Mussel‐Inspired Hydrogels for Self‐Adhesive Bioelectronics

Wearable and implantable bioelectronics are receiving a great deal of attention because they offer huge promise in personalized healthcare. Currently available bioelectronics generally rely on external aids to form an attachment to the human body, which leads to unstable performance in practical applications. Self‐adhesive bioelectronics are highly desirable for ameliorating these concerns by offering reliable and conformal contact with tissue, and stability and fidelity in the signal detection. However, achieving adequate and long‐term self‐adhesion to soft and wet biological tissues has been a daunting challenge. Recently, mussel‐inspired hydrogels have emerged as promising candidates for the design of self‐adhesive bioelectronics. In addition to self‐adhesiveness, the mussel‐inspired chemistry offers a unique pathway for integrating multiple functional properties to all‐in‐one bioelectronic devices, which have great implications for healthcare applications. In this report, the recent progress in the area of mussel‐inspired self‐adhesive bioelectronics is highlighted by specifically discussing: 1) adhesion mechanism of mussels, 2) mussel‐inspired hydrogels with long‐term and repeatable adhesion, 3) the recent advance in development of hydrogel bioelectronics by reconciling self‐adhesiveness and additional properties including conductivity, toughness, transparency, self‐healing, antibacterial properties, and tolerance to extreme environment, and 4) the challenges and prospects for the future design of the mussel‐inspired self‐adhesive bioelectronics.     

Conductive “Smart” Hybrid Hydrogels with PNIPAM and Nanostructured Conductive Polymers

Stimuli‐responsive hydrogels with decent electrical properties are a promising class of polymeric materials for a range of technological applications, such as electrical, electrochemical, and biomedical devices. In this paper, thermally responsive and conductive hybrid hydrogels are synthesized by in situ formation of continuous network of conductive polymer hydrogels crosslinked by phytic acid in poly(N‐isopropylacrylamide) matrix. The interpenetrating binary network structure provides the hybrid hydrogels with continuous transporting path for electrons, highly porous microstructure, strong interactions between two hydrogel networks, thus endowing the hybrid hydrogels with a unique combination of high electrical conductivity (up to 0.8 S m^?1), high thermoresponsive sensitivity (significant volume change within several seconds), and greatly enhanced mechanical properties. This work demonstrates that the architecture of the filling phase in the hydrogel matrix and design of hybrid hydrogel structure play an important role in determining the performance of the resulting hybrid material. The attractive performance of these hybrid hydrogels is further demonstrated by the developed switcher device which suggests potential applications in stimuli‐responsive electronic devices.     

Skin‐Inspired Antibacterial Conductive Hydrogels for Epidermal Sensors and Diabetic Foot Wound Dressings

Recently, artificial intelligence research has driven the development of stretchable and flexible electronic systems. Conductive hydrogels are a class of soft electronic materials that have emerging applications in wearable and implantable biomedical devices. However, current conductive hydrogels possess fundamental limitations in terms of their antibacterial performance and a mechanical mismatch with human tissues, which severely limits their applications in biological interfaces. Here, inspired by animal skin, a conductive hydrogel is fabricated from a supramolecular assembly of polydopamine decorated silver nanoparticles (PDA@Ag NPs), polyaniline, and polyvinyl alcohol, namely PDA@Ag NPs/CPHs. The resultant hydrogel has many desirable features, such as tunable mechanical and electrochemical properties, eye‐catching processability, good self‐healing ability as well as repeatable adhesiveness. Remarkably, PDA@Ag NPs/CPHs exhibit broad antibacterial activity against Gram‐negative and Gram‐positive bacteria. The potential application of this versatile hydrogel is demonstrated by monitoring large‐scale movements of the human body in real time. In addition, PDA@Ag NPs/CPHs have a significant therapeutic effect on diabetic foot wounds by promoting angiogenesis, accelerating collagen deposition, inhibiting bacterial growth, and controlling wound infection. To the best of the authors' knowledge, this is the first time that conductive hydrogels with antibacterial ability are developed for use as epidermal sensors and diabetic foot wound dressing.     

