijel capsules. These emulsions are stimuli responsive – they liberate their contained materials in response to changes in temperature and solvency, and hence they show potential for controlled release applications.     

Long-Lived Liquid Marbles for Green Applications

Liquid marbles allow for quantities of various liquids to be encapsulated by hydrophobic particles, thus ensuring isolation from the external environment. The unique properties provided by this soft solid has allowed for use in a wide array of different applications. Liquid marbles do however have certain drawbacks, with lifetime and robustness often being limited. Within this review, particle characteristics that impact liquid marble stability are critically discussed, in addition to other factors, such as internal and external environments, that can be engineered to achieve a robust long-lived liquid marble. New emerging applications, which will benefit from this improvement, are explored such as unconventional computing, cell mimicry, and soft lithography. Incorporation of liquid marbles and liquid crystal technologies shows promise in utilizing structural color for optical display applications, and within green and environmental applications, liquid marble technology is increasingly adapted for use in energy conversion, heavy metal recovery, CO₂ capture, and oil removal.     

Photoresponsive Sponge‐Like Coating for On‐Demand Liquid Release

Many publications report on stimuli responsive coatings, but only a few on the controlled release of species in order to change the coating surface properties. A sponge‐like coating that is able to release and absorb a liquid upon exposure to light has been developed. The morphology of the porous coating is controlled by the smectic liquid crystal properties of the monomer mixture prior to its polymerization, and homeotropic order is found to give the largest contraction. The fast release of the liquid can be induced by a macroscopic contraction of the coating caused by a trans to cis conversion of a copolymerized azobenzene moiety. The liquid secretion can be localized by local light exposure or by creating a surface relief. The uptake of liquid proceeds by stimulating the back reaction of the azo compound by exposure at higher wavelength or by thermal relaxation. The surface forces of the sponge‐like coating in contact with an opposing surface can be controlled by light‐induced capillary bridging revealing that the controlled release of liquid gives access to tunable adhesion.     

Liquid‐Filled Valence Tautomeric Microcapsules: A Solid Material with Solution‐Like Behavior

The integration of stimuli‐responsive valence tautomeric (VT) molecular systems into solid materials without compromising their functionality is a major bottleneck for the use of these compounds in high‐added value applications. In this work, an innovative, simple, and universal approach is described to tackle this challenge based on the confinement of the active species into liquid‐filled polymeric capsules. A microstructured solid with optimized solution‐like behavior is obtained in this way, whose VT properties can be rationally tuned upon variation of the encapsulated solvent. Incorporation of the resulting capsules into thin films or other matrices of interest allows successful transfer of valence tautomerism from the liquid phase to solid materials, thus paving the way to the fabrication of functional devices based on spin transition compounds.     

Stimuli‐Responsive Materials for Controlled Release of Theranostic Agents

Stimuli‐responsive materials are so named because they can alter their physicochemical properties and/or structural conformations in response to specific stimuli. The stimuli can be internal, such as physiological or pathological variations in the target cells/tissues, or external, such as optical and ultrasound radiations. In recent years, these materials have gained increasing interest in biomedical applications due to their potential for spatially and temporally controlled release of theranostic agents in response to the specific stimuli. This article highlights several recent advances in the development of such materials, with a focus on their molecular designs and formulations. The future of stimuli‐responsive materials will also be explored, including combination with molecular imaging probes and targeting moieties, which could enable simultaneous diagnosis and treatment of a specific disease, as well as multi‐functionality and responsiveness to multiple stimuli, all important in overcoming intrinsic biological barriers and increasing clinical viability.     

