Antigravity Autonomous Superwettable Pumps for Spontaneous Separation of Oil-Water Emulsions.

Oil-water separation based on superwettable materials offers a promising way for the treatment of oil-water mixtures and emulsions. Nevertheless, such separation techniques often require complex devices and external energy input. Therefore, it remains a great challenge to separate oil-water mixtures and emulsions through an energy-efficient, economical, and sustainable way. Here, a novel approach demonstrating the successful separation of oil-water emulsions using antigravity-driven autonomous superwettable pumps is presented. By transitioning from traditional gravity-driven to antigravity-driven separation, the study showcases the unprecedented success in purifying oil/water from emulsions by capillary/siphon-driven superwettable autonomous pumps. These pumps, composed of self-organized interconnected channels formed by the packing of superhydrophobic and superhydrophilic sand particles, exhibit outstanding separation flux, efficiency, and recyclability. The findings of this study not only open up a new avenue for oil-water emulsion separation but also hold promise for profound impacts in the field.

Relaxing Wrinkles in Jammed Interfacial Assemblies.

Dynamic covalent bonding has emerged as a mean by which stresses in a network can be relaxed. Here, the strength of the bonding of ligands to nanoparticles at the interface between two immiscible liquids affect the same results in jammed assemblies of nanoparticle surfactants. Beyond a critical degree of overcrowding induced by the compression of jammed interfacial assemblies, the bonding of ligands to nanoparticles (NPs) can be broken, resulting in a desorption of the NPs from the interface. This reduces the areal density of nanoparticle surfactants at the interface, allowing the assemblies to relax, not to a fluid state but rather another jammed state. The relaxation of the wrinkles caused by the compression reflects the tendency of these assemblies to eliminate areas of high curvature, favoring a more planar geometry. This enabled the generation of giant vesicular and multivesicular structures from these assemblies.

A Gemini-Type Superwettable Separator for Consecutive Purification of Water and Oil Phases from Oil-Water Mixtures and Emulsions.

Oil pollution results from daily activities and a variety of industries have caused not only severe environmental problems but also wastage of valuable petrochemical resources. Separation based on superwettable materials holds promise; however, practical applications of a single type of superwettable materials were often limited due to their ability in treatment of complicated oil-water systems. Herein, a Gemini-type separator was created through the cooperation of two kinds of superwettable sand particles with opposite wettability, i. e., one is superhydrophobic whereas the other is superhydrophilic. Cooperatively by the two types of superwettable sand, consecutive separation and purification of both water and oil phases from complicated oil-water systems (e. g., water mixed with a lighter or denser oil, water emulsified in oil, oil emulsified in water, and/or a combination of them in one batch) could be achieved with high flux and superior efficiency just in one single operation unit.

Aquabots.

Soft robots, made from elastomers, easily bend and flex, but deformability constraints severely limit navigation through and within narrow, confined spaces. Using aqueous two-phase systems we print water-in-water constructs that, by aqueous phase-separation-induced self-assembly, produce ultrasoft liquid robots, termed aquabots, comprised of hierarchical structures that span in length scale from the nanoscopic to microsciopic, that are beyond the resolution limits of printing and overcome the deformability barrier. The exterior of the compartmentalized membranes is easily functionalized, for example, by binding enzymes, catalytic nanoparticles, and magnetic nanoparticles that impart sensitive magnetic responsiveness. These ultrasoft aquabots can adapt their shape for gripping and transporting objects and can be used for targeted photocatalysis, delivery, and release in confined and tortuous spaces. These biocompatible, multicompartmental, and multifunctional aquabots can be readily applied to medical micromanipulation, targeted cargo delivery, tissue engineering, and biomimetics.

Continuous, autonomous subsurface cargo shuttling by nature-inspired meniscus-climbing systems.

