Conducting Polymer Hydrogels Research Articles

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.

One-step synthesis of MXene-functionalized PEDOT:PSS conductive polymer hydrogels for wearable and noninvasive monitoring of sweat glucose

Wearable biosensors have gained substantial attention for their capacity to deliver real-time and continuous physiological information through noninvasive and dynamic monitoring of biochemical markers in biological fluids. In particular, wearable and flexible electrochemical sensors have found extensive usage for the detection of biomarkers in human sweat in a quantifiable and noninvasive manner. Herein, we present a novel MXene-functionalized PEDOT:PSS conducting composite hydrogels-based electrochemical biosensor for continuous noninvasive monitoring of human glucose. Ethylene glycol (EG) was added to the hydrogel throughout the preparation process, aiding in the expansion of the polymer chains and resulting in excellent electrical conductivity and porous networks, which helps to increase the film-forming properties, flexibility and stability of the material, and also improves the stacking and peeling problems of powdered materials. The limit of the hydrogel biosensor for glucose detection was as low as 1.9 μM and the sensitivity was 21.7 μA⋅mM−1⋅cm−2. Furthermore, the hydrogel incorporated with screen-printed carbon electrodes (SPCE) was employed to the human body for continuous noninvasive sweat glucose monitoring as the skin patch in vitro. The results of the biosensor showed good correlation with glucose meter readings. We believe that this glucose biosensor lays the foundation for noninvasive wearable monitoring of glucose in diabetic patients.

Lignosulfonate sodium assisted PEDOT-based all-gel supercapacitors with enhanced supercapacitance and wide temperature tolerance

Conducting polymer hydrogels are typically employed in all-gel supercapacitors; however, Poly[3,4-ethylene-dioxythiophene] (PEDOT)-based hydrogel supercapacitors still suffer from low capacitance because of the low packing density of PEDOT in the electrodes. Here, we demonstrate lignosulfonate sodium (LS) as an excellent template to synthesize various LS-PEDOT conductive nanofillers for high mass-loading LS-PEDOT/PAAM hydrogel electrodes. Then, the optimum LS-PEDOT/PAAM electrode was assembled with a redox-active LS/PAAM/Fe3+ hydrogel electrolyte to form sandwich-structured all-gel supercapacitors, which could deliver a high specific capacitance of 672.5 mF/cm2 and an energy efficiency of 60 μWh/cm2, which are three times higher than the 220 mF/cm2 and 19.5 μWh/cm2 of the device without Fe3+ at the same condition. Such a device shows excellent temperature tolerance from −30 to 100 °C. Besides, the LS-PEDOT/PAAM electrode has excellent photothermal conversion effects under simulated solar illumination. The sluggish electrochemical performance of the SC under low temperatures could be significantly boosted by ~50 % under simulated solar light. All of these findings demonstrate that the capacitance performance of the PEDOT-based hydrogel device is successfully improved not only at room temperature but also under subzero conditions.

Resilient and Tough Conductive Polymer Hydrogel for a Low-Hysteresis Strain Sensor.

Conductive polymer hydrogels are vital in strain sensors, yet achieving high resilience and toughness is a challenge. This study employs a prestretch method to engineer a tough conductive polymer hydrogel with sufficient resilience. Initially, a blend film of polyvinylalcohol (PVA) and ethylene-vinyl alcohol copolymer (EVOH) is prepared through solution casting, followed by a swelling process to form a PVA-EVOH hydrogel. This hydrogel, with PVA crystallites as crosslinking points, exhibits high toughness. The hydrogel is then immersed in pyrrole and ferric chloride solutions for in-situ polymerization of polypyrrole (PPy), creating a conductive PPy/PVA-EVOH hydrogel. Finally, a 200% prestretch is applied, breaking short chains within the network, eliminating energy dissipation at low strains. This results in a hydrogel with a 100% elastic deformation range, while maintaining high fracture toughness (1700Jm-2 ). The prestretched PPy/PVA-EVOH hydrogel functions as a strain sensor with low hysteresis, providing consistent strain measurements during loading and unloading. This outperforms the non-prestretched sample, which shows inconsistent responses between stretching and releasing.

