Conducting Polymer Hydrogels Research Articles

Inside Front Cover: Conducting polymer hydrogels based on supramolecular strategies for wearable sensors (EXP2 5/2024)

Inside Front Cover: Conducting polymer hydrogels based on supramolecular strategies for wearable sensors (EXP2 5/2024)

High‐Performance Multipedal Shape Strain Sensors for Human Motion and Electrophysiological Signal Monitoring

AbstractStrain sensors from conducting polymer hydrogel have been widely employed in various wearable devices, electronic skins, and biomedical applications. These sensors provide outstanding flexibility and high sensitivity by integrating conducting polymer with hydrogels, making them particularly suitable for monitoring human motion and physiological signals like heart rate or muscle activity. Despite their extensive application potential, conducting polymer hydrogel face several technical challenges in practical use, including poor mechanical properties, lack of long‐term stability, and difficulty in customizable design. This work introduces a method for fabricating a multipedal strain sensor using poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS)/polyvinyl alcohol (PVA) dimethyl sulfoxide (DMSO)hydrogels through screen printing and demonstrates its application in human motion monitoring. The multipedal strain sensor demonstrates a low Young's modulus (200 kPa), high stretchability (400%), and excellent mechanical cyclic stability (3000 cycles). Furthermore, this strain sensor is further applied to detect human movements such as chewing, smiling, fist clenching, arm bending, and carotid pulse monitoring. Comparative analysis between the multipedal‐designed sensor and the non‐designed sensor highlights the enhanced sensing capabilities of the multipedal sensor. The design of this multipedal sensor holds the potential to broaden the design concepts for strain sensors and offers new insights for wearable devices and electronic skins.

Dual design strategy for carboxymethyl cellulose-polyaniline composite hydrogels as super-sensitive amphibious sensors

Conductive hydrogels as ideal candidate materials for flexible sensors have exhibited many promising applications. However, complex application environments, such as low temperatures or underwater conditions, have introduced new requirements for hydrogel sensors. Herein, a high-performance conductive hydrogel based on carboxymethyl cellulose-polyaniline (CMC-PANI) submicron spheres, poly (vinyl alcohol) (PVA) and phytic acid (PA) was designed and fabricated via a dual design strategy. CMC-PANI particles were introduced to not only empower the good electromechanical performance to the hydrogels, but also enhance the mechanical properties. The obtained hydrogel exhibited good mechanical property, anti-freezing, anti-swellable behavior and recyclable performance. Resistive-type strain sensors assembled by the prepared hydrogels exhibited high pressure sensitivity (34.17×10−2 kPa−1) and fast response time (100 ms), which can clearly detect the pulse beats. Moreover, the hydrogel sensors can achieve long-term stability, high sensitivity and fatigue resistance as an underwater sensor. Based on these favorable performances, the conductive polymer hydrogels may open up an enticing avenue for functional soft materials in health diagnostic and electronic components.

Engineering Conductive Hydrogels with Tissue‐like Properties: A 3D Bioprinting and Enzymatic Polymerization Approach

Hydrogels are promising materials for medical devices interfacing with neural tissues due to their similar mechanical properties. Traditional hydrogel‐based bio‐interfaces lack sufficient electrical conductivity, relying on low ionic conductivity, which limits signal transduction distance. Conducting polymer hydrogels offer enhanced ionic and electronic conductivities and biocompatibility but often face challenges in processability and require aggressive polymerization methods. Herein, we demonstrate in situ enzymatic polymerization of π‐conjugated monomers in a hyaluronan (HA)‐based hydrogel bioink to create cell‐compatible, electrically conductive hydrogel structures. These structures were fabricated using 3D bioprinting of HA‐based bioinks loaded with conjugated monomers, followed by enzymatic polymerization via horseradish peroxidase. This process increased the hydrogels’ stiffness from about 0.6 to 1.5 kPa and modified their electroactivity. The components and polymerization process were well‐tolerated by human primary dermal fibroblasts and PC12 cells. This work presents a novel method to fabricate cytocompatible and conductive hydrogels suitable for bioprinting. These hybrid materials combine tissue‐like mechanical properties with mixed ionic and electronic conductivity, providing new ways to use electricity to influence cell behavior in a native‐like microenvironment.

Highly Adhesive, Ultrafast Self-Healing, and Conductive Dopamine-Based Polymer Hydrogels for Sensitive Human Motion Sensing

Highly Adhesive, Ultrafast Self-Healing, and Conductive Dopamine-Based Polymer Hydrogels for Sensitive Human Motion Sensing

Conductive Polymer-Based Hydrogels for Wearable Electrochemical Biosensors.

