Multi-Layer PVA-PANI Conductive Hydrogel for Symmetrical Supercapacitors: Preparation and Characterization.

This work describes a simple, inexpensive, and robust method to prepare a flexible "all in one" integrated hydrogel supercapacitors (HySCs). Preparing smart hydrogels with high electrical conductivity, ability to stretch significantly, and excellent mechanical properties is the last challenge for tailored wearable devices. In this paper, we employed a physical crosslinking process that involves consecutive freezing and thawing cycles to prepare a polyvinyl alcohol (PVA)-based hydrogel. Exploiting the self-healing properties of these materials, the assembly of the different layers of the HySCs has been performed. The ionic conductivity within the electrolyte layer arises from the inclusion of an H2SO4 solution in the hydrogel network. Instead, the electronic conductivity is facilitated by the addition of the conductive polymer PANI-PAMPSA into the hydrogel layers. Electrochemical measures have highlighted newsworthy properties related to our HySCs, opening their use in wearable electronic applications.

Preparation and Characterization of Self-Healing PVA-H2SO4 Hydrogel for Flexible Energy Storage.

In the past decade, hydrogels have attracted growing interest for emerging applications in flexible electronic devices, human-machine interactions, energy supply, or energy storage. Developing a multifunctional gel architecture with superior ionic conductivity and good mechanical flexibility is a bottleneck to overcome. Herein, poly(vinyl alcohol)/sulfuric acid (PVA-H2SO4) hydrogels were prepared via a freeze-thaw method. With the aim of tuning the formulation in view of a possible application in energy storage, the effects of different combinations in terms of the molecular weight (MW) of PVA and PVA-H2SO4 weight ratio were investigated. Moreover, exploiting the self-healing properties of these hydrogels and the easy possibility of functionalizing them, i.e., introducing a conducting polymer such as poly(2-acrylamido-2-methyl-1-propane) sulfonic acid doped polyaniline (PANI_PAMPSA), a sandwiched all-in-one double-layer hydrogel (electrode/electrolyte configuration) was prepared (PVA-H2SO4-PANI_PAMPSA/PVA-H2SO4). Results showed that the water content is independent of the PVA amount and MW; the polymer concentration has a significant effect on the formation of crystalline domains and therefore on swelling degree, whereas the cross-linking degree depends on the MW. The PVA MW has the maximum effect on the swelling percentage normalized with respect to the polymer fraction and the tensile properties of the hydrogel. The assembled all-in-one electrode/electrolyte shows promising ionic conductivity (439.7 mS cm-1) and specific capacitance performance (0.297 mF cm-2 at a current density of 0.025 mA cm-2), as well as excellent flexibility and considerable self-healing properties. These results will promote the development of self-healing symmetrical supercapacitors for storage devices in wearable electronics.

High-Endurance Long-Term Potentiation in Neuromorphic Organic Electrochemical Transistors by PEDOT:PSS Electrochemical Polymerization on the Gate Electrode.

The brain exhibits extraordinary information processing capabilities thanks to neural networks that can operate in parallel with minimal energy consumption. Memory and learning require the creation of new neural networks through the long-term modification of the structure of the synapses, a phenomenon called long-term plasticity. Here, we use an organic electrochemical transistor to simulate long-term potentiation and depotentiation processes. Similarly to what happens in a synapse, the polymerization of the 3,4-ethylenedioxythiophene (EDOT) on the gate electrode modifies the structure of the device and boosts the ability of the gate potential to modify the conductivity of the channel. Operando AFM measurements were carried out to demonstrate the correlation between neuromorphic behavior and modification of the gate electrode. Long-term enhancement depends on both the number of pulses used and the gate potential, which generates long-term potentiation when a threshold of +0.7 V is overcome. Long-term depotentiation occurs by applying a +3.0 V potential and exploits the overoxidation of the deposited PEDOT:PSS. The induced states are stable for at least 2 months. The developed device shows very interesting characteristics in the field of neuromorphic electronics.