Fatigue‐Resistant Conducting Polymer Hydrogels as Strain Sensor for Underwater Robotics (Adv. Funct. Mater. 42/2023)

Fatigue‐Resistant Conducting Polymer Hydrogels as Strain Sensor for Underwater Robotics (Adv. Funct. Mater. 42/2023)

Mechanically‐Compliant Bioelectronic Interfaces through Fatigue‐Resistant Conducting Polymer Hydrogel Coating (Adv. Mater. 40/2023)

Mechanically‐Compliant Bioelectronic Interfaces through Fatigue‐Resistant Conducting Polymer Hydrogel Coating (Adv. Mater. 40/2023)

Self-Healable PEDOT:PSS-PVA Nanocomposite Hydrogel Strain Sensor for Human Motion Monitoring.

Strain sensors based on conducting polymer hydrogels are considered highly promising candidates for wearable electronic devices. However, existing conducting polymer hydrogels are susceptible to aging, damage, and failure, which can greatly deteriorate the sensing performance of strain sensors based on these substances and the accuracy of data collection under large deformation. Developing conductive polymer hydrogels with concurrent high sensing performance and self-healing capability is a critical yet challenging task to improve the stability and lifetime of strain sensors. Herein, we design a self-healable conducting polymer hydrogel by compositing poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) nanofibers and poly(vinyl alcohol) (PVA) via both physical and chemical crosslinking. This PEDOT:PSS-PVA nanocomposite hydrogel strain sensor displays an excellent strain monitoring range (>200%), low hysteresis (<1.6%), a high gauge factor (GF = 3.18), and outstanding self-healing efficiency (>83.5%). Electronic skins based on such hydrogel strain sensors can perform the accurate monitoring of various physiological signals, including swallowing, finger bending, and knee bending. This work presents a novel conducting polymer hydrogel strain sensor demonstrating both high sensing performance and self-healability, which can satisfy broad application scenarios, such as wearable electronics, health monitoring, etc.

Mechanically-Compliant Bioelectronic Interfaces through Fatigue-Resistant Conducting Polymer Hydrogel Coating.

Because of their distinct electrochemical and mechanical properties, conducting polymer hydrogels have been widely exploited as soft, wet, and conducting coatings for conventional metallic electrodes, providing mechanically compliant interfaces and mitigating foreign body responses. However, the long-term viability of these hydrogel coatings is hindered by concerns regarding fatigue crack propagation and/or delamination caused by repetitive volumetric expansion/shrinkage during long-term electrical interfacing. This study reports a general yet reliable approach to achieving a fatigue-resistant conducting polymer hydrogel coating on conventional metallic bioelectrodes by engineering nanocrystalline domains at the interface between the hydrogel and metallic substrates. It demonstrates the efficacy of this robust, biocompatible, and fatigue-resistant conducting hydrogel coating in cardiac pacing, showcasing its ability to effectively reduce the pacing threshold voltage and enhance the long-term reliability of electric stimulation. This study findings highlight the potential of its approach as a promising design and fabrication strategy for the next generation of seamless bioelectronicinterfaces.

Fatigue‐Resistant Conducting Polymer Hydrogels as Strain Sensor for Underwater Robotics

AbstractConducting polymer hydrogels are widely used as strain sensors in light of their distinct skin‐like softness, strain sensitivity, and environmental adaptiveness in the fields of wearable devices, soft robots, and human‐machine interface. However, the mechanical and electrical properties of existing conducting polymer hydrogels, especially fatigue‐resistance and sensing robustness during long‐term application, are unsatisfactory, which severely hamper their practical utilities. Herein, a strategy to fabricate conducting polymer hydrogels with anisotropic structures and mechanics is presented through a combined freeze‐casting and salting‐out process. The as‐fabricated conducting polymer hydrogels exhibit high fatigue threshold (&gt;300 J m−2), low Young's modulus (≈100 kPa), as well as long‐term strain sensing robustness (over 10 000 cycles). Such superior performance enables their application as strain sensors to monitor the real‐time movement of underwater robotics. The design and fabrication strategy for conducting polymer hydrogels reported in this study may open up an enticing avenue for functional soft materials in soft electronics and robotics.

Strong, Tough, and Anti-Swelling Supramolecular Conductive Hydrogels for Amphibious Motion Sensors.

