A Urease-Containing Fluorescent Hydrogel for Transient Information Storage.

The improper handling of decrypted information can lead to the leakage of confidential data. Thus, there is increasing interest in the development of self-erasing decrypted data. Herein, we report a urease-containing fluorescent hydrogel for multistage information security protection. Information can be input into the fluorescent hydrogel, which is based on the protonated 4-(N,N-dimethylaminoethylene) amino-N-allyl-1,8-naphthalimide (DEAN-H+ ) and doped with urease, using metal ions, such as Zn2+ that coordinate with DEAN. Upon exposure to urea, urease produces NH3 , which reduces the fluorescence of the hydrogel. In the presence of urea, metal-coordinated hydrogel fluorescence decreases more slowly than the fluorescence of the hydrogel alone, revealing the information. The displayed information is then automatically erased within a few minutes. This work opens up a new insights in designing and fabricating information storage materials.

Actuating Supramolecular Shape Memorized Hydrogel Toward Programmable Shape Deformation.

Inspired by nature, diverse biomimetic hydrogel actuators are fabricated and become one of the most essential components of bionics research. Usually, the anisotropic structure of a hydrogel actuator is generated at the early fabrication process, only a specific shape transformation behavior can be produced under external stimuli, and thus has limited the development of hydrogel actuators toward the biomimetic shape deformation behavior. Herein, a novel bilayer hydrogel having a thermoresponsive actuating layer and a metal ion-responsive memorizing layer is proposed, therefore, a 2D hydrogel film can be fixed into various 3D shapes via supramolecular metal-ligand coordination, with further realizing programmable 4D shape deformation under the stimulus of temperature. By manipulating the temporary shapes via shape memory behavior, various temporary anisotropic structures can be obtained via the bilayer hydrogel, thus producing diverse reversible shape deformation performances, which is expected to promote the development of intelligent polymeric materials.

Thermodynamics and kinetics of an oxygen adatom on pristine and functionalized graphene: insight gained into their anticorrosion properties.

The thermodynamic and kinetic stabilities of an O adatom on graphene are critical factors for the formation of oxide defects in graphene, which leads to the breakdown of a graphene protective coating. To systematically understand various behaviors of an O adatom on graphene under the space conditions, the adsorption energies, diffusion paths and barriers, and penetration paths and barriers of the O adatom on pristine and functionalized graphene (e.g., -O, -OH, -H, and -F) are calculated using density functional theory, and the electronic structures are also analyzed in depth to reveal the microscopic mechanisms. We find that chemical functionalization increases both the adsorption stability and diffusion mobility of the O adatom on graphene, implying the possibly exacerbated destructive oxidation and even breakdown of the graphene-based coating. Furthermore, the penetration of the O adatom through pristine and functionalized graphene is also calculated, the occurrence of which is proved to be impossible in reality due to the associated extremely high energetic barriers. The calculated results, revealed mechanisms, and the gained insight into the corrosion resistance of graphene will be helpful for the design, synthesis, and application of related graphene-based protective coatings.

Contribution of Surface Chemistry to the Shear Thickening of Silica Nanoparticle Suspensions.

Shear thickening is a general process crucial for many processed products ranging from food and personal care to pharmaceuticals. Theoretical calculations and mathematical simulations of hydrodynamic interactions and granular-like contacts have proved that contact forces between suspended particles dominate the rheological characteristic of colloidal suspensions. However, relevant experimental studies are very rare. This study was conducted to reveal the influence of nanoparticle (NP) interactions on the rheological behavior of shear-thickening fluids (STFs) by changing the colloidal surface chemistries. Silica NPs with various surface chemical compositions are fabricated and used to prepare dense suspensions. Rheological experiments are conducted to determine the influence of NP interactions on corresponding dense suspension systems. The results suggest that the surface chemistries of silica NPs determine the rheological behavior of dense suspensions, including shear-thickening behavior, onset stress, critical volume fraction, and jamming volume fraction. This study provides useful reference for designing effective STFs and regulating their characteristics.

