High-breathable, antimicrobial and water-repellent face mask for breath monitoring.

Face masks with multiple functionalities and exceptional durability have attracted increasing interests during the COVID-19 pandemic. How to integrate the antibacterial property, comfortability during long-time wearing, and breath monitoring capability together on a face mask is still challenging. Here we developed a kind of face mask that assembles the particles-free water-repellent fabric, antibacterial fabric, and hidden breath monitoring device together, resulting in the highly breathable, water-repellent, and antibacterial face mask with breath monitoring capability. Based on the rational design of the functional layers, the mask shows exceptional repellency to micro-fogs generated during breathing while maintaining high air permeability and inhibiting the passage of bacteria-containing aerogel. More importantly, the multi-functional mask can also monitor the breath condition in a wireless and real-time fashion, and collect the breath information for epidemiological analysis. The resultant mask paves the way to develop multi-functional breath-monitoring masks that can aid the prevention of the secondary transmission of bacteria and viruses while preventing potential discomfort and face skin allergy during long-period wearing.

Understanding Gel-Powers: Exploring Rheological Marvels of Acrylamide/Sodium Alginate Double-Network Hydrogels.

This study investigates the rheological properties of dual-network hydrogels based on acrylamide and sodium alginate under large deformations. The concentration of calcium ions affects the nonlinear behavior, and all gel samples exhibit strain hardening, shear thickening, and shear densification. The paper focuses on systematic variation of the alginate concentration-which serves as second network building blocks-and the Ca2+-concentration-which shows how strongly they are connected. The precursor solutions show a typical viscoelastic solution behavior depending on alginate content and pH. The gels are highly elastic solids with only relatively small viscoelastic components, i.e., their creep and creep recovery behavior are indicative of the solid state after only a very short time while the linear viscoelastic phase angles are very small. The onset of the nonlinear regime decreases significantly when closing the second network (alginate) upon adding Ca2+, while at the same time the nonlinearity parameters (Q0, I3/I1, S, T, e3/e1, and v3/v1) increase significantly. Further, the tensile properties are significantly improved by closing the alginate network by Ca2+ at intermediate concentrations.

GaOOH Crystallite Growth on Liquid Metal Microdroplets in Water: Influence of the Local Environment.

Gallium-based liquid metals form alloys with a melting point close to or below room temperature. On the surface of these liquid metals, a thin oxide skin is formed once in contact with oxygen, and this oxide skin can be leveraged to stabilize liquid metal micro- and nanodroplets in a liquid. During sonication and storage of these droplets in aqueous solution, gallium oxide hydroxide (GaOOH) forms on these droplets, and given enough time or treatment with heat, a full shape transition and dealloying are observed. In this article, we show that GaOOH can be grown at room temperature and that the growth is dependent on both the local environment and temperature. GaOOH growth on liquid metal microdroplets located at the air/water interface is considerably faster than in the bulk phase. Interestingly, hydrolysis to GaOOH is hampered and stops at 15 °C in bulk water after 6 h. In contrast, hydrolysis commences even at 15 °C for liquid metal microdroplets located at the air/water interface, and full surface coverage is obtained after around 24 h (compared to 12 h at 25 °C at the air/water interface). The X-ray photoelectron spectroscopy (XPS) measurement suggests that gallium oxide is dissolved and Ga(OH)3 is formed as a precursor that reacts in a downstream reaction toward GaOOH. This improved understanding of the GaOOH formation can be leveraged to control the liquid metal micro- and nanodroplet shape and composition (i.e., for biomedical applications).

Surface Tension of the Oxide Skin of Gallium-Based Liquid Metals.

Gallium-based alloys have garnered considerable attention in the scientific community, particularly as they are in an atypical liquid state at and near room temperature. Though physical parameters, such as thermal conductivity, electrical conductivity, viscosity, yield stress, and surface tension, of these alloys are broadly known, the surface tension (surface free energy) of the oxide skin remains intangible due to the high yield stress of the oxide skin. In this article, we propose to employ gradually attenuated vibrations to obtain equilibrium shapes, which are analyzed along the lines of the puddle height method. The surface tension of the oxide skin was determined on quartz glass and liquid metal-phobic diamond coating to be around 350-365 mN/m, thus independent of the substrate surface or employed liquid metal (i.e., eutectic Ga-In (EGaIn) and galinstan). The similarity of the surface tension for different alloys was ascribed to the composition of the oxide skin, which predominantly comprises gallium oxides due to thermodynamic constraints. We envision that this method can also be applied to other liquid metal alloys and liquid metal marble systems facilitating modeling, simulation, and optimization processes.