Conductive polymer hydrogels (CPHs) are widely employed in emerging flexible electronic devices because they possess both the electrical conductivity of conductors and the mechanical properties of hydrogels. However, the poor compatibility between conductive polymers and the hydrogel matrix, as well as the swelling behavior in humid environments, greatly compromises the mechanical and electrical properties of CPHs, limiting their applications in wearable electronic devices. Herein, a supramolecular strategy to develop a strong and tough CPH with excellent anti-swelling properties by incorporating hydrogen, coordination bonds, and cation-π interactions between a rigid conducting polymer and a soft hydrogel matrix is reported. Benefiting from the effective interactions between the polymer networks, the obtained supramolecular hydrogel has homogeneous structural integrity, exhibiting remarkable tensile strength (1.63MPa), superior elongation at break (453%), and remarkable toughness (5.5MJ m-3 ). As a strain sensor, the hydrogel possesses high electrical conductivity (2.16S m-1 ), a wide strain linear detection range (0-400%), and excellent sensitivity (gauge factor = 4.1), sufficient to monitor human activities with different strain windows. Furthermore, this hydrogel with high swelling resistance has been successfully applied to underwater sensors for monitoring frog swimming and underwater communication. These results reveal new possibilities for amphibious applications of wearable sensors.

Triple‐network‐based conductive polymer hydrogel for soft and elastic bioelectronic interfaces

AbstractConductive polymer hydrogels have greatly improved the compatibility of electronic devices with biological tissues for human–machine interfacing. Hydrogels that possess low Young's modulus, low interfacial impedance, and high tensile properties facilitate high‐quality signal transmission across dynamic biointerfaces. Direct incorporation of elastomers with conductive polymers may result in undesirable mechanical and/or electrical performance. Here, a covalent cross‐linking network and an entanglement‐driven network with conductive poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) have been combined. The triple‐network conductive hydrogel shows high stretchability (with fracture strain up to 900%), low impedance (down to 91.2 Ω cm2), and reversible adhesion. Importantly, ultra‐low modulus (down to 6.3 kPa) and strain‐insensitive electrical/electrochemical performance were achieved, which provides a guarantee for low current stimulation. The material design will contribute to the progression of soft and conformal bioelectronic devices, and pave the way to future implantable electronics.

3D printable high-performance conducting polymer hydrogel for all-hydrogel bioelectronic interfaces.

Owing to the unique combination of electrical conductivity and tissue-like mechanical properties, conducting polymer hydrogels have emerged as a promising candidate for bioelectronic interfacing with biological systems. However, despite the recent advances, the development of hydrogels with both excellent electrical and mechanical properties in physiological environments is still challenging. Here we report a bi-continuous conducting polymer hydrogel that simultaneously achieves high electrical conductivity (over 11 S cm-1), stretchability (over 400%) and fracture toughness (over 3,300 J m-2) in physiological environments and is readily applicable to advanced fabrication methods including 3D printing. Enabled by these properties, we further demonstrate multi-material 3D printing of monolithic all-hydrogel bioelectronic interfaces for long-term electrophysiological recording and stimulation of various organs in rat models.

Challenges and Opportunities of Implantable Neural Interfaces: From Material, Electrochemical and Biological Perspectives

AbstractThe desirable implantable neural interfaces can accurately record bioelectrical signals from neurons and regulate neural activities with high spatial/time resolution, facilitating the understanding of neuronal functions and dynamics. However, the electrochemical performance (impedance, charge storage/injection capacity) is limited with the miniaturization and integration of neural electrodes. The “crosstalk” caused by the uneven distribution of elctric field leads to lower electrical stimulation/recording efficiency. The mismatch between stiff electrodes and soft tissues exacerbates the inflammatory responses, thus weakening the transmission of signals. Though remarkable breakthroughs have been made through the incorporation of optimizing electrode design and functionalized nanomaterials, the chronic stability, and long‐term activity in vivo of the neural electrodes still need further development. In this review, the neural interface challenges mainly on electrochemistry and biology are discussed, followed by summarizing typical electrode optimization technologies and exploring recent advances in the application of nanomaterials, based on traditional metallic materials, emerging 2D materials, conducting polymer hydrogels, etc., for enhancing neural interfaces. The strategies for improving the durability including enhanced adhesion and minimized inflammatory response, are also summarized. The promising directions are finally presented to provide enlightenment for high‐performance neural interfaces in future, which will promote profound progress in neuroscience research.

