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.

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.

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.

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.

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.

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.

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.

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.

Ultrathin and Ion-Selective Janus Membranes for High-Performance Osmotic Energy Conversion.

The osmotic energy existing in fluids is recognized as a promising "blue" energy source that can help solve the global issues of energy shortage and environmental pollution. Recently, nanofluidic channels have shown great potential for capturing this worldwide energy because of their novel transport properties contributed by nanoconfinement. However, with respect to membrane-scale porous systems, high resistance and undesirable ion selectivity remain bottlenecks, impeding their applications. The development of thinner, low-resistance membranes, meanwhile promoting their ion selectivity, is a necessity. Here, we engineered ultrathin and ion-selective Janus membranes prepared via the phase separation of two block copolymers, which enable osmotic energy conversion with power densities of approximately 2.04 W/m2 by mixing natural seawater and river water. Both experiments and continuum simulation help us to understand the mechanism for how membrane thickness and channel structure dominate the ion transport process and overall device performance, which can serve as a general guiding principle for the future design of nanochannel membranes for high-energy concentration cells.

Sequential Recognition of Zinc and Pyrophosphate Ions in a Terpyridine-Functionalized Single Nanochannel.

A highly selective recognition system for zinc(II) and pyrophosphate ions is constructed using a single conical nanochannel covalently functionalized with N'-{4-[(2,2':6',2''-terpyridine)-4-yl]benzyl}ethane-1,2-diamine (TPYD). The immobilized TPYD acts as a specific coordination site for Zn2+ to form TPYD-Zn2+ complexes in preference over other metal ions, and subsequently, the resulting Zn2+ -coordinated nanochannel can be used as a selective recognition element for the pyrophosphate ion based on the coordination reaction between hydroxyl oxygen atoms of pyrophosphate and Zn2+ . Ion recognition is monitored by measuring the current-voltage curves of the solutions. The ionic current of the TPYD-functionalized system at -2.0 V undergoes a clear decrease after exposure to Zn2+ ions and is followed with an obvious increase after subsequent treatment with a pyrophosphate solution. The change of ionic current can be primarily attributed to the variation of charge density of the nanochannel. This functionalized single nanochannel might provide a simple and universal means to recognize other targets by modifying different functional molecules onto the inner surfaces of nanochannels.

A Tunable Ionic Diode Based on a Biomimetic Structure-Tailorable Nanochannel.

A tunable ionic diode is presented that is based on biomimetic structure-tailorable nanochannels, with precise ion-transport characteristics from ohmic behavior to bidirectional rectification as well as gating properties. The forward/reverse directions of the ionic diode and the degree of rectification can be well-regulated by combining the patterned surface charge and the sophisticated structure. This system creates an ideal platform for precise transportation of ions and molecules, and potential applications in analytical sciences are anticipated.

Adenosine-Activated Nanochannels Inspired by G-Protein-Coupled Receptors.

A bioinspired adenosine activated nanodevice is demonstrated in which the conformations of the designed aptamer change and cause signal transmission according to the emergence of adenosine. This bioinspired system exhibits very high response ratios (activated/nonactivated ratio up to 614) and excellent stability and reversibility, and shows promising applications in the fields of biosensors, pharmaceutica, and healthcare systems.

Light-Controlled Ion Transport through Biomimetic DNA-Based Channels.

Light-controlled nanochannels are fabricated through self-assembling azobenzene-incorporated DNA (Azo-DNA) strands to regulate ion transport. By switching between collapsed and relaxed states using visible and ultraviolet light alternately, the Azo-DNA channels can be opened and closed because the conformation of Azo-DNA changes, that is, Azo-DNA is used as switchable controlling unit. In addition to sharing short response time and reversibility with other photoresponsive apparatuses, the Azo-DNA-based nanochannel system has advantages in good biocompatibility and versatile design, which could potentially be applied in light-controlled drug release, optical information storage, and logic networks.