Conductive Graphitic Channel in Graphene Oxide‐Based Memristive Devices

Electrically insulating graphene oxide with various oxygen‐functional groups is a novel material as an active layer in resistive switching memories via reduction process. Although many research groups have reported on graphene oxide‐based resistive switching memories, revealing the origin of conducting path in a graphene oxide active layer remains a critical challenge. Here nanoscale conductive graphitic channels within graphene oxide films are reported using a low‐voltage spherical‐aberration‐corrected transmission electron microscopy. Simultaneously, these channels with reduced graphene oxide nanosheets induced by the detachment of oxygen groups are verified by Raman intensity ratio map and conductive atomic force microscopy. It is also clearly revealed that Al metallic protrusions, which are generated in the bottom interface layer, assist the local formation of conductive graphitic channels directly onto graphene oxide films by generating a local strong electric field. This work provides essential information for future carbon‐based nanoelectronic devices.     

Bio‐Inspired Stretchable,Adhesive, and Conductive Structural Color Film for Visually Flexible Electronics

The rapid progress in flexible electronic devices has attracted immense interest in many applications, such as health monitoring devices, sensory skins, and implantable apparatus. Here, inspired by the adhesion features of mussels and the color shift mechanism of chameleons, a novel stretchable, adhesive, and conductive structural color film is presented for visually flexible electronics. The film is generated by adding a conductive carbon nanotubes polydopamine (PDA) filler into an elastic polyurethane (PU) inverse opal scaffold. Owing to the brilliant flexibility and inverse opal structure of the PU layer, the film shows stable stretchability and brilliant structural color. Besides, the catechol groups on PDA impart the film with high tissue adhesiveness and self‐healing capability. Notably, because of its responsiveness, the resultant film is endowed with color‐changing ability that responds to motions, which can function as dual‐signal soft human‐motion sensors for real‐time color‐sensing and electrical signal monitoring. These features make the bio‐inspired hydrogel‐based electronics highly potential in the flexible electronics field.     

Black‐Phosphorus‐Incorporated Hydrogel as a Conductive and Biodegradable Platform for Enhancement of the Neural Differentiation of Mesenchymal Stem Cells

Conductive hydrogel scaffolds have important applications for electroactive tissue repairs. However, the development of conductive hydrogel scaffolds tends to incorporate nonbiodegradable conductive nanomaterials that will remain in the human body as foreign matters. Herein, a biodegradable conductive hybrid hydrogel is demonstrated based on the integration of black phosphorus (BP) nanosheets into the hydrogel matrix. To address the challenge of applying BP nanosheets in tissue engineering due to its intrinsic instability, a polydopamine (PDA) modification method is developed to improve the stability. Moreover, PDA modification also enhances interfacial bonding between pristine BP nanosheets and the hydrogel matrix. The incorporation of polydopamine‐modified black phosphorous (BP@PDA) nanosheets into the gelatin methacryloyl (GelMA) hydrogels significantly enhances the electrical conductivity of the hydrogels and improves the cell migration of mesenchymal stem cells (MSCs) within the 3D scaffolds. On the basis of the gene expression and protein level assessments, the BP@PDA‐incorporated GelMA scaffold can significantly promote the differentiation of MSCs into neural‐like cells under the synergistic electrical stimulation. This strategy of integrating biodegradable conductive BP nanomaterials within a biocompatible hydrogel provides a new insight into the design of biomaterials for broad applications in tissue engineering of electroactive tissues, such as neural, cardiac, and skeletal muscle tissues.     

Construction of Chitosan‐Based Hydrogel Incorporated with Antimonene Nanosheets for Rapid Capture and Elimination of Bacteria