A 3D phytic acid cross-linked high-porous conductive hydrogel integrating g-C3N4 for electrochemical multiplex sensing of heavy metal ions

It is a great challenge to develop an effective super-sensitive capture method for multiplex heavy metal ions (HMIs), because HMIs is extremely toxic to public health and the environment, what's more their contamination is usually multiplex ions pollution. In this work, a 3D high-porous conductive polymer hydrogel was designed and prepared with high-stable and easy mass production, which is very favorable for the industrialization. The polymer hydrogel (g–C3N4–P(Ani-Py)-PAAM) was formed from the mixture of aniline pyrrole copolymer and acrylamide cross-linked with phytic acid as dopant and cross-linker and integrated with g-C3N4. The 3D networked high-porous hydrogel not only exhibits excellent electrical conductivity, but also provides a large surface area for increasing the number of immobilized ions. Importantly, the 3D high-porous conductive polymer hydrogel was applied successfully in electrochemical multiplex sensing of HIMs. The prepared sensor used differential pulse anodic stripping voltammetry exhibited high sensitivities, low detection limit and wide detection ranges for Cd2+, Pb2+, Hg2+ and Cu2+, respectively. Moreover, the sensor showed a high accuracy in lake water test. The preparation and application of the hydrogel in electrochemical sensor provided an availability strategy to capture and detect the various HMIs by electrochemistry in solution and has great commercial application prospect.

Recent Progress in Biomedical Sensors Based on Conducting Polymer Hydrogels

Biosensors are increasingly taking a more active role in health science. The current needs for the constant monitoring of biomedical signals, as well as the growing spending on public health, make it necessary to search for materials with a combination of properties such as biocompatibility, electroactivity, resorption, and high selectivity to certain bioanalytes. Conducting polymer hydrogels seem to be a very promising materials, since they present many of the necessary properties to be used as biosensors. Furthermore, their properties can be shaped and enhanced by designing conductive polymer hydrogel-based composites with more specific functionalities depending on the end application. This work will review the recent state of the art of different biological hydrogels for biosensor applications, discuss the properties of the different components alone and in combination, and reveal their high potential as candidate materials in the fabrication of all-organic diagnostic, wearable, and implantable sensor devices.

Pure Conducting Polymer Hydrogels Increase Signal-to-Noise of Cutaneous Electrodes by Lowering Skin Interface Impedance.

Cutaneous electrodes are routinely used for noninvasive electrophysiological sensing of signals from the brain, the heart, and the neuromuscular system. These bioelectronic signals propagate as ionic charge from their sources to the skin-electrode interface where they are then sensed as electronic charge by the instrumentation. However, these signals suffer from low signal-to-noise ratio arising from the high impedance at the tissue-to-electrode contact interface. This paper reports that soft conductive polymer hydrogels made purely of poly(3,4-ethylenedioxy-thiophene) doped with poly(styrene sulfonate) present nearly an order of magnitude decrease in the skin-electrode contact impedance (88%, 82%, and 77% at 10, 100, and 1kHz, respectively) when compared to clinical electrodes in an ex vivo model that isolates the bioelectrochemical features of a single skin-electrode contact. Integrating these pure soft conductive polymer blocks into an adhesive wearable sensor enables high fidelity bioelectronic signals with higher signal-to-noise ratio (average 2.1dB increase, max 3.4dB increase) when compared to clinical electrodes across all subjects. The utility of these electrodes is demonstrated in a neural interface application. The conductive polymer hydrogels enable electromyogram-based velocity control of a robotic arm to complete a pick and place task. This work provides a basis for the characterization and use of conductive polymer hydrogels to better couple human and machine.

Simultaneous Polymerization Acceleration and Mechanical Enhancement for Printing a Biomimetic PEDOT Adhesive by Coordinative and Orthogonal Ruthenium Photochemistry

Conductive hydrogels are promising material candidates in fields ranging from flexible sensors and electronic skin applications to personalized medical monitoring. However, developing intrinsically conductive polymer hydrogels (ICPHs) with high mechanical properties and excellent printability is still challenging. Here, we introduce a simultaneous polymerization acceleration and mechanical enhancement (SPAME) strategy to construct PEDOT-based ICPHs via the rational design of coordinative and orthogonal ruthenium photochemistry (CORP). This orthogonal photochemistry triggers the oxidative polymerization of EDOT and the coupling of phenols within seconds under blue light irradiation. Benefiting from the bifunctional EDTA-Fe design, the photoreleased Fe(III) accelerated the EDOT polymerization and shortened the preparation time of ICPHs to a few seconds. At the same time, the addition of EDTA-Fe enhanced their mechanical properties, and both the critical strains and maximum stresses of the hydrogel doubled. Furthermore, the introduction of phenol residues in PAA-Ph significantly shortened the gelation time from several minutes to about 7 s. Thus, this fast and controllable CORP chemistry is compatible with standard printing techniques for engineering hydrogels for complex multifunctional structures for multifunctional bioelectronics and devices.