Attraction induced frictionless sliding of rare gas monolayer on metallic surfaces: an efficient strategy for superlubricity.

Friction on a nanoscale revealed rich load-dependent behavior, which departs strongly from the long-standing Amonton's law. Whilst electrostatic repulsion-induced friction collapse for rare gas sliding over metallic surfaces in a high-load regime was reported by Righi et al. (Phys. Rev. Lett., 2007, 99, 176101), the significant role of attraction on frictional properties has not been reported to date. In this study, the frictional motion of Xe/Cu(111), Xe/Pd(111) and Ar/Cu(111) was studied using van der Waals corrected density functional calculations. An attraction-induced zero friction, which is a signal of superlubricity, was found for the sliding systems. The superlubric state results from the disappearance of the potential corrugation along the favored sliding path as a consequence of the potential crossing in the attractive regime when the interfacial pressure approaches a critical-value. The finding of an attraction-driven friction drop, together with the repulsion-induced collapse in the high-load regime, which breaks down the classic Amonton's law, provides a distinct approach for the realization of inherent superlubricity in some adsorbate/substrate interfaces.

How solid-liquid adhesive property regulates liquid slippage on solid surfaces?

The influence of solid-liquid adhesive property on liquid slippage at solid surfaces has been investigated using experiment approach on well-defined model surfaces as well as theoretical analysis. Based on a classical molecular-kinetic description for molecular and hydrodynamic slip, we propose a simple theoretical model that directly relates the liquid slip length to the liquid adhesive force on solid surfaces, which yields an exponential decay function. Well-defined smooth surfaces with varied surface wettability/adhesion are fabricated by forming self-assembled monolayers on gold with different mole ratios of hydrophobic and hydrophilic thiols. The adhesive force of a water droplet and the molecular slippage on these surfaces are probed by surface force apparatus and quartz crystal microbalance measurements, respectively. The experiment results are well consistent with our theoretical prediction. Our finding benefits the understanding of the underlying mechanism of liquid slippage on solid surfaces at molecular level and the rational design of microfluidics with an aim to be frictionless or highly controllable.

Switching fluid slippage on pH-responsive superhydrophobic surfaces.

Two stimuli-responsive polymer brushes, poly(dimethylaminoethyl methacrylate) and poly(methacrylic acid), were grafted from initiator-modified anodized alumina substrates to prepare two pH-responsive surfaces. By regulating the swelling states of the two polymers, water droplets can roll off or adhere onto the textured surface because of different adhesion forces. These forces also strongly affect boundary slippage. To determine the different slippage effects of fluid on our pH-responsive surfaces, a series of rheological experiments are carried out on two kinds of surfaces. A large slip length is obtained and reversibly regulated by changing the fluid pH. These responsive superhydrophobic surfaces with considerable slip length and pH-responsive properties have extensive potential applications in intelligent micro- and nanofluidic devices or biodevices, which can solve fluid flow problems.

Bioinspired Slippery Surfaces for Liquid Manipulation from Tiny Droplet to Bulk Fluid.

Slippery surfaces, which originate in nature with special wettability, have attracted considerable attention in both fundamental research and practical applications in a variety of fields due to their unique characteristics of superlow liquid friction and adhesion. Although research on bioinspired slippery surfaces is still in its infancy, it is a rapidly growing and enormously promising field. Herein, a systematic review of recent progress in bioinspired slippery surfaces, beginning with a brief introduction of several typical creatures with slippery property in nature, is presented. Subsequently,this review gives a detailed discussion on the basic concepts of the wetting, friction, and drag from micro- and macro-aspects and focuses on the underlying slippery mechanism. Next, the state-of-the-art developments in three categories of slippery surfaces of air-trapped, liquid-infused, and liquid-like slippery surfaces, including materials, design principles, and preparation methods, are summarized and the emerging applications are highlighted. Finally, the current challenges and future prospects of various slippery surfaces are addressed.