Tough hybrid microgel-reinforced hydrogels dependent on the size and modulus of the microgels.

Microgel-reinforced (MR) hydrogels are tough hydrogels with dispersed rigid microgels embedded in a continuous soft matrix. MR gels have the great potential to provide not only mechanical toughness but also the desired functional matrix by incorporation of various functional microgels. Understanding the toughening mechanism of the MR hydrogels is critical for the rational design of the desired functionally tough MR gels. However, our current knowledge of the toughening mechanism of MR gels mainly comes from the MR hydrogels with both chemically crosslinked dispersed microgels and a continuous matrix. Little is known about the hybrid MR gels with physically crosslinked microgels embedded in a chemically crosslinked matrix. Herein, we synthesize such hybrid MR hydrogels with the ionic crosslinked calcium alginate microgels incorporated into the chemically crosslinked polyacrylamide (PAAm) matrix. The alginate microgels show strong size and modulus effects on the toughening enhancement: the larger microgels could toughen the MR gels more than the small ones, and the microgels with medium modulus could maximize the toughness of the MR gels. By comparison of the mechanical performances of the MR and the corresponding double network (DN) hydrogels, we have proposed that the hybrid MR gels may have the same toughening mechanism as the bulk DN gel. This work tries to better understand the structure-property relationships of both MR and DN gels and help in the design of more functionally tough MR gels with the desired properties.

Densely Populated Bismuth Nanosphere Semi-Embedded Carbon Felt for Ultrahigh-Rate and Stable Vanadium Redox Flow Batteries.

The elaborate spatial arrangement and immobilization of highly active electrocatalysts inside porous substrates are crucial for vanadium redox flow batteries capable of high-rate charging/discharging and stable operation. Herein, a type of bismuth nanosphere/carbon felt is devised and fabricated via the carbothermic reduction of nanostructured bismuth oxides. The bismuth nanospheres with sizes of ≈25 nm are distributed on carbon fiber surfaces in a highly dispersed manner and its density reaches up to ≈500 pcs µm-2 , providing abundant active sites. Besides, a unique bismuth nanosphere semi-embedded carbon fiber structure with strong interfacial BiC chemical bonding is spontaneously formed during carbothermic reactions, offering an excellent mechanical stability under flowing electrolytes. It shows that the bismuth nanosphere semi-embedded carbon felt can effectively promote V(II)/V(III) redox reactions with appreciable catalytic activity. The battery with the present electrode sustains an energy efficiency of 77.1 ± 0.2% and an electrolyte utilization of 57.2 ± 0.2% even when a current density up to 480 mA cm-2 is applied, which are remarkably higher than those of batteries with the bismuth nanoparticle/carbon felt synthesized by the electrodeposition method (62.6 ± 0.1%, 23.6 ± 0.2%). Further, the battery with the present electrode demonstrates a stable energy efficiency retention of 98.2% after 1000 cycles.

Liquid Metal-Based Soft Microfluidics.

Motivated by the increasing demand of wearable and soft electronics, liquid metal (LM)-based microfluidics has been subjected to tremendous development in the past decade, especially in electronics, robotics, and related fields, due to the unique advantages of LMs that combines the conductivity and deformability all-in-one. LMs can be integrated as the core component into microfluidic systems in the form of either droplets/marbles or composites embedded by polymer materials with isotropic and anisotropic distribution. The LM microfluidic systems are found to have broad applications in deformable antennas, soft diodes, biomedical sensing chips, transient circuits, mechanically adaptive materials, etc. Herein, the recent progress in the development of LM-based microfluidics and their potential applications are summarized. The current challenges toward industrial applications and future research orientation of this field are also summarized and discussed.

Recent progress in creating complex and multiplexed surface-grafted macromolecular architectures.

Surface-grafted macromolecules, including polymers, DNA, peptides, etc., are versatile modifications to tailor the interfacial functions in a wide range of fields. In this review, we aim to provide an overview of the most recent progress in engineering surface-grafted chains for the creation of complex and multiplexed surface architectures over micro- to macro-scopic areas. A brief introduction to surface grafting is given first. Then the fabrication of complex surface architectures is summarized with a focus on controlled chain conformations, grafting densities and three-dimensional structures. Furthermore, recent advances are highlighted for the generation of multiplexed arrays with designed chemical composition in both horizontal and vertical dimensions. The applications of such complicated macromolecular architectures are then briefly discussed. Finally, some perspective outlooks for future studies and challenges are suggested. We hope that this review will be helpful to those just entering this field and those in the field requiring quick access to useful reference information about the progress in the properties, processing, performance, and applications of functional surface-grafted architectures.