Water-walking insects can harness capillary forces by changing their body posture to climb or descend the meniscus between the surface of water and a solid object. Controlling surface tension in this manner is necessary for predation, escape and survival. Inspired by this behaviour, we demonstrate autonomous, aqueous-based synthetic systems that overcome the meniscus barrier and shuttle cargo subsurface to and from a landing site and a targeted drop-off site. We change the sign of the contact angle of a coacervate sac containing an aqueous phase or of a hydrogel droplet hanging from the surface by controlling the normal force acting on the sac or droplet. The cyclic buoyancy-induced cargo shuttling occurs continuously, as long as the supply of reactants diffusing to the sac or droplet from the surrounding aqueous phase is not exhausted. These findings may lead to potential applications in autonomously driven reaction or delivery systems and micro-/milli-robotics.

Visualizing Interfacial Jamming Using an Aggregation-Induced-Emission Molecular Reporter.

With the interfacial jamming of nanoparticles (NPs), a load-bearing network of NPs forms as the areal density of NPs increases, converting the assembly from a liquid-like into a solid-like assembly. Unlike vitrification, the lineal packing of the NPs in the network is denser, while the remaining NPs can remain in a liquid-like state. It is a challenge to determine the point at which the assemblies jam, since both jamming and vitrification lead to a solid-like behavior of the assemblies. Herein, we show a real-time fluorescence imaging method to probe the evolution of the interfacial dynamics of NP surfactants at the water/oil interface using aggregation-induced emission (AIE) as a reporter for the transition of the assemblies into the jammed state. The AIEgens show typical fluorescence behavior at densities at which they can move and rotate. However, when aggregation of these fluorophores occurs, the smaller intermolecular separation distance arrests rotation, and a significant enhancement in the fluorescence intensity occurs.

Surfactant-Induced Interfacial Aggregation of Porphyrins for Structuring Color-Tunable Liquids.

Locking nonequilibrium shapes of liquids into targeted architectures by interfacial jamming of nanoparticles is an emerging area in material science. 5,10,15,20-tetrakis(4-sulfonatophenyl) porphyrin (H6 TPPS) shows three different aggregation states that present an absorption imaging platform to monitor the assembly and jamming of supramolecular polymer surfactants (SPSs) at the liquid/liquid interface. The interfacial interconversion of H6 TPPS, specifically H4 TPPS2- dissolved in water, from J- to an H-aggregation was induced by strong electrostatic interactions with amine-terminated polystyrene dissolved in toluene at the water/toluene interface. This resulted in color-tunable liquids due to interfacial jamming of the SPSs formed between H4 TPPS2- and amine-terminated polystyrene. However, the formed SPSs cannot lock in nonequilibrium shapes of liquids. In addition, a self-wrinkling behavior was observed when amphiphilic triblock copolymers of PS-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) were used to interact with H4 TPPS2- . Subsequently, the SPSs formed can lock in nonequilibrium shapes of liquids.

Conductive Thin Films over Large Areas by Supramolecular Self-Assembly.

We report a "one-step" method for preparing conductive thin films with cylindrical microdomains oriented normal to the surface over large areas using the supramolecular assembly of poly(styrene-block-4-vinylpyridine) (PS19-b-P4VP5) and 5,10,15,20-tetrakis(4-hydroxyphenyl)-21H,23H-porphine (HOTPP). HOTPP interacts with the P4VP block by hydrogen bonding between the hydroxyl group of HOTPP and pyridine ring of PS19-b-P4VP5, forming cylindrical P4VP(HOTPP) domains having an average diameter of ∼17 nm in a PS matrix. Dynamic light scattering, contact angle, and in situ grazing incidence small-angle X-ray scattering measurements show a morphological transition from spherical micelles in solution to cylindrical microdomains oriented normal to the substrate surface during the drying process. From the dependence of current on voltage, an average current of ∼4.0 nA is found to pass through a single microdomain, pointing to a promising route for organic semiconductor device applications.

Correction: Bioinspired hydrogel-based nanofluidic ionic diodes: nano-confined network tuning and ion transport regulation.

Correction for 'Bioinspired hydrogel-based nanofluidic ionic diodes: nano-confined network tuning and ion transport regulation' by Congcong Zhu et al., Chem. Commun., 2020, 56, 8123-8126, DOI: 10.1039/D0CC01313G.

Bioinspired hydrogel-based nanofluidic ionic diodes: nano-confined network tuning and ion transport regulation.

