Bioinspired multi-scale interface design for wet gas sensing based on rational water management.

Natural organisms have evolved multi-scale wet gas sensing interfaces with optimized mass transport pathways in biological fluid environments, which sheds light on developing artificial counterparts with improved wet gas sensing abilities and practical applications. Herein, we highlighted current advances in wet gas sensing taking advantage of optimized mass transport pathways endowed by multi-scale interface design. Common moisture resistance (e.g., employing moisture resistant sensing materials, post-modifying moisture resistant coatings, physical heating for moisture resistance, and self-removing hydroxyl groups) and moisture absorption (e.g., employing moisture absorption sensing materials and post-modifying moisture absorption coatings) strategies for wet gas sensing were discussed. Then, the design principles of bioinspired multi-scale wet gas sensing interfaces were provided, including macro-level condensation mediation, micro/nano-level transport pathway adjustment and molecular level moisture-proof design. Finally, perspectives on constructing bioinspired multi-scale wet gas sensing interfaces were presented, which will not only deepen our understanding of the underlying principles, but also promote practical applications.

Synergistic effects of the bimetallic Ni-Fe systems and their application in the reductive amination of polyether polyols.

We report the synthesis of xNi-yFe/γ-Al2O3 catalysts which were applied to the reductive amination of polypropylene glycol (PPG) for the preparation of polyether amine (PEA). The catalysts were characterized by N2-sorption, X-ray diffraction, H2-temperature programmed reduction, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy to reveal the synergistic effect of the bimetallic Ni-Fe-loaded catalysts. It was found that in the reductive amination of PPG to PEA, the conversion and product selectivity of the reaction were closely related to the types of active centers of the catalyst. In particular, the surface Ni0 content increased by adding Fe as a promoter, with a maximum Ni0 content on the 15Ni-7.5Fe/Al2O3 catalyst, which also led to the highest conversion rate (>99%). In addition, no deactivation was observed after three cycles of reaction carried out by the catalyst.

Interfacial Water-Dictated Oil Adhesion Based on Ion Modulation.

Oil adhesion on ionic surfaces is ubiquitous in organisms and natural environments and is generally determined by surface chemical component and texture. However, when adhesion occurs, water molecules at the solid-liquid interface, acting as a bridge not only influenced by the structure and composition of the solid surface but also interacting with the neighboring oil molecules, play a crucial role but are always overlooked. Herein, we investigate the oil adhesion process on a carboxyl-terminated self-assembled monolayer surface (COOH-SAM) in ionic solutions and observe the interfacial water structure via surface-enhanced Raman scattering (SERS) in this system. It is found that the lower the tetracoordinated water content, the stronger the oil adhesion. Compared to monovalent ions, the strengthened binding of multivalent ions to the COOH-SAM surface makes the interfacial water more disordered, which eventually leads to a stronger oil adhesion. Notably, the amount of oil adhesion decreases with an increase in the thickness of the interfacial water region. The interfacial water-dictated oil adhesion has been demonstrated in capillary to simulate the water-driven oil recovery, providing a molecular-level explanation for enhanced oil recovery from low salinity water flooding and also indicating potential applications in intelligent microfluidic and seawater desalination.

Heterostructure particles enable omnidispersible in water and oil towards organic dye recycle.

Dispersion of colloidal particles in water or oil is extensively desired for industrial and environmental applications. However, it often strongly depends on indispensable assistance of chemical surfactants or introduction of nanoprotrusions onto the particle surface. Here we demonstrate the omnidispersity of hydrophilic-hydrophobic heterostructure particles (HL-HBPs), synthesized by a surface heterogeneous nanostructuring strategy. Photo-induced force microscopy (PiFM) and adhesion force images both indicate the heterogeneous distribution of hydrophilic domains and hydrophobic domains on the particle surface. These alternating domains allow HL-HBPs to be dispersed in various solvents with different polarity and boiling point. The HL-HBPs can efficiently adsorb organic dyes from water and release them into organic solvents within several seconds. The surface heterogeneous nanostructuring strategy provides an unconventional approach to achieve omnidispersion of colloidal particles beyond surface modification, and the omnidispersible HL-HBPs demonstrate superior capability for dye recycle merely by solvent exchange. These omnidispersible HL-HBPs show great potentials in industrial process and environmental protection.

Ultrafast Impact Superspreading on Superamphiphilic Silicon Surfaces for Effective Thermal Management.