Hydrogels are gaining popularity for use in wearable electronics owing to their inherent biomimetic characteristics, flexible physicochemical properties, and excellent biocompatibility. Among various hydrogels, conductive polymer-based hydrogels (CP HGs) have emerged as excellent candidates for future wearable sensor designs. These hydrogels can attain desired properties through various tuning strategies extending from molecular design to microstructural configuration. However, significant challenges remain, such as the limited strain-sensing range, significant hysteresis of sensing signals, dehydration-induced functional failure, and surface/interfacial malfunction during manufacturing/processing. This review summarizes the recent developments in polymer-hydrogel-based wearable electrochemical biosensors over the past five years. Initially serving as carriers for biomolecules, polymer-hydrogel-based sensors have advanced to encompass a wider range of applications, including the development of non-enzymatic sensors facilitated by the integration of nanomaterials such as metals, metal oxides, and carbon-based materials. Beyond the numerous existing reports that primarily focus on biomolecule detection, we extend the scope to include the fabrication of nanocomposite conductive polymer hydrogels and explore their varied conductivity mechanisms in electrochemical sensing applications. This comprehensive evaluation is instrumental in determining the readiness of these polymer hydrogels for point-of-care translation and state-of-the-art applications in wearable electrochemical sensing technology.

High-Performance Organic-Inorganic Hybrid Conductive Hydrogels for Stretchable Elastic All-Hydrogel Supercapacitors and Flexible Self-Powered Integrated Systems.

Conductive polymer hydrogels exhibit unique electrical, electrochemical, and mechanical properties, making them highly competitive electrode materials for stretchable high-capacity energy storage devices for cutting-edge wearable electronics. However, it remains extremely challenging to simultaneously achieve large mechanical stretchability, high electrical conductivity, and excellent electrochemical properties in conductive polymer hydrogels because introducing soft insulating networks for improving stretchability inevitably deteriorates the connectivity of rigid conductive domain and decreases the conductivity and electrochemical activity. This work proposes a distinct confinement self-assembly and multiple crosslinking strategy to develop a new type of organic-inorganic hybrid conductive hydrogels with biphase interpenetrating cross-linked networks. The hydrogels simultaneously exhibit high conductivity (2000 S m-1), large stretchability (200%), and high electrochemical activity, outperforming existing conductive hydrogels. The inherent mechanisms for the unparalleled comprehensive performances are thoroughly investigated. Elastic all-hydrogel supercapacitors are prepared based on the hydrogels, showing high specific capacitance (212.5 mF cm-2), excellent energy density (18.89 µWh cm-2), and large deformability. Moreover, flexible self-powered luminescent integrated systems are constructed based on the supercapacitors, which can spontaneously shine anytime and anywhere without extra power. This work provides new insights and feasible avenues for developing high-performance stretchable electrode materials and energy storage devices for wearable electronics.

Dual network hydrogel sensors based on borate ester bond: Multifunctional performance in high conductivity, stretchability, mechanical strength, and anti-freezing properties

Conductive polymer hydrogels have attracted great attention due to their application prospects in the fields of health care monitoring, wearable electronics and soft robots. Developing hydrogel sensors with robust mechanical characteristics, outstanding sensing abilities, the ability to self-heal and adhere effectively is critical, yet it remains a major challenge. Here, we present a simple one-pot method to prepare a dual-network flexible hydrogel based on polyvinyl alcohol (PVA), acrylamide (AM), pyridine-4-boronic acid derivatives (PBAD), and lithium chloride (LiCl). The cross-linked network is established through reversible and dynamic borate ester bonds, hydrogen bonds, electrostatic interactions and coordination bonds, imparting outstanding mechanical and self-healing characteristics to the material. The incorporation of PBAD not only imparts high conductivity (9.84 mS·cm−1) and sensitive sensing performance (GF = 13.89) to the hydrogel, but also synergistically improves its elongation (1689 %), tensile strength (0.6 MPa), and toughness (5.74 MJ/m3). In addition, based on the participation of LiCl, the hydrogel shows outstanding anti-freezing properties. This work is expected to provide new ideas for the assembly of high performance flexible sensor and to expand their application in electronic skin, wearable devices, and soft actuators.