Wet‐Responsive,Reconfigurable, and Biocompatible Hydrogel Adhesive Films for Transfer Printing of Nanomembranes

This study presents a wet‐responsive and biocompatible smart hydrogel adhesive that exhibits switchable and controllable adhesions on demand for the simple and efficient transfer printing of nanomembranes. The prepared hydrogel adhesives show adhesion strength as high as ≈191 kPa with the aid of nano‐ or microstructure arrays on the surface in the dry state. When in contact with water, the nano/microscopic and macroscopic shape reconfigurations of the hydrogel adhesive occur, which turns off the adhesion (≈0.30 kPa) with an extremely high adhesion switching ratio (>640). The superior adhesion behaviors of the hydrogels are maintained over repeating cycles of hydration and dehydration, indicating their ability to be used repeatedly. The adhesives are made of a biocompatible hydrogel and their adhesion on/off can be controlled with water, making the adhesives compatible with various materials and surfaces, including biological substrates. Based on these smart adhesion capabilities, diverse metallic and semiconducting nanomembranes can be transferred from donor substrates to either rigid or flexible surfaces including biological tissues in a reproducible and robust fashion. Transfer printing of a nanoscale crack sensor onto a bovine eye further demonstrates the potential of the reconfigurable hydrogel adhesive for use as a stimuli‐responsive, smart, and versatile functional adhesive for nanotransfer printing.     

Liquid Metal Marbles

Liquid metal marbles that are droplets of liquid metal encapsulated by micro‐ or nanoparticles are introduced. Droplets of galinstan liquid metal are coated with insulators (including Teflon and silica) and semiconductors (including WO₃, TiO_2, MoO₃, In₂O₃ and carbon nanotubes) by rolling over a powder bed and also by submerging in colloidal suspensions. It is shown that these marbles can be split and merged, can be suspended on water, and are even stable when moving under the force of gravity and impacting a flat solid surface. Furthermore, the marble coating can operate as an active electronic junction and the nanomaterial coated liquid metal marble can act as a highly sensitive electrochemical based heavy metal ion sensor. This new element thus represents a significant platform for the advancement of research into soft electronics.     

Highly Scalable,Closed‐Loop Synthesis of Drug‐Loaded,Layer‐by‐Layer Nanoparticles

Layer‐by‐layer (LbL) self‐assembly is a versatile technique from which multi­component and stimuli‐responsive nanoscale drug‐carriers can be constructed. Despite the benefits of LbL assembly, the conventional synthetic approach for fabricating LbL nanoparticles requires numerous purification steps that limit scale, yield, efficiency, and potential for clinical translation. In this report, a generalizable method for increasing throughput with LbL assembly is described by using highly scalable, closed‐loop diafiltration to manage intermediate purification steps. This method facilitates highly controlled fabrication of diverse nanoscale LbL formulations smaller than 150 nm composed from solid‐polymer, mesoporous silica, and liposomal vesicles. The technique allows for the deposition of a broad range of polyelectrolytes that included native polysaccharides, linear polypeptides, and synthetic polymers. The cytotoxicity, shelf life, and long‐term storage of LbL nanoparticles produced using this approach are explored. It is found that LbL coated systems can be reliably and rapidly produced: specifically, LbL‐modified liposomes could be lyophilized, stored at room temperature, and reconstituted without compromising drug encapsulation or particle stability, thereby facilitating large scale applications. Overall, this report describes an accessible approach that significantly improves the throughput of nanoscale LbL drug‐carriers that show low toxicity and are amenable to clinically relevant storage conditions.     

Phototunable Underwater Oil Adhesion of Micro/Nanoscale Hierarchical‐Structured ZnO Mesh Films with Switchable Contact Mode

Controllable surface adhesion of solid substrates has aroused great interest both in air and underwater in solving many challenging interfacial science problems such as robust antifouling, oil‐repellent, and highly efficient oil/water separation materials. Recently, responsive surface adhesion, especially switchable adhesion, under external stimulus in air has been paid more and more attention in fundamental research and industrial applications. However, phototunable underwater oil adhesion is still a challenge. Here, an approach to realize phototunable underwater oil adhesion on aligned ZnO nanorod array‐coated films is reported, via a special switchable contact mode between an unstable liquid/gas/solid tri‐phase contact mode and stable liquid/liquid/solid tri‐phase contact mode. The photo‐induced wettability transition to water and air exists (or does not) in the micro/nanoscale hierarchical structure of the mesh films, playing important role in controlling the underwater oil adhesion behavior. This work is promising in the design of novel interfacial materials and functional devices for practical applications such as photo‐induced underwater oil manipulation and release, with loss‐free oil droplet transportation.     