Controllable impact spreading behavior is critical for effective thermal management of spray cooling. However, splash and retraction are common problems on hydrophobic (HPB) and hydrophilic (HPL) surfaces. Herein, by regulation of surface wettability, we report a controllable ultrafast impact superspreading behavior (superspreading time of ∼3.0 ms) without splash and retraction on superamphiphilic (SAPL) silicon surfaces. Analysis of dynamic wetting processes combined with observation of lateral force microscopy images on SAPL surfaces reveals the existence of a precursor film at the spreading edge induced by heterogeneous surface wettability at nanoscale. Further study indicates that the inhibition of splash results from the high liquid flux in precursor film, which suppresses the interposition of air at the spreading edge. The reduction of Laplace forces owing to the presence of precursor film inhibits retraction at the spreading frontier. Taking advantage of this impact superspreading behavior on SAPL surfaces, effective heat dissipation is demonstrated, offering uniform and high heat flux for the spray cooling process.

Large-Scale Metal-Organic Framework Nanoparticle Monolayers with Controlled Orientation for Selective Transport of Rare-Earth Elements.

Long-range ordered membranes comprised of porous nanoparticles have been pursued in precise separations for a long time. Yet most of the fabrication methods suffer from limited substrates or lack of precise control over crystal orientation. Herein, large-scale metal-organic framework (MOF) monolayer membranes with controlled orientations are prepared through an interfacial self-assembly process confined by superlyophilic substrates. The superspreading of reactant microdroplets results in an ultrathin liquid layer under an immiscible oil as a confined reactor. The concomitant MOF (ZIF-8) particles spontaneously assemble into monolayers with controlled orientations, determined by the particles' contact angles at the liquid/liquid interface, which can be regulated by solvent compositions. Therein both gas-adsorption and ion-transport tests prove that the ⟨111⟩-oriented membrane exhibits a minimized mass-transfer resistance. The as-prepared membrane can selectively transport rare-earth elements (REEs), and a La3+/K+ selectivity of 14.3 is achieved. Molecular dynamics simulations reveal that the REEs-selectivity is associated with the distinct difference in ion-membrane binding energies, demonstrating the potential of ZIF-8 membranes for use in high-efficiency recovery of REEs from industrial wastes.

Bio-inspired adhesion control with liquids.

Bio-inspired surfaces enabling wet adhesion management are of significant interest for applications in the field of biomedicine, as components of bionic robots and as wearable devices. In the course of biological evolution, many organisms have evolved wet adhesive surfaces with strong attachment ability. Insects enhance their adhesion on contact substrates using secreted adhesive liquids. Here we discuss concepts of bio-inspired wet adhesion. First, remaining challenges associated with the understanding and the design of biological and artificial wet adhesive systems as well as strategies to supply adhesive liquids to their contact surfaces are reviewed. Then, future directions to construct wet adhesive surfaces with liquids are discussed in detail. Finally, a model of wet adhesion management with liquids is suggested, which might help the design of next-generation bio-inspired wet adhesive surfaces.

Crystal face dependent intrinsic wettability of metal oxide surfaces.

Knowledge of intrinsic wettability at solid/liquid interfaces at the molecular level perspective is significant in understanding crucial progress in some fields, such as electrochemistry, molecular biology and earth science. It is generally believed that surface wettability is determined by the surface chemical component and surface topography. However, when taking molecular structures and interactions into consideration, many intriguing phenomena would enrich or even redress our understanding of surface wettability. From the perspective of interfacial water molecule structures, here, we discovered that the intrinsic wettability of crystal metal oxide is not only dependent on the chemical components but also critically dependent on the crystal faces. For example, the [Formula: see text] crystal face of α-Al2O3 is intrinsically hydrophobic with a water contact angle near 90°, while another three crystal faces are intrinsically hydrophilic with water contact angles <65°. Based on surface energy analysis, it is found that the total surface energy, polar component and Lewis base portion of the hydrophobic crystal face are all smaller than the other three hydrophilic crystal faces indicating that they have different surface states. DFT simulation further revealed that the adsorbed interfacial water molecules on each crystal face hold various orientations. Herein, the third crucial factor for surface wettability from the perspective of the molecular level is presented, that is the orientations of adsorbed interfacial water molecules apart from the macro-level chemical component and surface topography. This study may serve as a source of inspiration for improving wetting theoretical models and designing controllable wettability at the molecular/atomic level.