To elaborately construct a novel and efficient photothermal antibacterial nanoplatform is a promising strategy for treating bacterial wound infections. In this work, a composite hydrogel (CS/AM NSs hydrogel) with outstanding antibacterial ability is constructed by incorporating antimonene nanosheets (AM NSs) with extraordinary photothermal properties into the network structure of chitosan (CS). When cultured with bacteria, the CS/AM NSs hydrogel can gather bacteria on the surface through the interaction of CS with the bacterial cell membrane. Subsequently, the intrinsic bactericidal property of CS will kill some of the bacteria. After the introduction of near‐infrared laser, the AM NSs effectively convert light energy into localized heat to eliminate residual bacteria. By virtue of the synergistic action between the capture effect of CS and the photothermal effect of AM NSs, the CS/AM NSs hydrogel shows predominant antibacterial behavior against Escherichia coli and Staphylococcus aureus. In vitro assay and in vivo tests of infected full‐thickness defect wound healing confirm the satisfactory biocompatibility and antibacterial ability. Overall, this work reveals that the CS/AM NSs hydrogel holds great potential as a broad‐spectrum antibacterial wound dressing for treating bacteria‐infected wounds. Additionally, this is the first report of the application of AM NSs in the field of antibacterial treatment.     

Fully Solution‐Processed Conductive Films Based on Colloidal Copper Selenide Nanosheets for Flexible Electronics

A novel colloidal synthesis of copper selenide nanosheets (NSs) with lateral dimensions of up to 3 μm is developed. This material is used for the fabrication of flexible conductive films prepared via simple drop‐casting of the NS dispersions without any additional treatment. The electrical performance of these coatings is benchmarked against copper selenide spherical nanocrystals (SNCs) in order to demonstrate the advantage of 2D morphology of the NSs for flexible electronics. In this contest, Cu_2?xSe SNC films exhibit higher conductivity but lower reproducibility due to the formation of cracks leading to discontinuous films. Furthermore, the electrical properties of the films deposited on different flexible substrates following their bending, stretching and folding are studied. A comparison of Cu_2?xSe SNC and CuSe NS films reveals an increased stability of the CuSe NS films under mechanical stress applied to the samples and their improved long‐term stability in air.     

Hierarchical Ordered Dual‐Mesoporous Polypyrrole/Graphene Nanosheets as Bi‐Functional Active Materials for High‐Performance Planar Integrated System of Micro‐Supercapacitor and Gas Sensor

Planar integrated systems of micro‐supercapacitors (MSCs) and sensors are of profound importance for 3C electronics, but usually appear poor in compatibility due to the complex connections of device units with multiple mono‐functional materials. Herein, 2D hierarchical ordered dual‐mesoporous polypyrrole/graphene (DM‐PG) nanosheets are developed as bi‐functional active materials for a novel prototype planar integrated system of MSC and NH₃ sensor. Owing to effective coupling of conductive graphene and high‐sensitive pseudocapacitive polypyrrole, well‐defined dual‐mesopores of ≈7 and ≈18 nm, hierarchical mesoporous network, and large surface area of 112 m² g^?1, the resultant DM‐PG nanosheets exhibit extraordinary sensing response to NH₃ as low as 200 ppb, exceptional selectivity toward NH₃ that is much higher than other volatile organic compounds, and outstanding capacitance of 376 F g^?1 at 1 mV s^?1 for supercapacitors, simultaneously surpassing single‐mesoporous and non‐mesoporous counterparts. Importantly, the bi‐functional DM‐PG‐based MSC‐sensor integrated system represents rapid and stable response exposed to 10–40 ppm of NH₃ after only charging for 100 s, remarkable sensitivity of NH₃ detection that is close to DM‐PG‐based MSC‐free sensor, impressive flexibility with ≈82% of initial response value even at 180°, and enhanced overall compatibility, thereby holding great promise for ultrathin, miniaturized, body‐attachable, and portable detection of NH₃.     

Wearable,Healable, and Adhesive Epidermal Sensors Assembled from Mussel‐Inspired Conductive Hybrid Hydrogel Framework