Evaluation of the Antioxidant Capacity of Fruit Juices by Two Original Analytical Methods.

Two analytical methods previously developed by our groups were employed to estimate the antioxidant capacity of commercial fruit juices. The electrochemical method, which measures the scavenging activity of antioxidants towards OH radicals generated by both hydrogen peroxide photolysis and Fenton's reaction, is based on the recovery of the cyclic voltametric response of the redox probe Ru(NH3)63+ at a Glassy Carbon electrode modified with a thin film of an insulating polyphenol, in the presence of compounds with antioxidant properties. The values of the antioxidant capacity of the fruit juices are expressed as vitamin C equivalents/L. The chromatographic method is based on the generation of OH radicals via Fenton's reaction in order to test the inhibition of their formation in the presence of antioxidant compounds by monitoring salicylate aromatic hydroxylation derivatives as markers of •OH production, by means of HPLC coupled to coulometric detection. The results are expressed as the percentage of inhibition of •OH production in the presence of the tested juice compared to the control sample. When OH radicals are produced by Fenton's reaction, the antioxidant capacity of the juices, estimated by both methods, displays an analogous trend, confirming that they can be considered an alternative for measuring the ability of antioxidants to block OH radical formation.

Focus Review on Nanomaterial-Based Electrochemical Sensing of Glucose for Health Applications.

Diabetes management can be considered the first paradigm of modern personalized medicine. An overview of the most relevant advancements in glucose sensing achieved in the last 5 years is presented. In particular, devices exploiting both consolidated and innovative electrochemical sensing strategies, based on nanomaterials, have been described, taking into account their performances, advantages and limitations, when applied for the glucose analysis in blood and serum samples, urine, as well as in less conventional biological fluids. The routine measurement is still largely based on the finger-pricking method, which is usually considered unpleasant. In alternative, glucose continuous monitoring relies on electrochemical sensing in the interstitial fluid, using implanted electrodes. Due to the invasive nature of such devices, further investigations have been carried out in order to develop less invasive sensors that can operate in sweat, tears or wound exudates. Thanks to their unique features, nanomaterials have been successfully applied for the development of both enzymatic and non-enzymatic glucose sensors, which are compliant with the specific needs of the most advanced applications, such as flexible and deformable systems capable of conforming to skin or eyes, in order to produce reliable medical devices operating at the point of care.

Smart Bandaid Integrated with Fully Textile OECT for Uric Acid Real-Time Monitoring in Wound Exudate.

Hard-to-heal wounds (i.e., severe and/or chronic) are typically associated with particular pathologies or afflictions such as diabetes, immunodeficiencies, compression traumas in bedridden people, skin grafts, or third-degree burns. In this situation, it is critical to constantly monitor the healing stages and the overall wound conditions to allow for better-targeted therapies and faster patient recovery. At the moment, this operation is performed by removing the bandages and visually inspecting the wound, putting the patient at risk of infection and disturbing the healing stages. Recently, new devices have been developed to address these issues by monitoring important biomarkers related to the wound health status, such as pH, moisture, etc. In this contribution, we present a novel textile chemical sensor exploiting an organic electrochemical transistor (OECT) configuration based on poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) for uric acid (UA)-selective monitoring in wound exudate. The combination of special medical-grade textile materials provides a passive sampling system that enables the real-time and non-invasive analysis of wound fluid: UA was detected as a benchmark analyte to monitor the health status of wounds since it represents a relevant biomarker associated with infections or necrotization processes in human tissues. The sensors proved to reliably and reversibly detect UA concentration in synthetic wound exudate in the biologically relevant range of 220-750 µM, operating in flow conditions for better mimicking the real wound bed. This forerunner device paves the way for smart bandages integrated with real-time monitoring OECT-based sensors for wound-healing evaluation.

ALP-Based Biosensors Employing Electrodes Modified with Carbon Nanomaterials for Pesticides Detection.