Self-healing surface hydrophobicity by consecutive release of hydrophobic molecules from mesoporous silica.

The paper reports a novel approach to achieve self-healing surface hydrophobicity. Mesoporous silica is used as the reservoir for hydrophobic molecules, i.e., octadecylamine (ODA), that can release and refresh the surface hydrophobicity consecutively. A polymdopamine layer is used to further encapsulate silica-ODA, providing a reactive layer, governing release of the underlying ODA, and improving the dispersivity of silica nanoparticles in bulk resin. The approach arrives at self-healing (super)hydrophobicity without using any fluoro-containing compounds.

Rapid control of switchable oil wettability and adhesion on the copper substrate.

We described a facile approach to rapidly achieve the reversible oil wettability and adhesion transition on the copper substrate. Plasma treatment and surface fluorination were used to tune the surface composition, and this tunability of the surface composition, along with the stable surface roughness, gave rise to the switchable wettability varying from superoleophobicity to superoleophilicity and reversible oil adhesion between sliding superoleophobicity and sticky superoleophobicity. It took only 1.25 min to realize the whole wettability transition and 5 min for the whole adhesion transition. Additionally, the application of a sticky superoleophobic surface was demonstrated. This study represents an important addition to the field of functional superoleophobic materials.

Effects of Oxygenated Acids on Graphene Oxide: The Source of Oxygen-Containing Functional Group.

Graphene oxide is an important member of the graphene family which has a wide range of applications. The chemical method, especially the liquid phase method, is one of the most common and important methods for its preparation. However, the complex solution environment not only gives them rich structure, but also brings great challenges for its large-scale industrial synthesis. In order to better realize its industrial application, it is important to understand its structure, such as the source of oxygen-containing functional groups. Here we studied the contribution of four oxygenated acids to oxygen-containing functional groups in Hummers' method using first principles. We found that the permanganic acid molecules that exist instantaneously due to energy fluctuations can be the source of oxygen-containing functional group. In addition, Stone-Wales defect have a certain effect on the formation of oxygen-containing functional groups, but this effect is not as good as that of solvation effect. This work provides a guide for exploring the source of oxygen-containing functional groups on graphene oxide.

Correction: The corrosion behaviors of multilayer diamond-like carbon coatings: influence of deposition periods and corrosive medium.

[This corrects the article DOI: 10.1039/C6RA05527C.].

Viscous Oil De-Wetting Surfaces Based on Robust Superhydrophilic Barium Sulfate Nanocoating.

Viscous oil adherence onto solid surfaces is ubiquitous and has caused intractable fouling problems, impairing the function of solid surfaces in various areas such as optics and separation membranes. Materials with superhydrophilicity and underwater superoleophobicity are very effective in elimination of oil fouling. However, most of them cannot dewet viscous oils and may malfunction without prehydration treatment. Herein, we report a facile and environmental strategy to prepare barium sulfate (BaSO4) nanocoating to dewet viscous oils on dry surfaces. Abundant surface polar groups (surface hydroxyl) on BaSO4 nanocoating enhance both hydrophilicity after oil fouling (underoil water contact angle <10°) and underwater superoleophobicity (underwater-oil contact angle >155°) and then facilitate oil dewetting ability. Different oils with viscosity up to 900 mPa·s can be easily eliminated after immersion into water. The results and force analysis also demonstrate that small surface roughness and ultrahydrophilicity under oil are beneficial to achieve oil dewetting property on dry surfaces. Furthermore, BaSO4 nanocoating displays excellent mechanical, thermal and chemical stability and can maintain oil repellency through various harsh conditions. Outstanding antioil fouling ability also enables the fabric coated by BaSO4 nanocoating to separate crude oil/water with flux higher than 28 000 Lm2-h-1 and separation efficiency larger than 99.9% and maintain effective separation performance even after 100 times of separation. Thus, the robust superhydrophilic BaSO4 nanocoating is potential in oil dewetting and waste oil remediation.