Healable, adhesive, wearable, and soft human‐motion sensors for ultrasensitive human–machine interaction and healthcare monitoring are successfully assembled from conductive and human‐friendly hybrid hydrogels with reliable self‐healing capability and robust self‐adhesiveness. The conductive, healable, and self‐adhesive hybrid network hydrogels are prepared from the delicate conformal coating of conductive functionalized single‐wall carbon nanotube (FSWCNT) networks by dynamic supramolecular cross‐linking among FSWCNT, biocompatible polyvinyl alcohol, and polydopamine. They exhibit fast self‐healing ability (within 2 s), high self‐healing efficiency (99%), and robust adhesiveness, and can be assembled as healable, adhesive, and soft human‐motion sensors with tunable conducting channels of pores for ions and framework for electrons for real time and accurate detection of both large‐scale and tiny human activities (including bending and relaxing of fingers, walking, chewing, and pulse). Furthermore, the soft human‐motion sensors can be enabled to wirelessly monitor the human activities by coupling to a wireless transmitter. Additionally, the in vitro cytotoxicity results suggest that the hydrogels show no cytotoxicity and can facilitate cell attachment and proliferation. Thus, the healable, adhesive, wearable, and soft human‐motion sensors have promising potential in various wearable, wireless, and soft electronics for human–machine interfaces, human activity monitoring, personal healthcare diagnosis, and therapy.     

Rational Design of a Printable,Highly Conductive Silicone‐based Electrically Conductive Adhesive for Stretchable Radio‐Frequency Antennas

Stretchable radio‐frequency electronics are gaining popularity as a result of the increased functionality they gain through their flexible nature, impossible within the confines of rigid and planar substrates. One approach to fabricating stretchable antennas is to embed stretchable or flowable conductive materials, such as conductive polymers, conductive polymer composites, and liquid metal alloys as stretchable conduction lines. However, these conductive materials face many challenges, such as low electrical conductivity under mechanical deformation and delamination from substrates. In the present study, a silicone‐based electrically conductive adhesive (silo‐ECA) is developed that have a conductivity of 1.51 × 10⁴ S cm^?1 and can maintain conductivity above 1.11 × 10³ S cm^?1, even at a large stain of 240%. By using the stretchable silo‐ECAs as a conductor pattern and pure silicone elastomers as a base substrate, stretchable antennas can be fabricated by stencil printing or soft‐lithography. The resulting antenna's resonant frequency is tunable over a wide range by mechanical modulation. This fabrication method is low‐cost, can support large‐scale production, has high reliability over a wide temperature range, and eliminates the concerns of leaking or delamination between conductor and substrate experienced in previously reported micro‐fluidic antennas.     

Self‐Assembling of Conductive Interlayer‐Expanded WS2 Nanosheets into 3D Hollow Hierarchical Microflower Bud Hybrids for Fast and Stable Sodium Storage

Transition‐metal dichalcogenides have emerged as promising anodes of sodium ion batteries (SIBs). Their practical SIB application calls for an easy‐to‐handle synthetic technique capable of fabricating favorable properties with high conductivity and stable structure. Here, a solvothermal strategy is reported for bottom‐up self‐assembling of nanoflowers' building block, i.e., conductive interlayer‐expanded 2D WS₂ nanosheets thanks to in situ interlayer modification by nitrogen‐doped carbon matrix, into 3D hollow microflower bud‐like hybrids (H‐WS₂@NC). The 3D nano/microhierarchical hollow structures are constructed by conductive interlayer‐expanded WS₂ nanosheets' building blocks, providing abundant channels facilitating mass transport/electrons transfer, robust protection layer to avoid the direct contact between WS₂ nanosheets and electrolyte, sufficient inner space for accommodating volume variation, and decreased ions diffusion energy barrier for accelerating electrochemical kinetics, as revealed by density functional theory calculations. As such, the 3D H‐WS₂@NC hybrids exhibit quite attractive sodium storage performance with high reversible capacity, superior rate capability, and impressively long cycling life. The 3D H‐WS₂@NC is further verified as anode of sodium‐ion full cell pairing with Na₃V₂(PO4)₃/rGO cathode, delivering a stable reversible capacity of 296 mAh g^?1 at 0.5 A g^?1 with high energy density of 128 Wh kg^?1_total at a power density of 386 W kg^?1_total.     

Self‐Assembly of DNA‐Templated Polypyrrole Nanowires: Spontaneous Formation of Conductive Nanoropes

Polypyrrole nanowires formed by polymerization of pyrrole on a DNA template self‐assemble into rope‐like structures. These ‘nanoropes’ may be quite smooth (diameters 5–30 nm) or may show frayed ends where individual strands are visible. A combination of electric force microscopy, conductive atomic force microscopy and two‐terminal current–voltage measurements show that they are conductive. Nanoropes adhere more weakly to hydrophobic surfaces prepared by silanization of SiO₂ than to the clean oxide; this effect can be used to aid the combing of the nanoropes across microelectrode devices for electrical characterization.     