Hydroxypropyl methyl cellulose reinforced conducting polymer hydrogels with ultra-stretchability and low hysteresis as highly sensitive strain sensors for wearable health monitoring

Conducting polymer hydrogels have emerged as promising materials to fabricate highly sensitive strain sensors. However, due to weak bindings between conducting polymer and gel network, they usually suffer from limited stretchability and large hysteresis, failing to achieve wide-range strain sensing. Herein, we combine hydroxypropyl methyl cellulose (HPMC), poly (3,4-ethylenedioxythiophene):poly (styrene sulfonic acid) (PEDOT: PSS) with chemically cross-linked polyacrylamide (PAM) to prepare a conducting polymer hydrogel for strain sensors. Owing to abundant hydrogen bonds between HPMC, PEDOT:PSS and PAM chains, this conducting polymer hydrogel exhibits high tensile strength (166 kPa), ultra-stretchability (>1600 %) and low hysteresis (<10 % at 1000 % cyclic tensile strain). The resultant hydrogel strain sensor shows ultra-high sensitivity, wide strain sensing ranges of 2–1600 %, and excellent durability and reproducibility. Finally, this strain sensor can be used as wearable sensor to monitor vigorous human movement and fine physiological activity, and services as bioelectrodes for electrocardiograph and electromyography monitoring. This work provides new horizons to design conducting polymer hydrogels for advanced sensing devices.

Electrically responsive release of proteins from conducting polymer hydrogels.

Electrically modulated delivery of proteins provides an avenue to target local tissues specifically and tune the dose to the application. This approach prolongs and enhances activity at the target site whilst reducing off-target effects associated with systemic drug delivery. The work presented here explores an electrically active composite material comprising of a biocompatible hydrogel, gelatin methacryloyl (GelMA) and a conducting polymer, poly(3,4-ethylenedioxythiophene), generating a conducting polymer hydrogel. In this paper, the key characteristics of electroactivity, mechanical properties, and morphology are characterized using electrochemistry techniques, atomic force, and scanning electron microscopy. Cytocompatibility is established through exposure of human cells to the materials. By applying different electrical-stimuli, the short-term release profiles of a model protein can be controlled over 4h, demonstrating tunable delivery patterns. This is followed by extended-release studies over 21 days which reveal a bimodal delivery mechanism influenced by both GelMA degradation and electrical stimulation events. This data demonstrates an electroactive and cytocompatible material suitable for the delivery of protein payloads over 3 weeks. This material is well suited for use as a treatment delivery platform in tissue engineering applications where targeted and spatio-temporal controlled delivery of therapeutic proteins is required. STATEMENT OF SIGNIFICANCE: Growth factor use in tissue engineering typically requires sustained and tunable delivery to generate optimal outcomes. While conducting polymer hydrogels (CPH) have been explored for the electrically responsive release of small bioactives, we report on a CPH capable of releasing a protein payload in response to electrical stimulus. The composite material combines the benefits of soft hydrogels acting as a drug reservoir and redox-active properties from the conducting polymer enabling electrical responsiveness. The CPH is able to sustain protein delivery over 3 weeks, with electrical stimulus used to modulate release. The described material is well suited as a treatment delivery platform to deliver large quantities of proteins in applications where spatio-temporal delivery patterns are paramount.

Controlling the Stem Cell Environment Via Conducting Polymer Hydrogels to Enhance Therapeutic Potential

AbstractStem cells are a promising treatment option for various neurological diseases such as stroke, spinal cord injury, and other neurodegenerative disorders. However, the ideal environment to optimize the therapeutic potential of the cells remains poorly understood. Stem cells in the native environment are influenced by a combination of mechanical, chemical, and electrical cues for proliferation and differentiation. Because of their controllable properties, conductive hydrogels are promising biomaterials to interact with stem cells. Herein, this work develops an interpenetrating conducting polymer hydrogel with tunable mechanical properties. The hydrogel serves as a platform to provide mechanical and electrical cues for interactions with mesenchymal stem cells (MSCs). This work optimizes the formulation of the hydrogel for maximum viability of MSCs and relatively higher cytoskeletal protein expression. The viability of cells is not affected due to electrical stimulation (ES). Further, ES alters the trophic factor secretion of MSCs, with significant increase in VEGF pathway genes—VEGFA and HSPB1. In addition, substrate stiffness of the hydrogel enhances the VEGFB secretion compared to control. Hence, the conducting polymer hydrogel system creates a tunable physical and electrical niche to enhance the therapeutic potential of stem cells for neurological injuries.