Biocompatible Electrodes Research Articles

Amino Acid Supported Conductive Nanocomposite for Developing Flexible Electrode Material for Energy Storage

Introduction: This study focused on synthesizing biocompatible, flexible and wearable electrode materials for energy storage applications. The unique zwitterionic structure of L-proline provides numerous interesting properties to the nanocomposite such as high ionic interactions through the various ion migration channels, and strong hydration characteristics. These features are key to thehigh performance of energy deposition systems.Methods: Binary nanocomposites containing L-proline (Pro) amino acid and polypyrrole (Ppy) were produced on rGO modified carbon textile (rGO-CC) to develop electroactive materials. Two step hydrothermal method was used to produce flexible electrodes. DRIFT spectroscopy andAFM analysis were performed to clarify the structural and the morphological characterization. Electrochemical behavior was evaluated utilizing CV, GCD and EIS methods.Results: ProPpy@rGO-CC electrode materials exhibit high electrochemical performances in aqueous electrolytes (0.1 M NaCl). The prepared electrode shows high specific capacitance of 500.4 Fg-1 (at 25 mVs−1) at the ambient conditions. Additionally, after 5,000 charge/discharge cycles the specific capacitance retains a high level of 95% confirming the good cycle stability. The energy and the power densities were found to be 278 Wh kg−1 and 12.5 kW kg−1, respectively.Conclusion: The results indicate that the ProPpy@rGO-CC electrode is a promising candidate for next-generation high-performance energy deposition systems. The unique structural features of L-proline contribute to the formation of a large number of electroactive sites and short diffusion pathways.

Bioactive Ion-Confined Ultracapacitive Memristors with Neuromorphic Functions.

The field of bioinspired iontronics, bridging electronic devices and ionic systems, has multiple biological applications. Carbon-based ultracapacitive devices hold promise for controlling bioactive ions via electric double layers due to their high-surface-area and biocompatible porous carbon electrodes. However, the interplay between complex bioactive ions and porous carbons remains unclear due to the variety of structures of bioactive ions present in biological systems. Herein, we investigate the adsorption behavior of a series of bioactive ammonium-based cations with varying alkyl chain lengths in nanoporous carbons. We find that strong physisorption results from the synergistic hydrophobic interaction and electrostatic attraction between porous carbons (with a negative zeta potential) and bioactive cations. Bioactive cations with varying alkyl chain lengths can be irreversibly physically adsorbed and confined within nanoporous carbons resulting in anion enrichment and depletion during electric polarization. This situation, in turn, results in a characteristic memristive behavior in all-carbon capacitive ionic memristor devices. Our findings highlight the relationship between the resistance state of the memristor and ion adsorption mechanisms in all-carbon capacitive devices, which hold potential for future transmitter delivery, biointerfacing, and neuromorphic devices.

Bioactive Ion‐Confined Ultracapacitive Memristors with Neuromorphic Functions

The field of bioinspired iontronics, bridging electronic devices and ionic systems, has multiple biological applications. Carbon‐based ultracapacitive devices hold promise for controlling bioactive ions via electric double layers due to their high‐surface‐area and biocompatible porous carbon electrodes. However, the interplay between complex bioactive ions and porous carbons remains unclear due to the variety of structures of bioactive ions present in biological systems. Herein, we investigate the adsorption behavior of a series of bioactive ammonium‐based cations with varying alkyl chain lengths in nanoporous carbons. We find that strong physisorption results from the synergistic hydrophobic interaction and electrostatic attraction between porous carbons (with a negative zeta potential) and bioactive cations. Bioactive cations with varying alkyl chain lengths can be irreversibly physically adsorbed and confined within nanoporous carbons resulting in anion enrichment and depletion during electric polarization. This situation, in turn, results in a characteristic memristive behavior in all‐carbon capacitive ionic memristor devices. Our findings highlight the relationship between the resistance state of the memristor and ion adsorption mechanisms in all‐carbon capacitive devices, which hold potential for future transmitter delivery, biointerfacing, and neuromorphic devices.