Due to the growing presence of pesticides in the environment and in food, the concern of their impact on human health is increasing. Therefore, the development of fast and reliable detection methods is needed. Enzymatic inhibition-based biosensors represent a good alternative for replacing the more complicated and time-consuming traditional methods (chromatography, spectrophotometry, etc.). This paper describes the development of an electrochemical biosensor exploiting alkaline phosphatase as the biological recognition element and a chemically modified glassy carbon electrode as the transducer. The biosensor was prepared modifying the GCE surface by a mixture of Multi-Walled-Carbon-Nanotubes (MWCNTs) and Electrochemically-Reduced-Graphene-Oxide (ERGO) followed by the immobilization of the enzyme by cross-linking with bovine serum albumin and glutaraldehyde. The inhibition of the biosensor response caused by pesticides was established using 2-phospho-L-ascorbic acid as the enzymatic substrate, whose dephosphorylation reaction produces ascorbic acid (AA). The MWCNTs/ERGO mixture shows a synergic effect in terms of increased sensitivity and decreased overpotential for AA oxidation. The response of the biosensor to the herbicide 2,4-dichloro-phenoxy-acetic-acid was evaluated and resulted in the concentration range 0.04-24 nM, with a limit of the detection of 16 pM. The determination of other pesticides was also achieved. The re-usability of the electrode was demonstrated by performing a washing procedure.

Micro- and nano-devices for electrochemical sensing.

Electrode miniaturization has profoundly revolutionized the field of electrochemical sensing, opening up unprecedented opportunities for probing biological events with a high spatial and temporal resolution, integrating electrochemical systems with microfluidics, and designing arrays for multiplexed sensing. Several technological issues posed by the desire for downsizing have been addressed so far, leading to micrometric and nanometric sensing systems with different degrees of maturity. However, there is still an endless margin for researchers to improve current strategies and cope with demanding sensing fields, such as lab-on-a-chip devices and multi-array sensors, brain chemistry, and cell monitoring. In this review, we present current trends in the design of micro-/nano-electrochemical sensors and cutting-edge applications reported in the last 10 years. Micro- and nanosensors are divided into four categories depending on the transduction mechanism, e.g., amperometric, impedimetric, potentiometric, and transistor-based, to best guide the reader through the different detection strategies and highlight major advancements as well as still unaddressed demands in electrochemical sensing.

A resistive sensor for humidity detection based on cellulose/polyaniline.

Ambient humidity is an important parameter that affects the manufacturing and storage of several industrial and agricultural goods. In the view of the Internet of Things (IoT), single sensors could be associated with an object for smart monitoring enabling optimum conditions to be maintained. Nevertheless, the production of cost-effective humidity sensors for indoor and outdoor environmental monitoring currently represents the main bottleneck in the development of this technology. Herein we report the results obtained with sensors exclusively made of cellulose and polyaniline (cell/PANI) under strictly controlled relative humidity (30-50 RH%) and temperature (21 ± 1 °C) achieved with a climatic chamber that simulates the conditions of indoor air humidity, and at different RH% in a lab test chamber set-up. Cell/PANI sensors, prepared with a simple, inexpensive, and easily scalable industrial paper process, show a linear trend with a slope of 1.41 µA RH%-1 and a percentage of sensitivity of 13%. Response time as well as percentage of sensitivity results are similar to those of a commercial digital-output relative humidity and temperature sensor (DHT22) employed in parallel for comparison. The commercial sensor DHT22 has a sensitivity of 14%. This low-cost sensor has potential applications in agriculture, food monitoring, and medical and industrial environments as a disposable sensor for humidity detection.

Oxygen Gas Sensing Using a Hydrogel-Based Organic Electrochemical Transistor for Work Safety Applications.