Light-Induced Shape Morphing of Liquid Metal Nanodroplets Enabled by Polydopamine Coating.

Shape morphing nanosystems have recently attracted much attention and a number of applications are developed, spanning from autonomous robotics to drug delivery. However, the fabrication of such nanosystems remains at an early stage owing to limited choices of strategies and materials. This work reports a facile method to fabricate liquid metal (LM) nanodroplets by sonication of bulk LM in an aqueous dopamine hydrochloride solution and their application in light-induced shape morphing at the nanoscale. In this method, dopamine acts as a surfactant, which stabilizes the LM nanodroplets dispersion during the sonication, and results in downsizing of the nanodroplets. Furthermore, by adding 2-amino-2-(hydroxymethyl)-1,3-propanediol to the suspension, self-polymerization of dopamine molecules occurs, resulting in the formation of polydopamine (PDA)-coated LM nanodroplets. Owing to the high photothermal conversion of the PDA, PDA-coated LM nanodroplets are transformed from spherical shapes to ellipsoids by NIR laser irradiation. This study paves a simple and reliable pathway for the preparation of functional LM nanodroplets and their application as shape-morphing nanosystems.

Biomimetic Extreme-Temperature- and Environment-Adaptable Hydrogels.

Recently, temperature-resistant hydrogels, hydrogels which are freezing- and dehydration-resistant, have garnered considerable attention in the scientific community as they extend the rage of application of hydrogels to arid and/or cold environments. Besides, these hydrogels exhibit tunable conductivity and mechanical performance while offering excellent biocompatibility and flexibility, making them interesting candidates for flexible and wearable electronics and (bio)sensors. Several biomimetic strategies were developed to fabricate anti-freezing and anti-dehydration hydrogels with a diversity of merits, such as high strain resistance and conductivity, even at sub-zero temperatures, and employed as (bio)sensors, electrodes, and energy-storage devices. This review summarizes the recent advances in the preparation and application of temperature-resistant hydrogels, indicates issues of the state-of-the-art hydrogels, and offers potential future research directions.

Electric Actuation of Liquid Metal Droplets in Acidified Aqueous Electrolyte.

The electric actuation of room-temperature liquid metals, such as Galinstan (gallium-indium-tin), has largely been conducted in alkaline electrolyte. Addition of surface-active anions and a proper acidic pH are expected to influence the interfacial tension of the liquid metal due to a high surface charge density. Hence, it should be possible to actuate liquid metals in such acidic environments. To ascertain this, at first, the dependence of the interfacial tension of Galinstan in NaOH, acidified KI, and acidified NaCl electrolyte on the concentration of the surface-active anions OH-, I-, and Cl-, respectively, were studied. Subsequently, a systematic study of the actuation of Galinstan in acidified KI electrolyte was executed and compared to actuation in alkaline medium. In the presence of HCl and acidified NaCl electrolyte, the interfacial tension of Galinstan is only marginally altered, while acidified KI solution reduced the interfacial tension of Galinstan significantly from 470.8 ± 1.4 (no KI) to 370.6 ± 4.1 mN/m (5 M KI) due to the high surface charge density of the electric double layer. Therefore, in acidified electrolyte in the presence of surface-active anions, the electrically actuated motion of LM can be realized. In particular, the actuation of Galinstan achieves a higher average and maximum speed at lower applied voltage and power consumption for acidified KI electrolyte. The formation of high surface charge density in acidified environments signifies a paradigm shift and opens up new possibilities to tune interfacial tension and controlled LM droplet motion of room-temperature liquid metals.

Liquid Metal-Mediated Mechanochemical Polymerization.