Tunable Anisotropic Wettability of Rice Leaf‐Like Wavy Surfaces

Rice leaves can directionally shed water droplets along the longitudinal direction of the leaf. Inspired by the hierarchical structures of rice leaf surfaces, synthetic rice leaf‐like wavy surfaces are fabricated that display a tunable anisotropic wettability by using electrostatic layer‐by‐layer assembly on anisotropic microwrinkled substrates. The nanoscale roughness of the rice leaf‐like surfaces is controlled to yield tunable anisotropic wettability and hydrophobic properties that transitioned between the anisotropic/pinned, anisotropic/rollable, and isotropic/rollable water droplet behavior states. These remarkable changes result from discontinuities in the three‐phase (solid–liquid–gas) contact line due to the presence of air trapped beneath the liquid, which is controlled by the surface roughness of the hierarchical nanostructures. The mechanism underlying the directional water‐rolling properties of the rice leaf‐like surfaces provides insight into the development of a range of innovative applications that require control over directional flow.     

Bio‐Inspired Nanospiky Metal Particles Enable Thin,Flexible, and Thermo‐Responsive Polymer Nanocomposites for Thermal Regulation

Safety issues remain a major obstacle toward large‐scale applications of high‐energy lithium‐ion batteries. Embedding thermo‐responsive polymer switching materials (TRPS) into batteries is a potential strategy to prevent thermal runaway, which is a major cause of battery failures. Here, thin, flexible, highly responsive polymer nanocomposites enabled by bio‐inspired nanospiky metal (Ni) particles are reported. These unique Ni particles are synthesized by a simple aqueous reaction at gram‐scale with controlled surface morphology and composition to optimize electrical properties of the nanocomposites. The Ni particles provide TRPS films with a high room‐temperature conductivity of up to 300 S cm^?1. Such TRPS composite films also have a high rate (<1 s) of resistance switching within a narrow temperature range, good reversibility upon on/off switching, and a tunable switching temperature (T_s; 75 to 170 °C) that can be achieved by tailing their compositions. The small size (≈500 nm) of Ni particles enables ready fabrication of thin and flexible TPRS films with thickness approaching 5 µm or less. These features suggest the great potential of using this new type of responsive polymer composite for more effective battery thermal regulation without sacrificing cell performance.     

Disulfide‐Bridged Organosilica Frameworks: Designed,Synthesis, Redox‐Triggered Biodegradation,and Nanobiomedical Applications

Over the past few years, silica‐based nanotheranostics have demonstrated their great potential for nano/biomedical applications. However, the uncontrollable and difficult degradability of their pure silica framework and long‐time in vivo retention still cause severe and unpredictable toxicity risks. Therefore, it is highly desirable to design and synthesize materials with safer framework structures and compositions. To this aim, the introduction of disulfide bonds into the silica framework can not only maintain high stability in physiological conditions, but also achieve a stimuli‐responsive biodegradation triggered by intracellular reducing microenvironment in living cells, especially in cancer cells. Once nanotheranostics with disulfide (i.e., thioether)‐bridged silsesquioxane framework are taken up by tumor cells via passive or active targeting, the disulfide bonds in the hybrid silica matrix can be cleaved by a high concentration of intracellular glutathione, enabling redox‐triggered biodegradation of the nanosystems for both concomitant release of the loaded therapeutic cargo and in vivo clearance. It is envisioned that such hybrid materials comprised of disulfide‐bridged silsesquioxane frameworks can become promising responsive and biodegradable nanotheranostics. This review summarizes the recent advances in the synthesis of hybrid organosilicas with disulfide‐bridged silsesquioxane frameworks, and discuss their redox‐triggered biodegradation behaviors combined with their biocompatibility and nanobiomedical applications.     