Synergistic material–microbe interface toward deeper anaerobic defluorination

Per- and polyfluoroalkyl substances (PFAS), particularly the perfluorinated ones, are recalcitrant to biodegradation. By integrating an enrichment culture of reductive defluorination with biocompatible electrodes for the electrochemical process, a deeper defluorination of a C6-perfluorinated unsaturated PFAS was achieved compared to the biological or electrochemical system alone. Two synergies in the bioelectrochemical system were identified: i) The in-series microbial-electrochemical defluorination and ii) the electrochemically enabled microbial defluorination of intermediates. These synergies at the material-microbe interfaces surpassed the limitation of microbial defluorination and further turned the biotransformation end products into less fluorinated products, which could be less toxic and more biodegradable in the environment. This material-microbe hybrid system brings opportunities in the bioremediation of PFAS driven by renewable electricity and warrants future research on mechanistic understanding of defluorinating and electroactive microorganisms at the material-microbe interface for system optimizations.

Ti2TaC2: A novel out-of-plane ordered MXene towards flexible and cytocompatible supercapacitors

Exploring biocompatible and flexible supercapacitor electrode material is crucial for expanding the development of health monitoring bioelectronics. MXene films, due to their low cost, high conductivity, and excellent durability under different deformation conditions, are highly competitive in bioelectronic device applications compared with traditional carbon-based materials. Herein, a novel out-of-plane ordered double transition metal MXene (Ti2TaC2) is elaborately designed and originally synthesized, where Ti atoms preferentially reside in the outer transition metal layer and Ta atoms occupy in the middle layer. Theoretical calculations prove that the introduction of Ta species into Ti3C2 MXene enlarges the work function, raises the d-band center close to Fermi level and increases the density of states of d-orbital. Consequently, the Ti2TaC2 film delivers high specific capacitance of 313 F g−1 at 2 mV s−1 and excellent cycling stability without capacitance loss after 10,000 cycles at 10 A/g. Furthermore, the safety and cytotoxicity of Ti2TaC2 material are innovatively evaluated in vitro multiple cell lines (e.g., 293T, bEnd.3, PC-12, BV2 and HUVEC cells) and implanted into the subcutaneous tissue of mice, proving its good biosafety and cytocompatibility. The results suggest that flexible Ti2TaC2 MXene film may be a promising cytocompatible electrode material for long-term health monitoring bioelectronics.

Highly Biocompatible Graphite Electrodes by Using Interface‐Stable Coating and the Application to Hemodialysis

AbstractIn the treatment of kidney diseases such as chronic kidney disease (CKD) and acute tubular necrosis (ATN), prolonged contact between conductivity sensors and patients' bodily fluids is required, necessitating high biocompatibility for the electrodes. However, the widely used graphite electrodes exhibit limited biocompatibility, showing a cell survival rate of only 88% under indirect contact conditions, and <56% under direct contact conditions. Here, the surface detachment of graphite electrodes in liquid environments leading to cell death upon contact is observed and a solution is proposed to enhance biocompatibility and ensure conductivity, by forming a layer of interface‐stable coating (ISC) as a conductive isolation membrane on their surface. For applications with contact requirements, graphite‐like carbon (GLC) coated graphite electrodes are investigated and developed, resulting in an exceptional cell survival rate exceeding 96% under indirect contact conditions, and a relatively high survival rate exceeding 91% under direct contact conditions, both accompanied by significant proliferation. GLC‐coated graphite electrodes are successfully to monitor the dialysate conductivity in a hemodialysis machine and achieve stable monitoring with temperature compensation. The results demonstrate ISC graphite electrodes' potential in biomedical fluid monitoring, with the developed process applicable to other fields.

