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.

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.

Organic Electrochemical Transistors as Versatile Tool for Real-Time and Automatized Viral Cytopathic Effect Evaluation.

In-vitro viral studies are still fundamental for biomedical research since studying the virus kinetics on cells is crucial for the determination of the biological properties of viruses and for screening the inhibitors of infections. Moreover, testing potential viral contaminants is often mandatory for safety evaluation. Nowadays, viral cytopathic effects are mainly evaluated through end-point assays requiring dye-staining combined with optical evaluation. Recently, optical-based automatized equipment has been marketed, aimed at the real-time screening of cell-layer status and obtaining further insights, which are unavailable with end-point assays. However, these technologies present two huge limitations, namely, high costs and the possibility to study only cytopathic viruses, whose effects lead to plaque formation and layer disruption. Here, we employed poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (Pedot:Pss) organic electrochemical transistors (OECTs) for the real-time, electrical monitoring of the infection of cytolytic viruses, i.e., encephalomyocarditis virus (EMCV), and non-cytolytic viruses, i.e., bovine coronavirus (B-CoV), on cells. OECT data on EMCV were validated using a commercially-available optical-based technology, which, however, failed in the B-CoV titration analysis, as expected. The OECTs proved to be reliable, fast, and versatile devices for viral infection monitoring, which could be scaled up at low cost, reducing the operator workload and speeding up in-vitro assays in the biomedical research field.

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.

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.

Organic Electrochemical Transistors for Real-Time Monitoring of In Vitro Silver Nanoparticle Toxicity.

Nanomaterials are being widely used in medical applications and consumer products such as cosmetics, fabrics, and food packaging, although their impact on health and the environment is yet to be understood. Strategies enabling reliable and reproducible safety assessment of nanomaterials are needed because predicting their toxic effects is challenging as there is no simple correlation between their properties and the interaction with living systems. Here, the real-time monitoring of toxic effects induced by nanoparticles on cells using organic electrochemical transistors (OECTs) is reported. Noteworthy, OECTs are able to assess the coating-dependent toxicity of nanoparticles on both barrier and non-barrier tissue cells and, moreover, to monitor the cell health status as a function of exposure time, allowing useful insight on the interaction processes between nanomaterials and cells. These results demonstrate that OECTs are effective devices for real-time cell monitoring and in vitro assessment of nanomaterial toxicity.

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.

Impact of Fabric Properties on Textile Pressure Sensors Performance.

In recent years, wearable technologies have attracted great attention in physical and chemical sensing applications. Wearable pressure sensors with high sensitivity in low pressure range (<10 kPa) allow touch detection for human-computer interaction and the development of artificial hands for handling objects. Conversely, pressure sensors that perform in a high pressure range (up to 100 kPa), can be used to monitor the foot pressure distribution, the hand stress during movements of heavy weights or to evaluate the cyclist's pressure pattern on a bicycle saddle. Recently, we developed a fully textile pressure sensor based on a conductive polymer, with simple fabrication and scalable features. In this paper, we intend to provide an extensive description on how the mechanical properties of several fabrics and different piezoresistive ink formulation may have an impact in the sensor's response during a dynamic operation mode. These results highlight the complexity of the system due to the presence of various parameters such as the fabric used, the conductive polymer solution, the operation mode and the desired pressure range. Furthermore, this work can lead to a protocol for new improvements and optimizations useful for adapting textile pressure sensors to a large variety of applications.

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.

Stretchable Low Impedance Electrodes for Bioelectronic Recording from Small Peripheral Nerves.

Monitoring of bioelectric signals in peripheral sympathetic nerves of small animal models is crucial to gain understanding of how the autonomic nervous system controls specific body functions related to disease states. Advances in minimally-invasive electrodes for such recordings in chronic conditions rely on electrode materials that show low-impedance ionic/electronic interfaces and elastic mechanical properties compliant with the soft and fragile nerve strands. Here we report a highly stretchable low-impedance electrode realized by microcracked gold films as metallic conductors covered with stretchable conducting polymer composite to facilitate ion-to-electron exchange. The conducting polymer composite based on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) obtains its adhesive, low-impedance properties by controlling thickness, plasticizer content and deposition conditions. Atomic Force Microscopy measurements under strain show that the optimized conducting polymer coating is compliant with the micro-crack mechanics of the underlying Au-layer, necessary to absorb the tensile deformation when the electrodes are stretched. We demonstrate functionality of the stretchable electrodes by performing high quality recordings of renal sympathetic nerve activity under chronic conditions in rats.