Oxygen depletion in confined spaces represents one of the most serious and underestimated dangers for workers. Despite the existence of several commercially available and widely used gas oxygen sensors, injuries and deaths from reduced oxygen levels are still more common than for other hazardous gases. Here, we present hydrogel-based organic electrochemical transistors (OECTs) made with the conducting polymer poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) as wearable and real-time oxygen gas sensors. After comparing OECT performances using liquid and hydrogel electrolytes, we identified the best PEDOT:PSS active layer and hydrogel coating (30 µm) combination for sensing oxygen in the concentration range of 13−21% (v/v), critical for work safety applications. The fast O2 solubilization in the hydrogel allowed for gaseous oxygen transduction in an electrical signal thanks to the electrocatalytic activity of PEDOT:PSS, while OECT architecture amplified the response (gain ~ 104). OECTs proved to have comparable sensitivities if fabricated on glass and thin plastic substrates, (−12.2 ± 0.6) and (−15.4 ± 0.4) µA/dec, respectively, with low power consumption (<40 µW). Sample bending does not influence the device response, demonstrating that our real-time conformable and lightweight sensor could be implemented as a wearable, noninvasive safety tool for operators working in potentially hazardous confined spaces.

A Wearable Electrochemical Gas Sensor for Ammonia Detection.

The next future strategies for improved occupational safety and health management could largely benefit from wearable and Internet of Things technologies, enabling the real-time monitoring of health-related and environmental information to the wearer, to emergency responders, and to inspectors. The aim of this study is the development of a wearable gas sensor for the detection of NH3 at room temperature based on the organic semiconductor poly(3,4-ethylenedioxythiophene) (PEDOT), electrochemically deposited iridium oxide particles, and a hydrogel film. The hydrogel composition was finely optimised to obtain self-healing properties, as well as the desired porosity, adhesion to the substrate, and stability in humidity variations. Its chemical structure and morphology were characterised by infrared spectroscopy and scanning electron microscopy, respectively, and were found to play a key role in the transduction process and in the achievement of a reversible and selective response. The sensing properties rely on a potentiometric-like mechanism that significantly differs from most of the state-of-the-art NH3 gas sensors and provides superior robustness to the final device. Thanks to the reliability of the analytical response, the simple two-terminal configuration and the low power consumption, the PEDOT:PSS/IrOx Ps/hydrogel sensor was realised on a flexible plastic foil and successfully tested in a wearable configuration with wireless connectivity to a smartphone. The wearable sensor showed stability to mechanical deformations and good analytical performances, with a sensitivity of 60 ± 8 µA decade-1 in a wide concentration range (17-7899 ppm), which includes the safety limits set by law for NH3 exposure.

Advanced Wound Dressing for Real-Time pH Monitoring.

The rapid evolution of wearable technologies is giving rise to a strong push for textile chemical sensors design targeting the real-time collection of vital parameters for improved healthcare. Among the most promising applications, monitoring of nonhealing wounds is a scarcely explored medical field that still lacks quantitative tools for the management of the healing process. In this work, a smart bandage is developed for the real-time monitoring of wound pH, which has been reported to correlate with the healing stages, thus potentially giving direct access to the wound status without disturbing the wound bed. The fully textile device is realized by integrating a sensing layer, including the two-terminal pH sensor made of a semiconducting polymer and iridium oxide particles, and an absorbent layer ensuring the delivery of a continuous wound exudate flow across the sensor area. The two-terminal sensor exhibits a reversible response with a sensitivity of (59 ± 4) µA pH-1 in the medically relevant pH range for wound monitoring (pH 6-9), and its performance is not substantially affected either by the presence of the most common chemical interferents or by temperature gradients from 22 to 40 °C. Thanks to the robust sensing mechanism based on potentiometric transduction and the simple device geometry, the fully assembled smart bandage was successfully validated in flow analysis using synthetic wound exudate.

Synthesis and Characterization of Layered Double Hydroxides as Materials for Electrocatalytic Applications.