Biocompatible supercapacitor engineered from marine collagen impregnated with polypyrrole and tungsten disulfide

There is an urgent demand for highly stable energy storage systems that are biocompatible, environmentally friendly, and made from affordable, sustainable materials. Research on biologically sourced materials as green energy storage devices such as supercapacitor (SC) technologies are emerging, but they are often expensive, complicated to manufacture, and fail to meet the required performance levels. This article presents a simple and innovative method to fabricate a human skin comfortable SC electrode using collagen extracted from hoki (Macruronus novaezelandiae) fish skin. Polypyrrole and tungsten disulfide nanoparticles were incorporated into the collagen matrix via early wetness impregnation to provide the required electrical properties. Electrochemical investigations revealed that the areal capacitance of the composite material was 348 mF cm−2 and cyclic testing showed that the capacitance retention is 98 % after 50,000 cycles. The collagen-based composite demonstrated excellent biocompatibility to HEK293 cells grown over a 1-week period. This novel technique for producing biodegradable and biocompatible SC electrodes from renewable source paves opportunities to utilize other sources of biomaterials for smart electronic applications.

Self‐adhesive and biocompatible dry electrodes with conformal contact to skin for epidermal electrophysiology

AbstractLong‐term biopotential monitoring requires high‐performance biocompatible wearable dry electrodes. But currently, it is challenging to establish a form‐preserving fit with the skin, resulting in high interface impedance and motion artifacts. This research aims to present an innovative solution using an all‐green organic dry electrode that eliminates the aforementioned challenges. The dry electrode is prepared by introducing biocompatible maltitol into the chosen conductive polymer, poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate). Thanks to the secondary doping and plasticizer effect of maltitol, the dry electrode exhibits good stretchability (62%), strong self‐adhesion (0.46 N/cm), high conductivity (102 S/cm), and low Young's modulus (7 MPa). It can always form a conformal contact with the skin even during body movements. Together with good electrical properties, the electrode enables a lower skin contact impedance compared to the current standard Ag/AgCl gel electrode. Consequently, the application of this dry electrode in bioelectrical signal measurement (electromyography, electrocardiography, electroencephalography) and long‐term biopotential monitoring was successfully demonstrated.

Dual-Site Biomacromolecule Doped Poly(3, 4-Ethylenedioxythiophene) for Bosting Both Anticoagulant and Electrochemical Performances.

Poly(3, 4-ethylenedioxythiophene) (PEDOT) as a new generation of intelligent conductive polymers, is attracting much attention in the field of tissue engineering. However, its water dispersibility, conductivity, and biocompatibility are incompatible, which limit its further development. In this work, biocompatible electrode material of PEDOT doped with sodium sulfonated alginate (SS) which contains two functional groups of sulfonic acid and carboxylic acid per repeat unit of the macromolecule. The as dual-site doping strategy simultaneously boosts anticoagulant and electrochemical performances, for example, good hydrophilicity (water contact angle of 59.40°), well dispersibility (dispersion solution unstratified in 30 days), high conductivity (4.45 S m-1), and enhanced anticoagulant property (extended activated partial thrombin time value of 59.0 s), forming an adjustable PEDOT: biomacromolecule interface; this fills the technical gap of implantable bioelectronics in terms of coagulation and thrombosis risk. At the same time, the assembled all-in-one supercapacitor with anticoagulant properties is prepared by PEDOT: sodium sulfonated alginate as electrode material and sodium alginate hydrogel as electrolyte layer. The dual-site doping strategy provides a new opinion for the design and optimization of functional conductive polymers and its applications in implantable energy storage fields.

3D printed PEDOT:PSS-based conducting and patternable eutectogel electrodes for machine learning on textiles

The proliferation of medical wearables necessitates the development of novel electrodes for cutaneous electrophysiology. In this work, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) is combined with a deep eutectic solvent (DES) and polyethylene glycol diacrylate (PEGDA) to develop printable and biocompatible electrodes for long-term cutaneous electrophysiology recordings. The impact of printing parameters on the conducting properties, morphological characteristics, mechanical stability and biocompatibility of the material were investigated. The optimised eutectogel formulations were fabricated in four different patterns —flat, pyramidal, striped and wavy— to explore the influence of electrode geometry on skin conformability and mechanical contact. These electrodes were employed for impedance and forearm EMG measurements. Furthermore, arrays of twenty electrodes were embedded into a textile and used to generate body surface potential maps (BSPMs) of the forearm, where different finger movements were recorded and analysed. Finally, BSPMs for three different letters (B, I, O) in sign-language were recorded and used to train a logistic regressor classifier able to reliably identify each letter. This novel cutaneous electrode fabrication approach offers new opportunities for long-term electrophysiological recordings, online sign-language translation and brain-machine interfaces.