On‐Body Bioelectronics: Wearable Biofuel Cells for Bioenergy Harvesting and Self‐Powered Biosensing

The growing power demands of wearable electronic devices have stimulated the development of on‐body energy‐harvesting strategies. This article reviews the recent progress on rapidly emerging wearable biofuel cells (BFCs), along with related challenges and prospects. Advanced on‐body BFCs in various wearable platforms, e.g., textiles, patches, temporary tattoo, or contact lenses, enable attractive advantages for bioenergy harnessing and self‐powered biosensing. These noninvasive BFCs open up unique opportunities for utilizing bioenergy or monitoring biomarkers present in biofluids, e.g., sweat, saliva, interstitial fluid, and tears, toward new biomedical, fitness, or defense applications. However, the realization of effective wearable BFC requires high‐quality enzyme‐electronic interface with efficient enzymatic and electrochemical processes and mechanical flexibility. Understanding the kinetics and mechanisms involved in the electron transfer process, as well as enzyme immobilization techniques, is essential for efficient and stable bioenergy harvesting under diverse mechanical strains and changing operational conditions expected in different biofluids and in a variety of outdoor activities. These key challenges of wearable BFCs are discussed along with potential solutions and future prospects. Understanding these obstacles and opportunities is crucial for transforming traditional bench‐top BFCs to effective and successful wearable BFCs.     

Adhesive,Flexible, and Robust Polysaccharide Nanosheets Integrated for Tissue‐Defect Repair

Recent developments in nanotechnology have led to a method for producing free‐standing polymer nanosheets as a macromolecular organization. Compared with bulk films, the large aspect ratio of such nanosheets leads to unique physical properties, such as transparency, noncovalent adhesion, and high flexibility. Here, a biomedical application of polymer nanosheets consisting of biocompatible and biodegradable polysaccharides is reported. Micro‐scratch and bulge tests indicate that the nanosheets with a thickness of tens of nanometers have sufficient physical adhesiveness and mechanical strength for clinical use. A nanosheet of 75 nm thickness, a critical load of 9.1 × 10⁴ N m^?1, and an elastic modulus of 9.6 GPa is used for the minimally invasive repair of a visceral pleural defect in beagle dogs without any pleural adhesion caused by wound repair. For the first time, clinical benefits of sheet‐type nano‐biomaterials based on molecular organization are demonstrated, suggesting that novel therapeutic tools for overlapping tissue wounds will be possible without the need for conventional surgical interventions.     

导电胶粘接可伐载板工艺的仿真与优化

导电胶是一种很有潜力的互连材料,其粘接可靠性是制约其应用的主要因素。基于对某混频模块粘接失效的分析,探索温度试验条件及载板尺寸对可伐载板粘接可靠性的影响。通过仿真和试验设计,研究不同温度试验条件下不同尺寸载板在粘接界面处的应力分布情况,并优化了可伐载板粘接工艺。结果表明,温度试验条件越严苛,载板尺寸越大,可伐载板粘接可靠性越差,可采取环氧绝缘胶加固或柔性导电胶粘接的方式对其粘接工艺进行优化。     

Muscle-Inspired MXene Conductive Hydrogels with Anisotropy and Low-Temperature Tolerance for Wearable Flexible Sensors and Arrays

Conductive hydrogels as flexible electronic devices, not only have unique attractions but also meet the basic need of mechanical flexibility and intelligent sensing. How to endow anisotropy and a wide application temperature range for traditional homogeneous conductive hydrogels and flexible sensors is still a challenge. Herein, a directional freezing method is used to prepare anisotropic MXene conductive hydrogels that are inspired by ordered structures of muscles. Due to the anisotropy of MXene conductive hydrogels, the mechanical properties and electrical conductivity are enhanced in specific directions. The hydrogels have a wide temperature resistance range of −36 to 25 °C through solvent substitution. Thus, the muscle-inspired MXene conductive hydrogels with anisotropy and low-temperature resistance can be used as wearable flexible sensors. The sensing signals are further displayed on the mobile phone as images through wireless technology, and images will change with the collected signals to achieve motion detection. Multiple flexible sensors are also assembled into a 3D sensor array for detecting the magnitude and spatial distribution of forces or strains. The MXene conductive hydrogels with ordered orientation and anisotropy are promising for flexible sensors, which have broad application prospects in human–machine interface compatibility and medical monitoring.     