Highly deformable bi-continuous conducting polymer hydrogels for electrochemical energy storage

Conducting polymer hydrogels with inherent flexibility, ionic conductivity and environment friendliness are promising materials in the fields of energy storage. However, a trade-off between mechanical and electrochemical properties has limited the development of flexible/stretchable conducting polymer hydrogel electrodes, owing to the intrinsic conflict among mechanical and electrical phases. Here, we report a reliable design to enable conducting polymer with both exceptional mechanical and electrical/electrochemical performance through the construction of bi-continuous conducting polymer crosslinked network. The resultant bi-continuous conducting polymer hydrogels (BCPH) demonstrate significantly improved mechanical and electrochemical properties compared to the conventional conducting polymer hydrogel (CPH) electrode. BCPH presents a high specific capacitance of 715 F g−1 at 0.5 A/g, a high mechanical strength (∼1 MPa) and a large stretchability (∼300%). Enabled by such intrinsically deformability and electrochemical properties, we further demonstrate its utility in flexible solid-state supercapacitor (FSSC), which exhibits an outstanding specific capacitance of 760 mF cm−2 at 2 mA cm−2, excellent electrochemical stability with 81% capacitance retention after 5000 charge/discharge cycles, and superior bending cycle stability. This simple and scalable strategy provides a platform for the fabrication of high-performance conducting hydrogel electrodes for various wearable electronic equipment.

Silver nanowire-doped conductive polymer hydrogel anode for increasing electron transfer and COD removal rate simultaneously in microbial fuel cell

Microbial fuel cell (MFC) can generate electrons through microbial metabolism of organic matter in sewage. In this paper, carbon felt as base material, the conductive polymers polyaniline and polypyrrole combined with silver nanowires were doped in hydrogel, a super hydrophilicity, low electron transfer resistance, good biocompatibility hydrogel MFC anode (PANI-PPy-Ag NWs/CF) were prepared. It showed a hand-torn bread structure, this three-dimensional (3D) porous structure increased microbial attachment amount. The anode could reach a maximum voltage output of 0.66 V in only 5.5 h, and produce a maximum power density of 2196.61 mW/m3. Due to the doping of silver nanowire, a new electronic mode was explored, coulomb efficiency of 31.01 % and an ultra-high COD removal rate (96.69 %) was obtained. This study introduces a conductive composite hydrogel MFC anode, which provides a new idea for the material diversity, electrical production and sewage removal performance of MFC anode.

Laser-induced wet stability and adhesion of pure conducting polymer hydrogels

Laser-induced wet stability and adhesion of pure conducting polymer hydrogels

Tailored wrinkles for tunable sensing performance by stereolithography

AbstractConducting polymer hydrogel can address the challenges of stricken biocompatibility and durability. Nevertheless, conventional conducting polymer hydrogels are often brittle and weak due to the intrinsic quality of the material, which exhibits viscoelasticity. This property may cause a delay in sensor response time due to hysteresis. To overcome these limitations, we have designed a wrinkle morphology three‐dimensional (3D) substrate using digital light processing technology and then followed by in situ polymerization to form interpenetrating polymer network hydrogels. This novel design results in a wrinkle morphology conducting polymer hydrogel elastomer with high precision and geometric freedom, as the size of the wrinkles can be controlled by adjusting the treating time. The wrinkle morphology on the conducting polymer hydrogel effectively reduces its viscoelasticity, leading to samples with quick response time, low hysteresis, stable cyclic performance, and remarkable resistance change. Simultaneously, the 3D gradient structure augmented the sensor's sensitivity under minimal stress while exhibiting consistent sensing performance. These properties indicate the potential of the conducting polymer hydrogel as a flexible sensor.

Antibacterial conductive polyacrylamide/quaternary ammonium chitosan hydrogel for electromagnetic interference shielding and strain sensing

The utilization of biomass-based conductive polymer hydrogels in wearable electronics holds great promise for advancing performance and sustainability. An interpenetrating network of polyacrylamide/2-hydroxypropyltrimethyl ammonium chloride chitosan (PAM/HACC) was firstly obtained through thermal-initiation polymerization of AM monomers in the presence of HACC. The positively charged groups on HACC provide strong electrostatic interactions and hydrogen bonding with the PAM polymer chains, leading to improved mechanical strength and stability of the hydrogel network. Subsequently, the PAM/HACC networks served as the skeletons for the in-situ polymerization of polypyrrole (PPy), and then the resulting conductive hydrogel demonstrated stable electromagnetic shielding performance (40 dB), high sensitivity for strain sensing (gauge factor = 2.56). Moreover, the incorporation of quaternary ammonium chitosan into PAM hydrogels enhances their antimicrobial activity, making them more suitable for applications in bacterial contamination or low-temperature environments. This conductive hydrogel, with its versatility and excellent mechanical properties, shows great potential in applications such as electronic skin and flexible/wearable electronics.

Conducting polymer hydrogels based on supramolecular strategies for wearable sensors.