LncRNA AFAP1-AS1 Promotes the Progression of Colorectal Cancer through miR-195-5p and WISP1.

OBJECTIVE: Colorectal cancer (CRC) is the most common cancer. But, the molecular mechanisms of CRC progression are not fully understood. This study was conducted to explore how the long noncoding RNA actin filament-associated protein 1-antisense RNA1 (lncRNA AFAP1-AS1) participates in CRC progression through the regulation of microRNA-195-5p (miR-195-5p) and wingless-type inducible signaling pathway protein-1 (WISP1). METHODS: The expressions of AFAP1-AS1, miR-195-5p, and WISP1 were detected by RT-qPCR or western blot. A dual-luciferase assay confirmed the target relationship of AFAP1-AS1, miR-195-5p, and WISP1. Colony formation, wound-healing, and Transwell assays were used to detect the growth, migration, and invasion abilities of cells, respectively. RESULTS: AFAP1-AS1 and WISP1 expressions were notably increased, and miR-195-5p expression was markedly reduced in CRC. The dual-luciferase assay verified that AFAP1-AS1 could bind to miR-195-5p. AFAP1-AS1 knockdown could inhibit the malignant behavior of CRC cells. miR-195-5p could target and regulate WISP1 expression. Overexpression of WISP1 or miR-195-5p inhibition reversed the inhibition effect of AFAP1-AS1 knockdown on the biological activity of CRC cells. CONCLUSIONS: AFAP1-AS1 knockdown may inhibit the proliferation, migration, and invasion of CRC cells through the miR-195-5p/WISP1 axis.

Evaporation-Induced rGO Coatings for Highly Sensitive and Non-Invasive Diagnosis of Prostate Cancer in the PSA Gray Zone.

The prostate-specific antigen (PSA) has been widely used for the early diagnosis of prostate cancer during routine check-ups. However, the low sensitivity of regular PSA tests in the PSA gray zone often means that patients are required to undergo further invasive needle biopsy for the diagnosis of prostate cancer, which may lead to potential overdiagnosis and overtreatment. In this study, a circulating tumor cell (CTC)-chip based on an evaporation-induced reduced graphene oxide (rGO) coating is presented, which enables a highly specific and non-invasive diagnosis of prostate cancer in the PSA gray zone. During the evaporation process of the rGO dispersion, the Marangoni effect induces the self-assembly of a hierarchical micro/nanowrinkled rGO coating, which can capture CTCs after subsequent surface modification of capture agents. Compared to the low diagnostic sensitivity (58.3%) of regular PSA tests, a combination of CTC detection and PSA-based hematological tests via machine-learning analysis can greatly upgrade the diagnostic sensitivity of this disease to 91.7% in clinical trial. Therefore, this study provides a non-invasive alternative with high sensitivity for the diagnosis of prostate cancer in the PSA gray zone.

Highly Efficient Hydroisomerization of Endo-Tetrahydrodicyclopentadiene to Exo-Tetrahydrodicyclopentadiene over Pt/HY.

The fast deactivation caused by serious formation of coke is a major challenge in catalytic isomerization of endo-tetrahydrodicyclopentadiene (endo-THDCPD) into exo-tetrahydrodicyclopentadiene (exo-THDCPD) over the HY zeolite. In order to suppress the coke formation for the isomerization process, the conventional HY zeolite was modified with Pt at 0.3 wt %. Then, the hydroisomerization of endo-THDCPD into exo-THDCPD was evaluated over a fixed-bed reactor. The catalytic stability of Pt/HY was greatly enhanced in comparison to that of the HY zeolite. The Pt/HY catalyst provided 97% endo-THDCPD conversion and 96% selectivity for exo-THDCPD without deactivation after 100 h. Moreover, the formation mechanism of coke on the HY zeolite during the isomerization process was proposed based on the results of the coke analysis. It was indicated that the coke was generated from the oligomerization and condensation of olefin species, which originated from the ß-scission reaction or hydride transfer reaction of intermediates. The lower coke formation over Pt/HY was attributed to the lower amount of coke precursors, which could be hydrogenated by activated H2 over Pt sites. Therefore, Pt on Pt/HY and H2 were two crucial factors in efficiently enhancing the catalytic stability of the HY zeolite for this isomerization reaction.