Engineered Ionic Gates for Ion Conduction Based on Sodium and Potassium Activated Nanochannels.

In living systems, ion conduction plays a major role in numerous cellular processes and can be controlled by biological ion channels in response to specific environmental stimuli. This article describes biomimetic ionic gates for ion conduction based on sodium and potassium activated nanochannels. The Na(+) activated ionic gate and K(+) activated ionic gate were developed by immobilizing the alkali metal cation-responsive functional molecules, 4'-aminobenzo-15-crown-5 and 4'-aminobenzo-18-crown-6, respectively, onto the conical polyimide nanochannels. When the ionic gate was in the presence of the specific alkali metal cation, positively charged complexes formed between the crown ether and the alkali metal cation. On the basis of the resulting changes in surface charge, wettability and effective pore size, the nanochannel can achieve reversible switching. The switching behaviors of the two complexes differed due to the differences in binding strength between the two complexes. The Na(+) activated ionic gate is able to open and close to control the ion conduction through the nanochannel, and the K(+) activated ionic gate enables selective cation and anion conduction through the nanochannel. The Na(+) and K(+) activated ionic gates show great promise for use in clinical medicine, biosensors and drug delivery based on their high sensitivity and selectivity of being activated, and good stability.

Engineered Asymmetric Heterogeneous Membrane: A Concentration-Gradient-Driven Energy Harvesting Device.

Engineered asymmetric membranes for intelligent molecular and ionic transport control at the nanoscale have gained significant attention and offer prospects for broad application in nanofluidics, energy conversion, and biosensors. Therefore, it is desirable to construct a high-performance heterogeneous membrane capable of coordinating highly selective and rectified ionic transport with a simple, versatile, engineered method to mimic the delicate functionality of biological channels. Here, we demonstrate an engineered asymmetric heterogeneous membrane by combining a porous block copolymer (BCP) membrane, polystyrene-b-poly(4-vinylpyridine) (PS48400-b-P4VP21300), with a track-etched asymmetric porous polyethylene terephthalate membrane. The introduction of chemical, geometrical, and electrostatic heterostructures provides our heterogeneous membrane with excellent anion selectivity and ultrahigh ionic rectification with a ratio of ca. 1075, which is considerably higher than that of existing ionic rectifying systems. This anion-selective heterogeneous membrane was further developed into an energy conversion device to harvest the energy stored in an electrochemical concentration gradient. The concentration polarization phenomenon that commonly exists in traditional reverse electrodialysis can be eliminated with an asymmetric bipolar structure, which considerably increases the output power density. This work presents an important paradigm for the use of versatile BCPs in nanofluidic systems and opens new and promising routes to various breakthroughs in the fields of chemistry, materials science, bioscience, and nanotechnology.

A bio-inspired, sensitive, and selective ionic gate driven by silver (I) ions.

By grafting specific response DNA on the interior surface of ion track-etched conical nanochannels, a highly sensitive and selective ionic gate that can be driven by silver (I) ions is demonstrated. The switches between the OFF-state and the ON-state are mainly dependent on silver (I) ions and cysteine. Such a biomimetic nanodevice shows potential for application in sensing, pharmaceuticals, and sterilization.

A Bioinspired Switchable and Tunable Carbonate-Activated Nanofluidic Diode Based on a Single Nanochannel.

A smart nanofluidic diode that exhibits both ion gating and ion current rectification has been developed using a 1-(4-amino-phenyl)-2,2,2-trifluoro-ethanone-functionalized, conical nanochannel in a polyimide (PI) membrane. The switch-like property can be tuned by controlling the wettability and charge distribution with carbonate ions. Such a nanodevice is advantageous for precisely controlling conductive states with an ultrahigh gating ratio of up to 5000, and a high rectification ratio of 27. By virtue of the high selectivity and sensitivity for carbonate ions, this nanofluidic diode may find applications in carbonate or carbon dioxide detection.

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.