Conductive adhesive with transient liquid‐phase sintering technology for high‐power device applications

A highly reliable conductive adhesive obtained by transient liquid‐phase sintering (TLPS) technologies is studied for use in high‐power device packaging. TLPS involves the low‐temperature reaction of a low‐melting metal or alloy with a high‐melting metal or alloy to form a reacted metal matrix. For a TLPS material (consisting of Ag‐coated Cu, a Sn96.5‐Ag3.0‐Cu0.5 solder, and a volatile fluxing resin) used herein, the melting temperature of the metal matrix exceeds the bonding temperature. After bonding of the TLPS material, a unique melting peak of TLPS is observed at 356 °C, consistent with the transient behavior of Ag₃Sn + Cu₆Sn₅ → liquid + Cu₃Sn reported by the National Institute of Standards and Technology. The TLPS material shows superior thermal conductivity as compared with other commercially available Ag pastes under the same specimen preparation conditions. In conclusion, the TLPS material can be a promising candidate for a highly reliable conductive adhesive in power device packaging because remelting of the SAC305 solder, which is widely used in conventional power modules, is not observed.     

Redox‐Active Iron‐Citrate Complex Regulated Robust Coating‐Free Hydrogel Microfiber Net with High Environmental Tolerance and Sensitivity

Stretchable hydrogel microfibers as a novel type of ionic conductors are promising in gaining skin‐like sensing applications in more diverse scenarios. However, it remains a great challenge to fabricate coating‐free but water‐retaining conductive hydrogel microfibers with a good balance of spinnability and mechanical strength. Here the old yet significant redox chemistry of Fe‐citrate complex is employed to solve this issue in the continuous draw‐spinning process of poly(acrylamide‐co‐sodium acrylate) hydrogel microfibers and microfiber nets from a water/glycerol solution. The resultant microfibers are ionically conductive, highly stretchable, and uniform with tunable diameters. Furthermore, the presence of redox‐reversible Fe‐citrate complex and glycerol endows the fibers with good anti‐freezing, water‐retaining, and environmentally intelligent properties. Humidity and UV light can finely mediate the stiffness of hydrogel microfibers; conversely, the ionic conductance of microfibers is also responsive to light, humidity, and strain, which enables the highly sensitive perception of environmental changes. The present draw‐spinning strategy provides more possibilities for coating‐free conductive hydrogel microfibers with a variety of responsive and sensing applications.     

Mussel‐Inspired Adhesive and Conductive Hydrogel with Long‐Lasting Moisture and Extreme Temperature Tolerance

Conductive hydrogels are a promising class of materials to design bioelectronics for new technological interfaces with human body, which are required to work for a long‐term or under extreme environment. Traditional hydrogels are limited in short‐term usage under room temperature, as it is difficult to retain water under cold or hot environment. Inspired by the antifreezing/antiheating behaviors from nature, and based on mussel chemistry, an adhesive and conductive hydrogel is developed with long‐lasting moisture lock‐in capability and extreme temperature tolerance, which is formed in a binary‐solvent system composed of water and glycerol. Polydopamine (PDA)‐decorated carbon nanotubes (CNTs) are incorporated into the hydrogel, which assign conductivity to the hydrogel and serve as nanoreinforcements to enhance the mechanical properties of the hydrogel. The catechol groups on PDA and viscous glycerol endow the hydrogel with high tissue adhesiveness. Particularly, the hydrogel is thermal tolerant to maintain all the properties under extreme wide tempreature spectrum (?20 or 60 °C) or stored for a long term. In summary, this mussel‐inspired hydrogel is a promising material for self‐adhesive bioelectronics to detect biosignals in cold or hot environments, and also as a dressing to protect skin from injuries related to frostbites or burns.