Superhydrophobic-Substrate-Assisted Construction of Free-Standing Microcavity-Patterned Conducting Polymer Films.

Patterned conducting polymer films with unique structures have promising prospects for application in various fields, such as actuation, water purification, sensing, and bioelectronics. However, their practical application is hindered because of the limitations of existing construction methods. Herein, a strategy is proposed for the superhydrophobic-substrate-assisted construction of free-standing 3D microcavity-patterned conducting polymer films (McPCPFs) at micrometer resolution. Easy-peeling and nondestructive transfer properties are achieved through electrochemical polymerization along the solid/liquid/gas triphase interface on micropillar-structured substrates. The effects of the wettability and geometrical parameters of the substrates on the construction of McPCPFs are systematically investigated in addition to the evolution of the epitaxial growth along the triphase interface at different polymerization times. The McPCPFs can be easily peeled from superhydrophobic surfaces using ethanol because of weak adhesion and nondestructively transferred to various substrates taking advantage of the capillarity. Furthermore, sensitive light-driven McPCPF locomotion on organic liquid surfaces is demonstrated. Ultimately, a facile strategy for the construction of free-standing 3D microstructure-patterned conducting polymer films is proposed, which can improve productivity and applicability of the films in different fields and expand the application scope of superwettable interfaces.

Super-spreading on superamphiphilic micro-organized nanochannel anodic aluminum oxide surfaces for heat dissipation.

Nature-inspired superamphiphilic surfaces have drawn tremendous attention owing to its extreme liquid-loving behaviors. Herein, a micro-organized nano-channel (Mo-Na) superamphiphilic anodic aluminum oxide (AAO) surface with long-lasting superamphiphilic property is prepared by a facile one-step anodization method with controllable temperature change. Analysis of dynamic wetting behaviors on superamphiphilic Mo-Na AAO surfaces for various liquids reveals that the spreading factor is in negative correlation with the surface tension and liquid polarity. Detailed observation of the three-phase contact line shows a micro-scale capillary film on superamphiphilic Mo-Na AAO surfaces, which results from the horizontal component of the capillary force. Taking advantage of the superamphiphilic property, water droplets can spread completely on these Mo-Na AAO surfaces within a short time, which can be applied for efficient heat dissipation. Moreover, the unique AAO surface with Mo-Na structures also offers an effective template for future efforts in AAO-based composite devices.

Microchannel and Nanofiber Array Morphology Enhanced Rapid Superspreading on Animals' Corneas.

The dynamic spreading phenomenon of liquids is vital for both understanding wetting mechanisms and visual reaction time-related applications. However, how to control and accelerate the spreading process is still an enormous challenge. Here, a unique microchannel and nanofiber array morphology enhanced rapid superspreading (RSS) effect on animals' corneas with a superspreading time (ST) of 830 ms is found, and the respective roles of the nanofiber array and the microchannel in the RSS effect are explicitly demonstrated. Specifically, the superspreading is induced by in-/out-of-plane nanocapillary forces among the nanofiber array; the microchannel is responsible for tremendously speeding up the superspreading process. Inspired by the RSS strategy, not only is an RSS surface fabricated with an ST of only 450 ms, which is, respectively, more than 26 and 1.8 times faster than conventional superamphiphilic surfaces and animal's corneas and can be applied as RSS surfaces on video monitors to record clear videos, but also it is demonstrated that the RSS effect has tremendous potential as advanced ophthalmic material surfaces to enhance its biocompatibility for clear vision.

Ferrocene-based conjugated microporous polymer and its multiwalled carbon nanotube composite for direct photocatalytic benzene hydroxylation to phenol.

Ferrocene is used as a catalytically active site and building block to construct a new conjugated microporous polymer (CMP), named Fc-POP. A corresponding carbon nanotube composite (CNTs@Fc-POP) with tubular structure was obtained through the π-π interaction between multi-walled carbon nanotubes (MWCNTs) and reactive molecules. This innovative modification method of carbon nanotubes provides a way to construct functionalized carbon materials. The two materials can achieve high conversion and selectivity of benzene hydroxylation to phenol under light irradiation using hydrogen peroxide (H2O2) as an oxidant. Due to the synergistic effect between the carbon nanotubes and the ferrocene group, the incorporation of MWCNTs can improve the yield of phenol significantly. This work explores a new photocatalystic system and expands the related photocatalytic application of CNTs.

Rational ion transport management mediated through membrane structures.