Layered double hydroxides (LDHs) are anionic clays which have found applications in a wide range of fields, including electrochemistry. In such a case, to display good performances they should possess electrical conductivity which can be ensured by the presence of metals able to give reversible redox reactions in a proper potential window. The metal centers can act as redox mediators to catalyze reactions for which the required overpotential is too high, and this is a key aspect for the development of processes and devices where the control of charge transfer reactions plays an important role. In order to act as redox mediator, a material can be present in solution or supported on a conductive support. The most commonly used methods to synthesize LDHs, referring both to bulk synthesis and in situ growth methods, which allow for the direct modification of conductive supports, are here summarized. In addition, the most widely used techniques to characterize the LDHs structure and morphology are also reported, since their electrochemical performance is strictly related to these features. Finally, some electrocatalytic applications of LDHs, when synthesized as nanomaterials, are discussed considering those related to sensing, oxygen evolution reaction, and other energy issues.

Textile Chemical Sensors Based on Conductive Polymers for the Analysis of Sweat.

Wearable textile chemical sensors are promising devices due to the potential applications in medicine, sports activities and occupational safety and health. Reaching the maturity required for commercialization is a technology challenge that mainly involves material science because these sensors should be adapted to flexible and light-weight substrates to preserve the comfort of the wearer. Conductive polymers (CPs) are a fascinating solution to meet this demand, as they exhibit the mechanical properties of polymers, with an electrical conductivity typical of semiconductors. Moreover, their biocompatibility makes them promising candidates for effectively interfacing the human body. In particular, sweat analysis is very attractive to wearable technologies as perspiration is a naturally occurring process and sweat can be sampled non-invasively and continuously over time. This review discusses the role of CPs in the development of textile electrochemical sensors specifically designed for real-time sweat monitoring and the main challenges related to this topic.

Textile sensors platform for the selective and simultaneous detection of chloride ion and pH in sweat.

The development of wearable sensors, in particular fully-textile ones, is one of the most interesting open challenges in bioelectronics. Several and significant steps forward have been taken in the last decade in order to achieve a compact, lightweight, cost-effective, and easy to wear platform for healthcare and sport activities real-time monitoring. We have developed a fully textile, multi-thread biosensing platform that can detect different bioanalytes simultaneously without interference, and, as an example, we propose it for testing chloride ions (Cl-) concentration and pH level. The textile sensors are simple threads, based on natural and synthetic fibers, coated with the conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS) and properly functionalized with either a nano-composite material or a chemical sensitive dye to obtain Cl- and pH selective sensing functionality, respectively. The single-thread sensors show excellent sensitivity, reproducibility, selectivity, long term stability and the ability to work with small volumes of solution. The performance of the developed textile devices is demonstrated both in buffer solution and in artificial human perspiration to perform on-demand and point-of-care epidermal fluids analysis. The possibility to easily knit or sew the thread sensors into fabrics opens up a new vision for a textile wearable multi-sensing platform achievable in the near future.

Layered Double Hydroxide-Modified Organic Electrochemical Transistor for Glucose and Lactate Biosensing.

Biosensors based on Organic Electrochemical Transistors (OECTs) are developed for the selective detection of glucose and lactate. The transistor architecture provides signal amplification (gain) with respect to the simple amperometric response. The biosensors are based on a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) channel and the gate electrode is functionalised with glucose oxidase (GOx) or lactate oxidase (LOx) enzymes, which are immobilised within a Ni/Al Layered Double Hydroxide (LDH) through a one-step electrodeposition procedure. The here-designed OECT architecture allows minimising the required amount of enzyme during electrodeposition. The output signal of the biosensor is the drain current (Id), which decreases as the analyte concentration increases. In the optimised conditions, the biosensor responds to glucose in the range of 0.1-8.0 mM with a limit of detection (LOD) of 0.02 mM. Two regimes of proportionality are observed. For concentrations lower than 1.0 mM, a linear response is obtained with a mean gain of 360, whereas for concentrations higher than 1.0 mM, Id is proportional to the logarithm of glucose concentration, with a gain of 220. For lactate detection, the biosensor response is linear in the whole concentration range (0.05-8.0 mM). A LOD of 0.04 mM is reached, with a net gain equal to 400.

Needle-type organic electrochemical transistor for spatially resolved detection of dopamine.