Conductive polymer hydrogels (CPHs) are gaining considerable attention in developing wearable electronics due to their unique combination of high conductivity and softness. However, in the absence of interactions, the incompatibility between hydrophobic conductive polymers (CPs) and hydrophilic polymer networks gives rise to inadequate bonding between CPs and hydrogel matrices, thereby significantly impairing the mechanical and electrical properties of CPHs and constraining their utility in wearable electronic sensors. Therefore, to endow CPHs with good performance, it is necessary to ensure a stable and robust combination between the hydrogel network and CPs. Encouragingly, recent research has demonstrated that incorporating supramolecular interactions into CPHs enhances the polymer network interaction, improving overall CPH performance. However, a comprehensive review focusing on supramolecular CPH (SCPH) for wearable sensing applications is currently lacking. This review provides a summary of the typical supramolecular strategies employed in the development of high-performance CPHs and elucidates the properties of SCPHs that are closely associated with wearable sensors. Moreover, the review discusses the fabrication methods and classification of SCPH sensors, while also exploring the latest application scenarios for SCPH wearable sensors. Finally, it discusses the challenges of SCPH sensors and offers suggestions for future advancements.

Free-standing and flexible polyvinyl alcohol-sodium alginate-polypyrrole electrodes based on interpenetrating network hydrogels

Flexible supercapacitors (FSCs) have attracted much attention due to their strong mechanical flexibility, wearability and portability, which greatly rely on the employed flexible electrodes. The conductive polymer hydrogels with excellent flexibility, processability and capacitive performance are one of the most promising candidates, which are still limited by their poor mechanical properties. Constructing robust interpenetrating polymer networks (IPN) is an effective approach to promote their mechanical properties. Herein, interpenetrating polyvinyl alcohol (PVA)-sodium alginate (SA)-polypyrrole (PPy) hydrogels are prepared by the freeze–thaw and in-situ polymerization method. The IPN structure composed of PVA and SA not only enhances the mechanical properties of hydrogels, but also provides substantial active sites for electrochemical reactions. Moreover, the hydrogen-bonding interaction between different components in the PVA-SA-PPy hydrogel boosts the charge/ion transfer. The optimal PVA-SA-PPy hydrogels show an elongation at break of 380 %, a tensile strength of 1.5 MPa, and a specific capacitance of 2646 mF cm−2 at 2 mA cm−2. The symmetric PVA-SA-PPy FSCs show an energy density of 96.7 μWh cm−2 at a power density of 999.9 μW cm−2, and the capacitance retention is 66.3 % after 10,000 cycles. These exceptional mechanical and electrochemical properties make the PVA-SA-PPy hydrogels a promising candidate for FSCs.

Fabrication of Sodium Trimetaphosphate-Based PEDOT:PSS Conductive Hydrogels.

Conductive hydrogels are highly attractive for biomedical applications due to their ability to mimic the electrophysiological environment of biological tissues. Although conducting polymer polythiophene-poly-(3,4-ethylenedioxythiophene) (PEDOT) and polystyrene sulfonate (PSS) alone exhibit high conductivity, the addition of other chemical compositions could further improve the electrical and mechanical properties of PEDOT:PSS, providing a more promising interface with biological tissues. Here we study the effects of incorporating crosslinking additives, such as glycerol and sodium trimetaphosphate (STMP), in developing interpenetrating PEDOT:PSS-based conductive hydrogels. The addition of glycerol at a low concentration maintained the PEDOT:PSS conductivity with enhanced wettability but decreased the mechanical stiffness. Increasing the concentration of STMP allowed sufficient physical crosslinking with PEDOT:PSS, resulting in improved hydrogel conductivity, wettability, and rheological properties without glycerol. The STMP-based PEDOT:PSS conductive hydrogels also exhibited shear-thinning behaviors, which are potentially favorable for extrusion-based 3D bioprinting applications. We demonstrate an interpenetrating conducting polymer hydrogel with tunable electrical and mechanical properties for cellular interactions and future tissue engineering applications.

Manipulation of Conducting Polymer Hydrogels with Different Shapes and Related Multifunctionality.

Maneuver of conducting polymers (CPs) into lightweight hydrogels can improve their functional performances in energy devices, chemical sensing, pollutant removal, drug delivery, etc. Current approaches for the manipulation of CP hydrogels are limited, and they are mostly accompanied by harsh conditions, tedious processing, compositing with other constituents, or using unusual chemicals. Herein, a two-step route is introduced for the controllable fabrication of CP hydrogels in ambient conditions, where gelation of the shape-anisotropic nano-oxidants followed by in-situ oxidative polymerization leads to the formation of polyaniline (PANI) and polypyrrole hydrogels. The method is readily coupled with different approaches for materials processing of PANI hydrogels into varied shapes, including spherical beads, continuous wires, patterned films, and free-standing objects. In comparison with their bulky counterparts, lightweight PANI items exhibit improved properties when those with specific shapes are used as electrodes for supercapacitors, gas sensors, or dye adsorbents. The current study therefore provides a general and controllable approach for the implementation of CP into hydrogels of varied external shapes, which can pave the way for the integration of lightweight CP structures with emerging functional devices.