Correction: Corrosion and tribocorrosion performance of multilayer diamond-like carbon film in NaCl solution.

[This corrects the article DOI: 10.1039/C5RA21207C.].

On-site marine oil spillage monitoring probes formed by fixing oxygen sensors into hydrophobic/oleophilic porous materials for early-stage spotty pollution warning.

In this study, an efficient on-site marine oil spillage monitoring probe was developed by fixing oxygen consumption sensors into hydrophobic/oleophilic oil-absorbing porous materials. The impact of thickness and characters of the porous materials, the types of spilled oil, and the presence of salts and vibration in water on the parameters of the obtained signals was investigated. The probe could be used to detect the various representative types of spilled oils including lubricating oil, corn oil, soybean oil, n-hexane, petroleum ether and toluene, even in simulated sea water vibrating at different levels, having over 33 times reduced reliable low detection limit (RLDL) in detecting soybean oil in water (from 36.5 g L-1 to 1.1 g L-1). The response time and signal-to-noise ratios (SNRs) of the probe varied greatly with the dynamic absorbing speed and oxygen barrier property of the spilled oils in the porous material, respectively. The probe showing the highest SNR of 190 dB for a 50 g L-1 on-site soybean oil spillage and the fastest response time of 9 s for a 50 g L-1 on-site toluene spillage in water may potentially be used as a key component in near-shore marine oil spillage monitoring systems to provide early-stage pollution warning.

Multifunctional superhydrophobic adsorbents by mixed-dimensional particles assembly for polymorphic and highly efficient oil-water separation.

Supra-wetting materials, especially superhydrophobic absorption materials, as an emerging advanced oil-water separation material have attracted extensive concern in the treatment of oil spillage and industrial oily wastewater. However, it is still a challenge to fabricate robust and multifunctional superhydrophobic materials for the multitasking oil-water separation and fast clean-up of the viscous crude oil by an environment-friendly and scalable method. Herein, a solid-solid phase ball-milling strategy without chemical reagent-free modification was proposed to construct heterogeneous superhydrophobic composites by using waste soot as the solid-phase superhydrophobic modifier. A series of covalent bond restricted soot-graphene (S-GN) or soot-Fe3O4 (S-Fe3O4) composite materials with a peculiar micro-nano structure are prepared. Through "glue+superhydrophobic particles" method, the prepared soot-based composite particles are facilely loaded on the porous skeleton of the sponge to obtain multifunctional superhydrophobic adsorbents. The reported superhydrophobic adsorbents exhibited robust chemical and mechanical stability, convenient magnetic collection, the high oil absorption capacity of 60-142 g g-1, durable recyclability (>250 cycles), efficient separation efficiency (>99.5%) and outstanding self-heated performance, which enable them to be competent for oil-water separation in multitasking and complex environment (floating oils, continuous oil collection, oil-in-water emulsion, and viscous oil-spills).

Multiscale Structural Modulation of Anisotropic Graphene Framework for Polymer Composites Achieving Highly Efficient Thermal Energy Management.

Graphene is usually embedded into polymer matrices for the development of thermally conductive composites, preferably forming an interconnected and anisotropic framework. Currently, the directional self-assembly of exfoliated graphene sheets is demonstrated to be the most effective way to synthesize anisotropic graphene frameworks. However, achieving a thermal conductivity enhancement (TCE) over 1500% with per 1 vol% graphene content in polymer matrices remains challenging, due to the high junction thermal resistance between the adjacent graphene sheets within the self-assembled graphene framework. Here, a multiscale structural modulation strategy for obtaining highly ordered structure of graphene framework and simultaneously reducing the junction thermal resistance is demonstrated. The resultant anisotropic framework contributes to the polymer composites with a record-high thermal conductivity of 56.8-62.4 W m-1 K-1 at the graphene loading of ≈13.3 vol%, giving an ultrahigh TCE per 1 vol% graphene over 2400%. Furthermore, thermal energy management applications of the composites as phase change materials for solar-thermal energy conversion and as thermal interface materials for electronic device cooling are demonstrated. The finding provides valuable guidance for designing high-performance thermally conductive composites and raises their possibility for practical use in thermal energy storage and thermal management of electronics.

