RESUMO
Hufu, serving as evidence of imperial authorization in ancient China, comprises two parts in the form of tiger-shaped tallies that only become effective when matched. Drawing inspiration from the concept of Hufu, a reconfigurable electroluminescent (EL) device is designed by separating conventional integral devices into two parts that contain the EL layer (part A) and the transparent electrode (part B), respectively. The key to realizing such strategy is employing an adhesive and stretchable polymer gel composite as the transparent electrodes for the EL devices. The polymer gel composite facilitates robust yet reversible contact between the EL layer and transparent electrode, enabling high-performance and stretchable EL devices that can be readily disassembled and reassembled: the EL devices can maintain ≈81% of their initial luminance after 1000 times of repeated disassembly and reassembly. Moreover, the precursor ink of the polymer gel composite is compatible with a wide variety of coating and printing technologies, such as spin-coating, inkjet printing, dispensing, and brush painting. Importantly, the reconfigurable feature of the devices opens up a new path to encryption display systems, and as a proof-of-concept, EL encrypted password, and content-changeable digital clock are demonstrated.
RESUMO
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.
RESUMO
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.
RESUMO
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.
RESUMO
Small-scale robots (SSRs) have emerged as promising and versatile tools in various biomedical, sensing, decontamination, and manipulation applications, as they are uniquely capable of performing tasks at small length scales. With the miniaturization of robots from the macroscale to millimeter-, micrometer-, and nanometer-scales, the viscous and surface forces, namely adhesive forces and surface tension have become dominant. These forces significantly impact motion efficiency. Surface engineering of robots with both hydrophilic and hydrophobic functionalization presents a brand-new pathway to overcome motion resistance and enhance the ability to target and regulate robots for various tasks. This review focuses on the current progress and future perspectives of SSRs with hydrophilic and hydrophobic modifications (including both tethered and untethered robots). The study emphasizes the distinct advantages of SSRs, such as improved maneuverability and reduced drag forces, and outlines their potential applications. With continued innovation, rational surface engineering is expected to endow SSRs with exceptional mobility and functionality, which can broaden their applications, enhance their penetration depth, reduce surface fouling, and inhibit bacterial adhesion.
RESUMO
A series of ester-ether copolymers were obtained via the reaction between α,ω-dihydroxyl poly(ϵ-caprolactone) (PCL) and ethylene oxide (EO) or monosubstituted epoxides catalyzed by strong phosphazene bases. The two types of monomeric units were distributed in highly random manners due to the concurrence of epoxide ring-opening and fast transesterification reactions. The substituent of epoxide showed an interesting bidirectional effect on the enzymatic degradability of the copolymer. Compared with PCL, copolymers derived from EO exhibited enhanced hydrophilicity and decreased crystallinity which then resulted in higher degradability. For the copolymers derived from propylene oxide and 1,2-butylene oxide, the hydrophobic alkyl pendant groups also allowed lower crystallinity of the copolymers thus higher degradation rates. However, further enlarging the pendant groups by using styrene oxide or 2-ethylhexyl glycidyl ether caused a decrease in the degradation rate, which might be ascribed to the higher bulkiness hindering the contact of ester groups with lipase.
Assuntos
Ésteres , Polímeros , Polímeros/química , Poliésteres/química , Compostos de EpóxiRESUMO
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).
RESUMO
Adhesion and spreading of liquid metals (LMs) on substrates are essential steps for the generation of flexible electronics and thermal management devices. However, the controlled deposition is limited by the high surface tension and peculiar wetting and adhesion behavior of LMs. Herein, we introduce gelatin-regulated LM droplet deposition and sintering (GLMDDS), for the upscalable production of conformally adhesive, solidlike, yet transient LM thin films and patterns on diverse substrates. This method involves four steps: homogeneous deposition of LM microdroplets, gelation of the LM-gelatin solution, toughening of the gelatin hydrogel by solvent displacement, and peeling-induced sintering of LM microdroplets. The LM thin film exhibits a three-layer structure, comprising an LM microdroplet-embedded tough organohydrogel adhesion layer, a continuous LM layer, and an oxide skin. The composite exhibits high stretchability and mechanical robustness, conformal adhesion to various substrates, high conductivity (4.35 × 105 S·m-1), and transience (86% LM recycled). Large-scale deposition (i.e., 5.6 dm2) and the potential for patterns on diverse substrates demonstrate its upscalability and broad suitability. Finally, the LM thin films and patterns are applied for flexible and wearable devices, i.e., pressure sensors, heaters, human motion tracking devices, and thermal management devices, illustrating the broad applicability of this strategy.