Spatially Precise Genetic Engineering at the Electrode-Tissue Interface.

The interface between electrodes and neural tissues plays a pivotal role in determining the efficacy and fidelity of neural activity recording and modulation. While considerable efforts have been made to improve the electrode-tissue interface, the majority of studies have primarily concentrated on the development of biocompatible neural electrodes through abiotic materials and structural engineering. In this study, an approach is presented that seamlessly integrates abiotic and biotic engineering principles into the electrode-tissue interface. Specifically, ultraflexible neural electrodes with short hairpin RNAs (shRNAs) designed to silence the expression of endogenous genes within neural tissues are combined. The system facilitates shRNA-mediated knockdown of phosphatase and tensin homolog deleted on chromosome 10 (PTEN) and polypyrimidine tract-binding protein 1 (PTBP1), two essential genes associated in neural survival/growth and neurogenesis, within specific cell populations located at the electrode-tissue interface. Additionally, it is demonstrated that the downregulation of PTEN in neurons can result in an enlargement of neuronal cell bodies at the electrode-tissue interface. Furthermore, the system enables long-term monitoring of neuronal activities following PTEN knockdown in a mouse model of Parkinson's disease and traumatic brain injury. The system provides a versatile approach for genetically engineering the electrode-tissue interface with unparalleled precision, paving the way for the development of regenerative electronics and next-generation brain-machine interfaces.

Highly flexible and transparent amorphous indium doped tin oxide on bio-compatible polymers for transparent wearable sensors

Highly transparent and flexible amorphous Sn-doped In2O3 (a-ITO) films deposited on flexible and bio-compatible cyclic olefin polymer (COP) substrate using a direct-current magnetron sputtering at room temperature were used as flexible and transparent electrodes for transparent wearable sensors. The figure of merits (FoM) value was calculated to determine the optimal sputtering process for the a-ITO electrodes by varying the direct current power, working pressure, oxygen flow rate, and a-ITO thickness. The optimized a-ITO/COP with a high FoM value of 8.9 exhibited a low sheet resistance of 36 Ohm/square, average transmittances of 89.5 % in the visible wavelength region, and a small critical bending radius of 7 mm, which are acceptable transparent electrodes for fabrication of wearable and transparent wearable sensors. To demonstrate the feasibility of the a-ITO/COP substrate as a promising wearable sensor, we examined the performance of wearable temperature sensors, wearable heaters, and wearable glucose sensors. The successful operation of a-ITO/COP-based temperature sensors with high sensitivity, transparent heaters with a saturation temperature of 87.8 °C at 6 V, and glucose sensors with high sensitivity indicates that a-ITO/COP is a promising bio-compatible electrode for next-generation wearable bionic electronics.

Bacterial-Polyhydroxybutyrate for Biocompatible Microbial Electrodes

The development of bioelectrochemical systems requires careful selection of both their biotic and abiotic components to obtain sustainable devices. Herein, we report a biophotoelectrode obtained with polyhydroxybutyrate (PHB), a biopolymer, which purple non-sulphur bacteria produce as an energy stock under specific environmental conditions. The electrode was obtained by casting a mixture composed of PHB and carbon fibers in a 3:2 mass ratio. Following, the composite material was modified with polydopamine and thermally treated to obtain a hydrophilic electrode with improved electrochemical behavior. The bio-based electrode was tested with metabolically active cells of Rhodobacter capsulatus embedded in a biohybrid matrix of polydopamine. The system achieved enhanced catalytic activity under illumination, with an 18-fold increase in photocurrent production compared to biophotoelectrodes based on glassy carbon, reaching a current density of 12 ± 3 μA cm−2, after 30 min of light exposure at +0.32 V. The presented biocompatible electrode provides a sustainable alternative to metal-based and critical raw material-based electrodes for bioelectrochemical systems.