3D Printed Implantable Hydrogel Bioelectronics for Electrophysiological Monitoring and Electrical Modulation

AbstractElectronic devices based on conducting polymer hydrogels have emerged as one of the most promising implantable bioelectronics for electrophysiological monitoring and diagnosis of a wide spectrum of diseases, in light of their distinct conductivity and biocompatibility. However, most conducting polymer hydrogels‐based bioelectronics are routinely fabricated through conventional techniques, which are challenged by its intrinsic poor processability of conducting polymers, as well as the essentially fragile biointerface, thus hampering their rapid innovation and application in advanced implantable bioelectronics. Here, 3D printable hydrogels based on poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is reported, featuring superior 3D printability for direct ink writing (DIW), tissue‐like mechanical compliance (Young's modulus of 650 kPa), instant and tough bioadhesion (interfacial toughness of 200 J m−2 and shear strength of 120 kPa), highly‐tunable electrical properties, as well as long‐term in vitro and in vivo structural and electrochemical robustness. Electro‐physiological studies rat heart models with normal or arrhythmic conditions highlight the capabilities of establishing conformal biointerface with the dynamic organs, allowing for long‐term and high‐precision spatiotemporary epicardial electrophysiological monitoring, as well as electrical modulation of acute myocardial infarction (MI) model. These advances provide a promising strategy to improve the tissue‐electronics interfacing, and could serve as the basis for the next generation bioelectronics toward healthcare monitoring, diagnosis and medical therapies.

Improving EET kinetics and energy conversion efficiency of 3D hydrophilic composite hydrogel through 2D direction biofilm growth

The limited power output of microbial fuel cells (MFCs) has impeded their widespread adoption application. Thoughtful selection of a suitable anode material not only enhances extracellular electron transfer (EET) efficiency but also stimulates microbial adhesion and proliferation. Herein, a three-dimensional conductive polymer hydrogel MXene/(polypyrrole)-(polyacrylamide) (MPP) is proposed, which can enhance the power generation performance of the bioanode by promoting the enrichment of microorganisms in the two-dimensional direction. The integration of hydrogel molecular chains within the layers of MXene effectively inhibits the self-aggregation of MXene layers, thereby facilitating the formation of ion transport channels for expedited charge storage. As a result, the maximum power density increases from 3.12 W/m3 (CF) to 6.71 W/m3 (MPP-25), the protein content of MPP-25 bioanode (59.66 ± 2.39 mg/cm2) is 3.34 times higher than that of CF (17.85 ± 1.53 mg/cm2), and the exchange current density value increases from 0.06 mA/cm2 (CF) to 0.26 mA/cm2. Conductive hydrogels prepared by MXene as a modifier are a promising bioelectrocatalyst for high-performance MFCs.

3D Printing of Robust High-Performance Conducting Polymer Hydrogel-Based Electrical Bioadhesive Interface for Soft Bioelectronics.

Electrical bioadhesive interface (EBI), especially conducting polymer hydrogel (CPH)-based EBI, exhibits promising potential applications in various fields, including biomedical devices, neural interfaces, and wearable devices. However, current fabrication techniques of CPH-based EBI mostly focus on conventional methods such as direct casting, injection, and molding, which remains a lingering challenge for further pushing them toward customized practical bioelectronic applications and commercialization. Herein, 3D printable high-performance CPH-based EBI precursor inks are developed through composite engineering of PEDOT:PSS and adhesive ionic macromolecular dopants within tough hydrogel matrices (PVA). Such inks allow the facile fabrication of high-resolution and programmable patterned EBI through 3D printing. Upon successive freeze-thawing, the as-printed PEDOT:PSS-based EBI simultaneously exhibits high conductivity of 1.2 S m-1, low interfacial impedance of 20 Ω, high stretchability of 349%, superior toughness of 109kJ m-3, and satisfactory adhesion to various materials. Enabled by these advantageous properties and excellent printability, the facile and continuous manufacturing of EBI-based skin electrodes is further demonstratedvia 3D printing, and the fabricated electrodes display excellent ECG and EMG signal recording capability superior to commercial products. This work may provide a new avenue for rational design and fabrication of next-generation EBI for soft bioelectronics, further advancing seamless human-machine integration.