Mechanically controlled polymerization that employs the mechanical energy to fabricate novel synthetic materials has attracted considerable interest. However, only a few examples have been achieved so far, owing to the limited choices of materials and strategies. Herein, a versatile, liquid metal (LM)-mediated mechanochemical polymerization method (LMMMP) is developed for the air-compatible, robust preparation of polymers in an aqueous solution. This method involves the simultaneous disruption of bulk LMs into micro- and nanodroplets and the combination of monomers into polymers during ultrasonic irradiation. The pristine and reactive LM surface continuously generated by ultrasound endows this polymerization method with excellent oxygen tolerance, high reaction rate, and the ability to produce polymers with high molecular weight from a wide variety of water-soluble monomers. Besides, LM droplets are readily reclaimed and reused for polymerization. The authors envision that the LMMMP promotes the utilization of mechanical energy for the synthesis of functional polymers, constitutes a novel fabrication approach for polymer-LM nanocomposites, and provides new insight into the design of LM-based platforms for polymerization.

Analysis and Transformations of Room-Temperature Liquid Metal Interfaces - A Closer Look through Interfacial Tension.

Room-temperature gallium-based liquid metals (e. g. Galinstan) are emerging materials for a wide range of applications spanning from soft robotics to a medium for running chemical reactions. However, Galinstan suffers from rapid oxide formation at the surface, limiting its application. Similarly, this surface oxidation renders it difficult to determine the surface free energy of Galinstan. Herein, the interfacial properties of Galinstan in contact with argon, acid, base, water, and organic solvents were investigated, yielding kinetic information regarding the removal by acids and bases, knowledge about oxo-hydroxide/hydroxide species at the Galinstan/water interface, and an estimated value of the dispersive contribution of the surface free energy. The dispersive contribution of the surface free energy of Galinstan was calculated to be (239.7±9.1) mN/m, around 40 % of the total surface free energy. By employing the dispersive surface tension of Galinstan, the interfacial tension between a liquid and Galinstan can be easily obtained, facilitating the design and application of liquid metal-based devices.

Controlling Directional Liquid Motion on Micro- and Nanocrystalline Diamond/ß-SiC Composite Gradient Films.

In this Article, we report the synthesis of micro- and nanocrystalline diamond/ß-SiC composite gradient films, using a hot filament chemical vapor deposition (HFCVD) technique and its application as a robust and chemically inert means to actuate water and hazardous liquids. As revealed by scanning electron microscopy, the composition of the surface changed gradually from pure nanocrystalline diamond (hydrophobic) to a nanocrystalline ß-SiC surface (hydrophilic). Transmission electron microscopy and Raman spectroscopy were employed to determine the presence of diamond, graphite, and ß-SiC phases. The as-prepared gradient films were evaluated for their ability to actuate water. Indeed, water was transported via the gradient from the hydrophobic (hydrogen-terminated diamond) to the hydrophilic side (hydroxyl-terminated ß-SiC) of the gradient surface. The driving distance and velocity of water is pivotally influenced by the surface roughness. The nanogradient surface showed significant promise as the lower roughness combined with the longer gradient yields in transport distances of up to 3.7 mm, with a maximum droplet velocity of nearly 250 mm/s measured by a high-speed camera. As diamond and ß-SiC are chemically inert, the gradient surfaces can be used to drive hazardous liquids and reactive mixtures, which was signified by the actuation of hydrochloric acid and sodium hydroxide solution. We envision that the diamond/ß-SiC gradient surface has high potential as an actuator for water transport in microfluidic devices, DNA sensors, and implants, which induce guided cell growth.

Red and Near-Infrared Light-Cleavable Polymers.

Photocleavable polymers have attracted much attention in drug delivery, photopatterning, and controlling cell behavior. Photolysis is usually induced by UV light. However, UV light cannot penetrate deeply into biological tissue and may damage biological components. Therefore, conventional UV-light-cleavable polymers are problematic for deep-tissue biomedical applications. In this feature article, red and near-infrared light-cleavable polymers are reviewed, and their potential applications are highlighted. The remaining challenges in the field of photocleavable polymers are discussed.

Softening and Shape Morphing of Stiff Tough Hydrogels by Localized Unlocking of the Trivalent Ionically Cross-Linked Centers.

The mechanical properties (e.g., stiffness, stretchability) of prefabricated hydrogels are of pivotal importance for diverse applications in tissue engineering, soft robotics, and medicine. This study reports a feasible method to fabricate ultrasoft and highly stretchable structures from stiff and tough hydrogels of low stretchability and the application of these switchable hydrogels in programmable shape-morphing systems. Stiff and tough hydrogel structures are first fabricated by the mechanical strengthening of Ca2+ -alginate/polyacrylamide tough hydrogels by addition of Fe3+ ions, which introduces Fe3+ ionically cross-linked centers into the Ca2+ divalent cross-linked hydrogel, forming an additional and much less flexible trivalent ionically cross-linked network. The resulting stiff and tough hydrogels are exposed to an L-ascorbic acid (vitamin C, VC) solution to rapidly reduce Fe3+ to Fe2+ . As a result, flexible divalent ionically cross-linked networks are formed, leading to swift softening of the stiff and tough hydrogels. Moreover, localized stiffness variation of the tough hydrogels can be realized by precise patterning of the VC solution. To validate this concept, sequential steps of VC patterning are carried out for local tuning of the stiffness of the hydrogels. With this strategy, localized softening, unfolding, and sequential folding of the tough hydrogels into complex 3D structures is demonstrated.