An electrochemical biosensor based on DNA tetrahedron nanoprobe for sensitive and selective detection of doxorubicin

Doxorubicin (DOX) is a clinical chemotherapeutic drug and patients usually suffer from dose-dependent cytotoxic and side effects during chemotherapy process with DOX. Therefore, developing a reliable strategy for DOX analysis in biological samples for dosage guidance during chemotherapy process is of great significance. Herein, a sensitive and selective electrochemical biosensor for DOX detection was designed based on gold nanoparticles (AuNPs) and DNA tetrahedron (TDN) nanoprobe bifunctional glassy carbon electrode that could detect DOX in human serum and cell lysate samples. AuNPs not only could enhance electron transfer efficiency and detection sensitivity, but also could improve the biocompatibility of electrode. TDN nanoprobes were employed as specific DOX bind sites that could bind abundant DOX through intercalative characteristics to contribute to sensitive and selective detection. Under the optimal conditions, the proposed TDN nanoprobes-based DOX biosensor exhibited a wide linear range that ranged from 1.0 nM to 50 μM and a low detection limit that was 0.3 nM. Moreover, the proposed DOX biosensor displayed nice selectivity, reproducibility and stability, and was successfully applied for DOX detection in human serum and cell lysate samples. These promising results maybe pave a way for DOX dosage guidance and therapeutic efficacy optimization in clinic.

High-performing fiber electrodes based on a gold-shelled silver nanowire framework for bioelectronics.

Flexible fiber electrodes offer new opportunities for bioelectronics and are reliable in vivo applications, high flexibility, high electrical conductivity, and satisfactory biocompatibility are typically required. Herein, we present an all-metal flexible and biocompatible fiber electrode based on a metal nanowire hybrid strategy, i.e., silver nanowires were assembled on a freestanding framework, and further to render them inert, they were plated with a gold nanoshell. Our fiber electrodes exhibited a low modulus of ∼75 MPa and electrical conductivity up to ∼4.8 × 106 S m-1. They can resist chemical erosion with negligible leakage of biotoxic silver ions in the physiological environment, thus ensuring satisfactory biocompatibility. Finally, we demonstrated the hybrid fiber as a neural electrode that stimulated the sciatic nerve of a mouse, proving its potential for applications in bioelectronics.

A Wearable Integrated Microneedle Electrode Patch for Exercise Management in Diabetes.

Exercise is one of the preferred management strategies for diabetic patients, but the exercise mode including type, intensity, and duration time is quite different for each patient because of individual differences. Inadequate exercise has no effect on the blood glucose control, while overexercise may cause serious side effects, such as hypoglycemia and loss of blood glucose control. In this work, we report a closed-loop feedback mode for exercise management in diabetes. A minimally invasive, biocompatible microneedle electrode patch was fabricated and used for continuously monitoring the glucose in the interstitial fluid. Further, in conjunction with using a wireless electrochemical device, the glucose signals can be analyzed to output the potency of exercise and give advice on exercise management. A custom exercise given by this closed-loop feedback mode can reduce the used dose of insulin and avoid side effect during and after exercise. We believe that this work can provide a novel comprehensive guidance for diabetic patients.

Implantable Neural Electrodes Fabrication Based on Perfluoroalkoxyalkane Film.

In this paper, the fabrication of perfluoro-alkoxy alkane (PFA) film-based planar neural electrodes was proposed. The fabrication of PFA-based electrodes started with cleaning of PFA film. The argon plasma pretreatment was performed on the PFA film surface and attached to a dummy silicon wafer. Metal layers were deposited and patterned using the standard Micro Electro Mechanical Systems (MEMS) process. Electrode-sites and pads were opened using reactive ion etching (RIE). Lastly, the electrode patterned PFA substrate film was thermally laminated with the other bare PFA film. Electrical-physical evaluation tests were conducted along with in vitro tests, ex vivo tests and soak tests to evaluate the electrode performance and biocompatibility. The electrical and physical performance of PFA-based electrodes had better performances compared to other biocompatible polymer-based electrodes. Also, the biocompatibility and longevity were verified by cytotoxicity test, elution test, and accelerated life test. The PFA film-based planar neural electrode fabrication was established and evaluated. The PFA based electrodes showed excellent benefits such as long-term reliability, low water absorption rate, and flexibility using the neural electrode. For implantable neural electrodes, hermetic sealing is required for in vivo durability. PFA fulfilled a low water absorption rate with relatively low Young's modulus to increase the longevity and biocompatibility of the devices.