Simply Adjusting the Unidirectional Liquid Transport of Scalable Janus Membranes toward Moisture-Wicking Fabric, Rapid Demulsification, and Fast Oil/Water Separation.

Inspired by nature, Janus membranes with unidirectional liquid transport (ULT) were developed to be used in the fields of fog collection, moisture-wicking fabrics, demulsification, etc. However, the obtained Janus membranes are often unifunctional, and it is still a great challenge to adjust the ULT of Janus membranes for multifunctional applications. Herein, a scalable, low-cost, and machine-washable Janus membrane was developed by combining the cyclic self-assembly of phytic acid and FeIII and a one-side spraying coating of poly(dimethylsiloxane) (PDMS), featuring adjustable ULT upon challenge for multifunctional applications. By controlling the amount of PDMS, the Janus membranes exhibit two different performances, ULT and switchable permeation. The prepared Janus membranes achieved an excellent moisture-wicking fabric (1.6× the water evaporation rate of cotton), fast water collection under oil, rapid demulsification, and the efficient separation of an oil/water mixture. The separation efficiency of a light or heavy oil from water was higher than 99.9% even after 10 separation cycles, and the flux of the separation was up to 2.55 × 104 or 2.38 × 104 L m-2 h-1, respectively. This study could provide an idea for the development of more Janus membranes with adjustable performances to realize multifunctional applications.

One-Step Transformation of Metal Meshes to Robust Superhydrophobic and Superoleophilic Meshes for Highly Efficient Oil Spill Cleanup and Oil/Water Separation.

Phytic acid (PA), which is a natural and innoxious plant constituent, can strongly adsorb on the metal surface because of its six phosphate groups. In this work, based on the chelating properties of PA and the reaction between PA and hydrolyzable vinyltriethoxysilane (VTES), we developed a novel and facial strategy to generate hierarchical-layer nanospheres on the metal mesh surface and fabricated robust superhydrophobic and superoleophilic miniature metal mesh ships. Because of their superwetting properties, the modified meshes could easily remove and recycle the oil spills from the water surface (>90% collection efficiency), and have high oil/water separation capacity (>96%). The excellent stability, corrosion resistance, and robust mechanical durability endow the modified mesh ships with more advantages in a marine environment. We envision that these superhydrophobic meshes modified with PA and VTES are sustainable, environmentally friendly, and easy to scale up and hence display great potential in practical application.

Three-dimensional adsorbent with pH induced superhydrophobic and superhydrophilic transformation for oil recycle and adsorbent regeneration.

With the development of research on superwettability materials, superhydrophobic and superoleophilic materials show superior separation ability in oil-water separation due to their excellent oil-water selectivity. However, due to the super wetting ability of the oil to the material, it is difficult to clean and reuse after adsorbing the oil spill. Therefore, how to realize the complete regeneration of superhydrophobic and superoleophilic materials is still a worldwide problem. In this paper, the controlled adsorption-desorption process of oil and the complete regeneration of materials are realized by pH induced superwettability transformation. We fabricate a pH-responsive oil-water separation sponge by a method of simply impregnating the carboxyl and alkyl group modified SiO2 nanoparticles on the surface of melamine sponge (MS) skeleton, which can change the wettability from superhydrophobicity and superhydrophilicity through protonation and deprotonation in different pH solutions. The experiment results indicate that the sponge is superhydrophobic and superoleophilic in acid and neutral solution, and can adsorb oil in water. While in basic solution, it becomes superhydrophilic and underwater superoleophobic, which can release the adsorbed oil. With the help of a vacuum pump, we can use this wettability transition to achieve a continuous oil adsorption and desorption process. These findings offer a new preparation method of regenerative 3D adsorption materials like MS in oil-water separation.