Reconfigurable Anisotropic Coatings via Magnetic Field‐Directed Assembly and Translocation of Locking Magnetic Chains

A method for the generation of remotely reconfigurable anisotropic coatings is developed. To form these coatings, locking magnetic nanoparticles (LMNPs) made of a superparamagnetic core and a two‐component polymer shell are employed. Two different polymers form phase‐separated coaxial shells. The outer shell provides repulsive interactions between the LMNPs while the inner shell exerts attractive forces between the particles. Applying a non‐uniform magnetic field, one gathers the particles together, pushing them to come in contact when the internal shells could effectively hold the particles together. When the magnetic field is turned off, the particles remain locked due to these strong interactions between internal shells. The shells are thus made stimuli‐responsive, so this locking can be made reversible and the chains can be disintegrated on demand. In a non‐uniform magnetic field, the assembled chains translocate, bind to the solid substrate and form anisotropic coatings with a “locked” anisotropic structure. The coatings can be constructed, aligned, realigned, degraded, and generated again on demand by changing the magnetic field and particle environment. The mechanism of the coating formation is explained using experimental observations and a theoretical model.     

Liquid‐Infused Smooth Coating with Transparency,Super‐Durability,and Extraordinary Hydrophobicity

Liquid‐infused coatings are because of their fluidity of considerable technological importance for hydrophobic materials with multifunctional properties, such as self‐healing, transmittance, and durability. However, conventional coatings absorb viscous liquid into their sponge‐like structured surface, causing uncontrollable liquid layer formation or liquid transport. In addition, a hydrophobic‐liquid‐retained surface can cause instability and lead to limitation of the hydrophobicity, optical properties, and flexibility due to liquid layer evaporation. Here, we report a strategy for controllable liquid‐layer formation on smooth surfaces (R _rms < 1 nm) by π ‐electron interactions. Using this technology, superoleophilic wetting of decyltrimethoxysilane results in the design of a surface with π ‐interaction liquid adsorption, smoothness, and hydrophobicity (SPLASH), that shows extraordinary hydrophobicity (CAH = 0.75°), and stable repellence for various water‐based solutions including micrometer‐sized mist. The smoothness of the solid under a liquid layer enabled the SPLASH to exhibit stable hydrophobicity, transparency (>90%), structure damage durability and flexibility, regardless of the liquid layer thickness by bending or evaporation. Furthermore, the patterned π ‐electrons' localization on the smooth coating enables controlled liquid‐layer formation and liquid transport. This strategy may provide new insights into designing functional liquid surfaces and our designed surface with multifunctional properties could be developed for various applications.     

Microgel‐Based Stimuli‐Responsive Capsules

In this paper, a preparation of stimuli‐responsive capsules based on aqueous microgels is described. Microgel particles act as stabilizers for oil‐in‐water emulsion and organize themselves on the surface of chloroform droplets containing the biodegradable polymer poly(4‐hydroxybutyrate‐co‐4‐hydroxyvalerate) (PHBV). After chloroform evaporation, composite capsules consisting of a thin PHBV wall with integrated microgels are obtained. Due to the presence of microgels acting as sensitive building blocks, the capsules respond to different stimuli (temperature, solvent concentration). Preliminary results indicate that the capsule dimensions and morphology can be tuned by microgel and PHBV concentration in water and chloroform, respectively.     

Modulating the Properties of Azulene‐Containing Polymers through Controlled Incorporation of Regioisomers

Two libraries of random conjugated polymers are presented that incorporate varying ratios of regioisomeric azulene units connected via the 5‐membered or 7‐membered ring in combination with bithiophene or fluorene comonomers. It is demonstrated that the optoelectronic and stimuli‐responsive properties of the materials can be systematically modulated by tuning the relative percentage of each azulene building block in the polymer backbone. Significantly, these materials exhibit stimuli‐responsive behavior in the solid state with spin‐coated thin films undergoing rapid and reversible color switching. Ultimately, this work introduces a new design strategy in which the optoelectronic properties of conjugated polymers can be modulated by varying only the regiochemistry of the constituent building blocks along a polymer chain.     

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.