Biological ion channel-based mass transport and signal transduction play a crucial role in physiological activities, and biomimetic nanochannels in aqueous solutions for ion transport regulation have been extensively studied. Few studies on non-aqueous systems, gel-based nanochannels, mainly focus on the charged gel network or embedded electrolytes. However, the basic issue of how a nanoscale gel network affects the ion transport in nanochannels has been neglected. Here, we demonstrate a non-aqueous biomimetic nanochannel system by employing the agarose hydrogel in conical nanochannels. To tune the hydrogel network by adjusting the gel concentration, the ion transport behavior in gel-based nanochannels is systemically investigated. The experimental results show that the ion transport behaviors in gel-nanochannels with 2% gel present similar ion selectivity and rectification performance to the aqueous system, indicating fast investigation of gel-based systems with the knowledge of the extensively studied aqueous systems. Furthermore, a gel-based solid-state diode and logic circuits were fabricated.

Rapid Multilevel Compartmentalization of Stable All-Aqueous Blastosomes by Interfacial Aqueous-Phase Separation.

Producing artificial multicellular structures to process multistep cascade reactions and mimic the fundamental aspects of living systems is an outstanding challenge. Highly biocompatible, artificial systems consisting of all-aqueous, compartmentalized multicellular systems have yet to be realized. Here, a rapid multilevel compartmentalization of an all-aqueous system where a 3D sheet of subcolloidosomes encloses a mother colloidosome by interfacial phase separation is demonstrated. These spatially organized multicellular structures are termed "blastosomes" since they are similar to blastula in appearance. The barrier to nanoparticle assembly at the water-water interface is overcome using oppositely charged polyelectrolytes that form a coacervate-nanoparticle-composite network. The conditions required to trigger interfacial phase separation and form blastosomes are quantified in a mapped state diagram. We show a versatile model for constructing artificial multicellular spheroids in all-aqueous systems. The rapid interfacial assembly of charged particles and polyelectrolytes can lock in nonequilibrium shapes of water, which also enables top-down technologies, such as 3D printing and microfluidics, to program flexible compartmentalized structures.

Hanging droplets from liquid surfaces.

Natural and man-made robotic systems use the interfacial tension between two fluids to support dense objects on liquid surfaces. Here, we show that coacervate-encased droplets of an aqueous polymer solution can be hung from the surface of a less dense aqueous polymer solution using surface tension. The forces acting on and the shapes of the hanging droplets can be controlled. Sacs with homogeneous and heterogeneous surfaces are hung from the surface and, by capillary forces, form well-ordered arrays. Locomotion and rotation can be achieved by embedding magnetic microparticles within the assemblies. Direct contact of the droplet with air enables in situ manipulation and compartmentalized cascading chemical reactions with selective transport. Applications including functional microreactors, motors, and biomimetic robots are evident.

Stabilizing Liquids Using Interfacial Supramolecular Polymerization.

The strong electrostatic interactions at the oil-water interface between a small molecule, 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin, H6 TPPS, dissolved in water, and an amine terminated hydrophobic polymer dissolved in oil are shown to produce a supramolecular polymer surfactant (SPS) of H6 TPPS at the interface with a binding energy that is sufficiently strong to allow an intermolecular aggregation of the supramolecular polymers. SPSs at the oil-water interface are confirmed by in situ real-space atomic force microcopy imaging. The assemblies of these aggregates can jam at the interface, opening a novel route to kinetically trap the liquids in non-equilibrium shapes. The elastic film, comprised of SPSs, wrinkles upon compression, providing a strategy to stabilize liquids in non-equilibrium shapes.

Building Reconfigurable Devices Using Complex Liquid-Fluid Interfaces.

Liquid-fluid interfaces provide a platform both for structuring liquids into complex shapes and assembling dimensionally confined, functional nanomaterials. Historically, attention in this area has focused on simple emulsions and foams, in which surface-active materials such as surfactants or colloids stabilize structures against coalescence and alter the mechanical properties of the interface. In recent decades, however, a growing body of work has begun to demonstrate the full potential of the assembly of nanomaterials at liquid-fluid interfaces to generate functionally advanced, biomimetic systems. Here, a broad overview is given, from fundamentals to applications, of the use of liquid-fluid interfaces to generate complex, all-liquid devices with a myriad of potential applications.