In this work, the advantages of carbon nanoelectrodes (CNEs) and orgonic electrochemical transistors (OECTs) were merged to realise nanometre-sized, spearhead OECTs based on single- and double-barrel CNEs functionalised with a conducting polymer film. The needle-type OECT shows a high aspect ratio that allows its precise positioning by means of a macroscopic handle and its size is compatible with single-cell analysis. The device was characterised with respect to its electrolyte-gated behaviour and was employed as electrochemical sensor for the proof-of-concept detection of dopamine (DA) over a wide concentration range (10-12-10-6 M). Upon application of fixed drain and gate voltages (Vd = - 0.3 V, Vg = - 0.9 V, respectively), the nano-sized needle-type OECT sensor exhibited a linear response in the low pM range and from 0.002 to 7 µM DA, with a detection limit of 1 × 10-12 M. Graphical abstract.

Organic Electrochemical Transistors as Versatile Analytical Potentiometric Sensors.

Potentiometric transduction is an important tool of analytical chemistry to record chemical signals, but some constraints in the miniaturization and low-cost fabrication of the reference electrode are a bottleneck in the realization of more-advanced devices such as wearable and lab-on-a-chip sensors. Here, an organic electrochemical transistor (OECT) has been designed with an alternative architecture that allows to record the potentiometric signals of gate electrodes, which have been chemically modified to obtain Ag/AgnX interfaces (X = Cl-, Br-, I-, and S2-), without the use of a reference electrode. When the OECT is immersed in a sample solution, it reaches an equilibrium state, because PEDOT:PSS exchanges charges with the electrolyte until its Fermi level is aligned to the one of Ag/AgnX. The latter is controlled by Xn- concentration in the solution. As a consequence, in this spontaneous process, the conductivity of PEDOT:PSS changes with the electrochemical potential of the modified gate electrode without any external bias. The sensor works by applying only a fixed drain current or drain voltage and thus the OECT sensor operates with just two terminals. It is also demonstrated that, in this configuration, gate potential values extracted from the drain current are in good agreement with the ones measured with respect to a reference electrode being perfectly correlated (linear slope equal to 1.00 ± 0.03). In the case of the sulfide anion, the OECT performance overcomes the limit represented by the Nernst equation, with a sensitivity of 0.52 V decade-1. The presented results suggest that OECTs could be a viable option to fabricate advanced sensors based on potentiometric transduction.

Electrochemical Approach for the Production of Layered Double Hydroxides with a Well-Defined Co/MeIII Ratio.

Layered double hydroxides (LDHs) have been widely studied for their plethora of fascinating features and applications. The potentiostatic electrodeposition of LDHs has been extensively applied in the literature as a fast and direct method to substitute classical chemical routes. However, the electrochemical approach does not usually allow for a fine control of the MII /MIII ratio in the synthesized material. By employing a recently proposed potentiodynamic method, LDH films of controlled composition are herein prepared with good reproducibility, using different ratios of the trivalent (Fe or Al) to bivalent (Co) cations in the electrolytic solution. All the obtained materials are shown to be effective oxygen evolution reaction (OER) catalysts, and are thoroughly characterized by a multi-technique approach, including FE-SEM, XRD, Raman, AES and a wide range of electrochemical procedures.

Microscopic Determination of Carrier Density and Mobility in Working Organic Electrochemical Transistors.

A comprehensive understanding of electrochemical and physical phenomena originating the response of electrolyte-gated transistors is crucial for improved handling and design of these devices. However, the lack of suitable tools for direct investigation of microscale effects has hindered the possibility to bridge the gap between experiments and theoretical models. In this contribution, a scanning probe setup is used to explore the operation mechanisms of organic electrochemical transistors by probing the local electrochemical potential of the organic film composing the device channel. Moreover, an interpretative model is developed in order to highlight the meaning of electrochemical doping and to show how the experimental data can give direct access to fundamental device parameters, such as local charge carrier concentration and mobility. This approach is versatile and provides insight into the organic semiconductor/electrolyte interface and useful information for materials characterization, device scaling, and sensing optimization.