RESUMO
Soft electronics are rising electronic technologies towards applications spanning from healthcare monitoring to medical implants. However, poor adhesion strength and significant mechanical mismatches inevitably cause the interface failure of devices. Herein we report a self-adhesive conductive polymer that possesses low modulus (56.1-401.9 kPa), high stretchability (700%), high interfacial adhesion (lap-shear strength >1.2 MPa), and high conductivity (1-37 S/cm). The self-adhesive conductive polymer is fabricated by doping the poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) composite with a supramolecular solvent (ß-cyclodextrin and citric acid). We demonstrated the solution process-based fabrication of self-adhesive conductive polymer-based electrodes for various soft devices, including alternating current electroluminescent devices, electromyography monitoring, and an integrated system for the visualization of electromyography signals during muscle training with an array of alternating current electroluminescent devices. The self-adhesive conductive polymer-based electronics show promising features to further develop wearable and comfortable bioelectronic devices with the physiological electric signals of the human body readable and displayable during daily activities.
RESUMO
As one of the most outstanding materials, the analysis of the structure and function of hydrogels has been extensively carried out to tailor and adapt them to various fields of application. The high water content, which is beneficial for plenty of applications in the biomedical setting, prevents the adoption of hydrogels in flexible electronics and sensors in real life applications, because hydrogels lose their excellent properties, including conductivity, transparency, flexibility, etc., upon freezing at sub-zero temperatures. Therefore, depressing the liquid-solid phase transition temperature is a powerful means to expand the application scope of hydrogels, and will benefit the chemical engineering and materials science communities. This review summarizes the recent research progress of anti-freezing hydrogels. At first, approaches for the generation of anti-freezing (hydro)gels are introduced and their anti-freezing mechanisms and performances are briefly discussed. These approaches are either based on addition of salts, alcohols (cryoprotectants and organohydrogels), and ionic liquids (ionogels), modification of the polymer network or a combination of several techniques. Then, a concise overview of applications leveraged by the widened temperature resistance is provided and future research areas and developments are envisaged.
Assuntos
Hidrogéis , Líquidos Iônicos , Biomimética , Condutividade Elétrica , PolímerosRESUMO
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.
RESUMO
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.
RESUMO
Electronic materials and devices that can mimic biological systems featured with elasticity, toughness, self-healing, degradability, and environmental friendliness drive the technological developments in fields spanning from bioelectronics, biomedical diagnosis and therapy, electronic skin, and soft robotics to Internet-of-Things with "green" electronics. Among them, ionic devices based on gel electrolytes have emerged as attractive candidates for biomimetic systems. Herein, we presented a straightforward approach to demonstrate soft ionic microdevices based on a versatile organohydrogel platform acting as both a free-standing, stretchable, adhesive, healable, and entirely degradable support and a highly conductive, dehydration- and freezing-tolerant electrolyte. This is achieved by forming a gelatin/ferric-ion-cross-linked polyacrylic acid (GEL/PAA) dual dynamic supramolecular network followed by soaking into a NaCl glycerol/water solution to further toughen the gelatin network via solvent displacement, thus obtaining a high toughness of 1.34 MJ·cm-3 and a high ionic conductivity (>7 mS·cm-1). Highly stretchable and multifunctional ionic microdevices are then fabricated based on the organohydrogel electrolytes by simple transfer printing of carbon-based microelectrodes onto the prestretched gel surface. Proof-of-concept microdevices including resistive strain sensors and microsupercapacitors are demonstrated, which displayed outstanding stretchability to 300% strain, resistance to dehydration for >6 months, autonomous self-healing, and rapid room-temperature degradation within hours. The present material design and fabrication approach for the organohydrogel-based ionic microdevices will provide promising scope for life-like and sustainable electronic systems.
Assuntos
Eletrólitos/química , Eletrônica , Hidrogéis/química , Resinas Acrílicas/química , Elasticidade , Condutividade Elétrica , Gelatina/química , Glicerol/química , Íons/químicaRESUMO
Icing of water (moisture) at subzero temperatures with different length scales is harmful to a variety of applications spanning from large-scale aircraft to small camera lens. Existing strategies relying on controlling the surface structure and material are encumbered with shortcomings of short frost delay time, poor durability, and difficulty in large-scale production. Inspired from the mucus secretion of mollusks, we introduce organohydrogel dynamic interfaces that can perform dynamic and reversible exchange of the cryoprotectant and water at the interface, resulting in exceptional antifrosting, antiadhesion, and deicing properties with long-term durability. The replenishable coating shows superlubrication to the surface ice with a sliding angle up to 1.9 ± 0.4o and a frost delay time up to 970 ± 31 min in the presence of water spray (99% relative humidity) at subzero temperatures. The strategy offers a reliable and scalable solution to prevent engineering surfaces, i.e., aircraft, pavement, bridge, and other public facilities, from icing/frosting and ice adhesion, even under extreme cold environments.