Bacteriorhodopsin-Inspired Light-Driven Artificial Molecule Motors for Transmembrane Mass Transportation.

In nature, biological machines and motors can selectively transport cargoes across the lipid membranes to efficiently perform various physiological functions via ion channels or ion pumps. It is interesting and challengeable to develop artificial motors and machines of nanodimensions to controllably regulate mass transport in compartmentalized systems. In this work, we show a system of artificial molecular motors that uses light energy to perform transmembrane molecule transport through synthetical nanochannels. After functionalizing the polymer nanochannels with azobenzene derivatives, these nanomachines exhibit autonomous selective transport behavior over a long distance upon simultaneous irradiation with UV (365 nm) and visible (430 nm) light. With new strategies or suitable materials for directed molecular movement, such device can be regarded as a precursor of artificial light-driven molecular pumps.

Light-Driven ATP Transmembrane Transport Controlled by DNA Nanomachines.

In nature, biological machines can perform sophisticated and subtle functions to maintain the metabolism of organisms. Inspired from these gorgeous works of nature, scientists have developed various artificial molecular motors and machines. However, selective transport of biomolecules across membrane has remained a great challenge. Here, we establish an ATP transport system by assembling photocontrolled DNA nanomachines into the artificial nanochannels. With alternant light irradiation, these ATP transport lines can selectively shepherd cargoes across the polymer membrane. These findings point to new opportunities for manipulating and improving the mass transportation and separation with light-controlled biomolecular motors, and can be used for other molecules and ions transmembrane transport powered by light.

A bio-inspired dumbbell-shaped nanochannel with a controllable structure and ionic rectification.

Inspired by the potassium ion channel, here, we firstly report a structure-tailorable dumbbell-shaped nanochannel with controllable ionic rectification. This system creates an ideal experimental and theoretical platform for the precision transportation of ions, which have potential applications in analytical sciences.

Light- and Electric-Field-Controlled Wetting Behavior in Nanochannels for Regulating Nanoconfined Mass Transport.

Water wetting behavior in nanoconfined environments plays an important role in mass transport and signal transmission of organisms. It is valuable and challenging to investigate how water behaves in such a nanometer-scale with external stimuli, in particular with electric field and light. Unfortunately, the mechanism of hydrophobic reaction inside the nanospaces is still obscure and lacks experimental support for the current electric-field- or photoresponsive nanochannels which suffer from fragility or monofunctionality. Here, we design functionalized hydrophobic nanopores to regulate ion transport by light and electric field using azobenzene-derivatives-modified polymer nanochannels. With these addressable features, we can control the pore surface wetting behavior to switch the nanochannels between nonconducting and conducting states. Furthermore, we found these hydrophobic nanochannels are rough with a contact angle of 67.3°, making them extremely different from the familiar ones with a smooth pore surface and larger contact angles (>90°). These findings point to new opportunities for studying and manipulating water behavior in nanoconfined environments.

Bioinspired Heterogeneous Ion Pump Membranes: Unidirectional Selective Pumping and Controllable Gating Properties Stemming from Asymmetric Ionic Group Distribution.

The creation of an artificial solid-state ion pump that mimics the delicate ion transport behaviors of a biological protein-based ion pump is drawing more and more research attention due to its potential applications in energy conversion, biosensor, and desalination. However, the reported bioinspired double-gated ion pump systems are generally very primary and can only realize nonselective ion pumping functions with no directionality and uncontrollable ion gating functions, which are far from their biological counterparts. To make the bioinspired device "smart" in a real sense, the implementation of high-level selectivity and directionality in the ion pumping process, while achieving great controllability in the ion gating process, is a necessity. Here, we developed a bioinspired heterogeneous ion pump membrane by combining block copolymer membrane sacrificial coating and plasma grafting technique. The system has unidirectional selective ion pumping and controllable ion gating properties. The introduction of asymmetric ionic group distribution is the key reason for its novel transport behaviors. Such a heterogeneous ion pump could not only provide a basic platform that potentially sparks further efforts to simulate the smart ion transport processes in living bodies but also promote the application of artificial nanofluidic devices in energy conversion, water treatment, and biosensing.