Rational Fabrication of Anti-Freezing, Non-Drying Tough Organohydrogels by One-Pot Solvent Displacement.

Tough hydrogels, polymeric network structures with excellent mechanical properties (such as high stretchability and toughness), are emerging soft materials. Despite their remarkably mechanical features, tough hydrogels exhibit two flaws (freezing around the icing temperatures of water and drying under arid conditions). Inspired by cryoprotectants (CPAs) used in the inhibition of the icing of water in biological samples, a versatile and straightforward method is reported to fabricate extreme anti-freezing, non-drying CPA-based organohydrogels with long-term stability by partially displacing water molecules within the pre-fabricated hydrogels. CPA-based Ca-alginate/polyacrylamide (PAAm) tough hydrogels were successfully fabricated with glycerol, glycol, and sorbitol. The CPA-based organohydrogels remain unfrozen and mechanically flexible even up to -70 °C and are stable under ambient conditions or even vacuum.

Large-Area Patterning of Metal Nanostructures by Dip-Pen Nanodisplacement Lithography for Optical Applications.

Au nanostructures are remarkably important in a wide variety of fields for decades. The fabrication of Au nanostructures typically requires time-consuming and expensive electron-beam lithography (EBL) that operates in vacuum. To address this challenge, this paper reports the development of massive dip-pen nanodisplacement lithography (DNL) as a desktop fabrication tool, which allows high-throughput and rational design of arbitrary Au nanopatterns in ambient condition. Large-area (1 cm2 ) and uniform (<10% variation) Au nanostructures as small as 70 nm are readily fabricated, with a throughput 100-fold higher than that of conventional EBL. As a proof-of-concept of the applications in the opitcal field, we fabricate discrete Au nanorod arrays that show significant plasmonic resonance in the visible range, and interconnected Au nanomeshes that are used for transparent conductive electrode of solar cells.

Construction of 3D polymer brushes by dip-pen nanodisplacement lithography: understanding the molecular displacement for ultrafine and high-speed patterning.

Dip-pen nanodisplacement lithography (DNL) is a versatile scanning probe-based technique that can be employed for fabricating ultrafine 3D polymer brushes under ambient conditions. Many fundamental studies and applications require the large-area fabrication of 3D structures. However, the fabrication throughput and uniformity are still far from satisfactory. In this work, the molecular displacement mechanism of DNL is elucidated by systematically investigating the synergistic effect of z extension and contact time. The in-depth understanding of molecular displacement results in the successful achievement of ultrafine control of 3D structures and high-speed patterning at the same time. Remarkably, one can prepare arbitrary 3D polymer brushes on a large area (1.3 mm × 1.3 mm), with <5% vertical and lateral size variations, and a patterning speed as much as 200-fold faster than the current state-of-the-art.

Rapid self-assembly of self-healable and transferable liquid metal epidermis.

Healable electronic skins, an essential component for future soft robotics, implantable bioelectronics, and smart wearable systems, necessitate self-healable and pliable materials that exhibit functionality at intricate interfaces. Although a plethora of self-healable materials have been developed, the fabrication of highly conformal biocompatible functional materials on complex biological surfaces remains a formidable challenge. Inspired by regenerative properties of skin, we present the self-assembled transfer-printable liquid metal epidermis (SALME), which possesses autonomous self-healing capabilities at the oil-water interface. SALME comprises a layer of surfactant-grafted liquid metal nanodroplets that spontaneously assemble at the oil-water interface within a few seconds. This unique self-assembly property facilitates rapid restoration (<10 s) of SALME following mechanical damage. In addition to its self-healing ability, SALME exhibits excellent shear resistance and can be seamlessly transferred to arbitrary hydrophilic/hydrophobic curved surfaces. The transferred SALME effectively preserves submicron-scale surface textures on biological substrates, thus displaying tremendous potential for future epidermal bioelectronics.