RESUMO
Recently, numerous research studies have contributed to engineering hydrogels by soaking strategies to obtain designed properties, from mechanical strengthening to environmentally adapting. Hydrogels are three-dimensional hydrophilic polymer networks dispersed in water with widespread applications. However, most of the traditional hydrogels possess limited mechanical strength and poor temperature and environmental tolerance, which limits their applications. Due to their unique water-rich property, the physical and chemical properties of hydrogels can be post-engineered by facile soaking strategies. The soaking strategies can be divided into two categories: the first involves soaking salt solutions into the aqueous phase of the gel, and the second involves soaking in organic solvents to displace the water in the gel, forming organohydrogels. In this feature article, we aim to summarize the most recent progress in designing and engineering hydrogels using soaking strategies, including strengthening hydrogels with superior mechanical properties, and providing the hydrogels with environmentally adapting properties, such as anti-freezing and anti-dehydration. The first section summarizes some common design principles and fabrication methods to strengthen hydrogels by soaking, and then it introduces some successful applications of these soaking-induced tough hydrogels. In the second section, the soaking strategy to engineer hydrogels with environmentally adapting properties is discussed. In the end, a brief outlook is proposed based on current challenges and the pros and cons of the soaking strategy.
RESUMO
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.
RESUMO
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.
RESUMO
Gallium-based liquid metals (GLMs) exist as atypical liquid-phase metals at and near room temperature while being electrically and thermally conductive, enabling copious applications in soft electronics and thermal management systems. Yet, solid metals are affected by interfacing with GLMs, resulting in liquid metal embrittlement and device failure. To avert this issue, mechanically durable and electrically tunable diffusion barriers for long-term reliable liquid metal-solid metal interfacing based on the deposition of various diamond coatings are designed and synthesized, as they feature high chemical inertness and extraordinary mechanical resistance. The diamond coatings show superlyophobicity (GLM contact angle ≥ 155°) and are nonstick toward GLMs, thereby achieving high mobility of GLM droplets (sliding angle 8-12°). The excellent barrier and anti-adhesion performance of the diamond coatings are proven in long-term experiments (3 weeks) of coated titanium alloy (Ti) samples in contact with GLMs. The electrical performance of the conductive diamond coating deposited on Ti is reliable and stable over a period of 50 h. As proof-of-concept applications a switch and a thermal management device based on liquid metals are demonstrated, signifying that coating diamond films on metals is a potent means to achieve stable integration of solid metals with GLMs.
RESUMO
Outer membrane vesicles (OMVs) are produced by Gram-negative bacteria both in vitro and in vivo. OMVs are nano-sized spherical vehicles formed by lipid bilayer membranes and contain multiple parent bacteria-derived components. Based on the presence of bacterial antigens, pathogen-associated molecular patterns (PAMPs), adhesins, various proteins and the vesicle structure, OMVs have been developed for biomedical applications as bacterial vaccines, adjuvants, cancer immunotherapy agents, drug delivery vehicles, and anti-bacteria adhesion agents. In this review, we analyze the contributions of the structure and composition of OMVs to their applications, summarize the methods used to isolate and characterize OMVs, and highlight recent progress and future perspectives of OMVs in biomedical applications.
Assuntos
Membrana Externa Bacteriana , Vesículas Extracelulares , Proteínas da Membrana Bacteriana Externa , Vacinas Bacterianas , Bactérias Gram-NegativasRESUMO
The efficacy of nano-mediated drug delivery has been impeded by multiple biological barriers such as the mononuclear phagocyte system (MPS), as well as vascular and interstitial barriers. To overcome the abovementioned obstacles, we report a nano-pathogenoid (NPN) system that can in situ hitchhike circulating neutrophils and supplement photothermal therapy (PTT). Cloaked with bacteria-secreted outer membrane vesicles inheriting pathogen-associated molecular patterns of native bacteria, NPNs are effectively recognized and internalized by neutrophils. The neutrophils migrate towards inflamed tumors, extravasate across the blood vessels, and penetrate through the tumors. Then NPNs are rapidly released from neutrophils in response to inflammatory stimuli and subsequently taken up by tumor cells to exert anticancer effects. Strikingly, due to the excellent targeting efficacy, cisplatin-loaded NPNs combined with PTT completely eradicate tumors in all treated mice. Such a nano-platform represents an efficient and generalizable strategy towards in situ cell hitchhiking as well as enhanced tumor targeted delivery.