Unique membrane structures endow membranes with controlled ion transport properties in both biological and artificial systems, and they have shown broad application prospects from industrial production to biological interfaces. Herein, current advances in nanochannel-structured membranes for manipulating ion transport are reviewed from the perspective of membrane structures. First, the controllability of ion transport through ion selectivity, ion gating, ion rectification, and ion storage is introduced. Second, nanochannel-structured membranes are highlighted according to the nanochannel dimensions, including single-dimensional nanochannels (i.e., 1D, 2D, and 3D) functioning by the controllable geometrical parameters of 1D nanochannels, the adjustable interlayer spacing of 2D nanochannels, and the interconnected ion diffusion pathways of 3D nanochannels, and mixed-dimensional nanochannels (i.e., 1D/1D, 1D/2D, 1D/3D, 2D/2D, 2D/3D, and 3D/3D) tuned through asymmetric factors (e.g., components, geometric parameters, and interface properties). Then, ultrathin membranes with short ion transport distances and sandwich-like membranes with more delicate nanochannels and combination structures are reviewed, and stimulus-responsive nanochannels are discussed. Construction methods for nanochannel-structured membranes are briefly introduced, and a variety of applications of these membranes are summarized. Finally, future perspectives to developing nanochannel-structured membranes with unique structures (e.g., combinations of external macro/micro/nanostructures and the internal nanochannel arrangement) for mediating ion transport are presented.

Photo-Irresponsive Molecule-Amplified Cell Release on Photoresponsive Nanostructured Surfaces.

Cell manipulation has raised extensive concern owing to its underlying applications in numerous biological situations such as cell-matrix interaction, tissue engineering, and cell-based diagnosis. Generally, light is considered as a superior candidate for manipulating cells (e.g., cell release) due to their high spatiotemporal precision and non-invasion. However, it remains a big challenge to release cells with high efficiency due to their potential limitation of the light-triggered wettability transition on photoresponsive surfaces. In this study, we report a photoresponsive spiropyran-coated nanostructured surface that enables highly efficient release of cancer cells, amplified by the introduction of a photo-irresponsive molecule. On one hand, structural recognition stems from topological interaction between nanofractal surfaces and the protrusions of cancer cells. On the other, molecular recognition can be amplified by a photo-irresponsive and hydrophilic molecule by reducing the steric hindrance of photoresponsive components and resisting nonspecific cell adhesion. Therefore, this study may afford a novel avenue for developing advanced smart materials for high-quality biological analysis and clinical diagnosis.

Ion/Molecule Transportation in Nanopores and Nanochannels: From Critical Principles to Diverse Functions.

Nanopores and nanochannels are ubiquitous, from biological systems to various artificial materials. Taking advantage of size confinement and tailoring the interior components, numerous functions can be achieved such as selectivity, gating, rectification, and so on, which result from diverse interactions between ion/molecule and nanopore/nanochannel. In this Perspective, on account of the summarized critical principles, namely size/shape, wettability, charge, recognition, and other interactions during ion/molecule transportation in nanopores and nanochannels, we introduce four main sections of applications: selective transportation in separation, controllable gating systems, energy conversion devices, and sensors. In addition, some typical challenges and possible future research endeavors in the related fields will also be discussed.

Bioinspired Self-Healing Liquid Films for Ultradurable Electronics.

Resistive strain sensors play a crucial role in the development of flexible and stretchable electronics because of their excellent sensitivity and conformability. However, such sensors suffer from poor durability because of the low adhesion strength between the solid conductive layer and polymer and the irreparable dry friction inside the conventional solid conductive layers. Here, inspired from the structures and excellent abrasion resistance of tear films on animal corneas, we demonstrate ultradurable strain sensors based on uniform self-healing wear-free liquid films formed on biomimetic microvilli made from modified polydimethylsiloxane (PDMS). Ethanol solutions containing ionic liquids (ILs) are added to PDMS microvilli, which are superlyophilic due to the surface chemistry and special structures. During evaporation, ILs are driven upward by Laplace pressure and join into continuous conductive films. As the sensing layer, when repeatedly stretched and released, the capillary-stabilized liquid film is lossless because of wet friction, and the cracks will recover completely after release due to the capillary-force-induced self-healing capability, allowing the strain sensors to exhibit high durability of over 22 500 loading-unloading cycles. This work presents an approach for the construction of ultradurable electronics.