Electrogelated drug-embedded silk/gelatin/rGO degradable electrode for anti-inflammatory applications in brain-implant systems.

Implantable electrodes have raised great interest over the last years with the increasing incidence of neurodegenerative disorders. For brain implant devices, some key factors resulting in the formation of glial scars, such as mechanical mismatch and acute injury-induced inflammation, should be considered for material design. Therefore, in this study, a new biocompatible flexible electrode (e-SgG) with arbitrary shapes on a positive electrode was developed via electrogelation by applying a direct electrical voltage on a silk fibroin/gelatin/reduced graphene oxide composite hydrogel. The implantable flexible e-SgG-2 film with 1.23% rGO content showed high Young's modulus (11-150 MPa), which was sufficient for penetration under dried conditions but subsequently became a biomimetic brain tissue with low Young's modulus (50-3200 kPa) after insertion in the brain. At the same time, an anti-inflammatory drug (DEX) incorporated into the e-SgG-2 film can be electrically stimulated to exhibit two-stage release to overcome tissue inflammation during cyclic voltammetry via degradation by applying an AC field. The results of cell response to the SF/gelatin/rGO/DEX composite film showed that the released DEX could interrupt astrocyte growth to reduce the inflammatory response but showed non-toxicity toward neurons, which demonstrated a great potential for the application of the biocompatible and degradable e-SgG-D electrodes in the improvement of nerve tissue repair.

A Hyperflexible Electrode Array for Long-Term Recording and Decoding of Intraspinal Neuronal Activity.

Neural interfaces for stable access to the spinal cord (SC) electrical activity can benefit patients with motor dysfunctions. Invasive high-density electrodes can directly extract signals from SC neuronal populations that can be used for the facilitation, adjustment, and reconstruction of motor actions. However, developing neural interfaces that can achieve high channel counts and long-term intraspinal recording remains technically challenging. Here, a biocompatible SC hyperflexible electrode array (SHEA) with an ultrathin structure that minimizes mechanical mismatch between the interface and SC tissue and enables stable single-unit recording for more than 2 months in mice is demonstrated. These results show that SHEA maintains stable impedance, signal-to-noise ratio, single-unit yield, and spike amplitude after implantation into mouse SC. Gait analysis and histology show that SHEA implantation induces negligible behavioral effects and Inflammation. Additionally, multi-unit signals recorded from the SC ventral horn can predict the mouse's movement trajectory with a high decoding coefficient of up to 0.95. Moreover, during step cycles, it is found that the neural trajectory of spikes and low-frequency local field potential (LFP) signal exhibits periodic geometry patterns. Thus, SHEA can offer an efficient and reliable SC neural interface for monitoring and potentially modulating SC neuronal activity associated with motor dysfunctions.

Skin-integrated, biocompatible, and stretchable silicon microneedle electrode for long-term EMG monitoring in motion scenario

Electromyography (EMG) signal is the electrical potential generated by contracting muscle cells. Long-term and accurate EMG monitoring is desirable for neuromuscular function assessment in clinical and the human–computer interfaces. Herein, we report a skin-integrated, biocompatible, and stretchable silicon microneedle electrode (SSME) inspired by the plant thorns. The silicon microneedles are half encapsulated by the polyimide (PI) to enhance the adaptability to deformation and resistance to fatigue. Thorn-like SSME is realized by the semi-additive method with a stretchability of not less than 36%. The biocompatibility of SSME has been verified using cytotoxicity tests. EMG monitoring in motion and long-term has been conducted to demonstrate the feasibility and performance of the SSME, which is compared with a commercial wet electrode. Hopefully, the strategies reported here can lead to accurate and long-term EMG monitoring, facilitating an effective and reliable human–computer interface.