PEDOT: Dye-Based, Flexible Organic Electrochemical Transistor for Highly Sensitive pH Monitoring.

Organic electrochemical transistors (OECTs) are bioelectronic devices able to bridge electronic and biological domains with especially high amplification and configurational versatility and thus stand out as promising platforms for healthcare applications and portable sensing technologies. Here, we have optimized the synthesis of two pH-sensitive composites of PEDOT (poly(3,4-ethylenedioxythiophene)) doped with pH dyes (BTB and MO, i.e., Bromothymol Blue and Methyl Orange, respectively), showing their ability to successfully convert the pH into an electrical signal. The PEDOT:BTB composite, which exhibited the best performance, was used as the gate electrode to develop an OECT sensor for pH monitoring that can reliably operate in a two-fold transduction mode with super-Nernstian sensitivity. When the OECT transconductance is employed as analytical signal, a sensitivity of 93 ± 8 mV pH unit-1 is achieved by successive sampling in aqueous electrolytes. When the detection is carried out by dynamically changing the pH of the same medium, the offset gate voltage of the OECT shifts by (1.1 ± 0.3) × 102 mV pH unit-1. As a further step, the optimized configuration was realized on a PET substrate, and the performance of the resulting flexible OECT was assessed in artificial sweat within a medically relevant pH range.

Synthesis and characterization of benzodithiophene and benzotriazole-based polymers for photovoltaic applications.

Two high bandgap benzodithiophene-benzotriazole-based polymers were synthesized via palladium-catalysed Stille coupling reaction. In order to compare the effect of the side chains on the opto-electronic and photovoltaic properties of the resulting polymers, the benzodithiophene monomers were substituted with either octylthienyl (PTzBDT-1) or dihexylthienyl (PTzBDT-2) as side groups, while the benzotriazole unit was maintained unaltered. The optical characterization, both in solution and thin-film, indicated that PTzBDT-1 has a red-shifted optical absorption compared to PTzBDT-2, likely due to a more planar conformation of the polymer backbone promoted by the lower content of alkyl side chains. The different aggregation in the solid state also affects the energetic properties of the polymers, resulting in a lower highest occupied molecular orbital (HOMO) for PTzBDT-1 with respect to PTzBDT-2. However, an unexpected behaviour is observed when the two polymers are used as a donor material, in combination with PC61BM as acceptor, in bulk heterojunction solar cells. Even though PTzBDT-1 showed favourable optical and electrochemical properties, the devices based on this polymer present a power conversion efficiency of 3.3%, considerably lower than the efficiency of 4.7% obtained for the analogous solar cells based on PTzBDT-2. The lower performance is presumably attributed to the limited solubility of the PTzBDT-1 in organic solvents resulting in enhanced aggregation and poor intermixing with the acceptor material in the active layer.

Enhanced Ultraviolet Stability of Air-Processed Polymer Solar Cells by Al Doping of the ZnO Interlayer.

Photostability of organic photovoltaic devices represents a key requirement for the commercialization of this technology. In this field, ZnO is one of the most attractive materials employed as an electron transport layer, and the investigation of its photostability is of particular interest. Indeed, oxygen is known to chemisorb on ZnO and can be released upon UV illumination. Therefore, a deep analysis of the UV/oxygen effects on working devices is relevant for the industrial production where the coating processes take place in air and oxygen/ZnO contact cannot be avoided. Here we investigate the light-soaking stability of inverted organic solar cells in which four different solution-processed ZnO-based nanoparticles were used as electron transport layers: (i) pristine ZnO, (ii) 0.03 at %, (iii) 0.37 at %, and (iv) 0.8 at % aluminum-doped AZO nanoparticles. The degradation of solar cells under prolonged illumination (40 h under 1 sun), in which the ZnO/AZO layers were processed in air or inert atmosphere, is studied. We demonstrate that the presence of oxygen during the ZnO/AZO processing is crucial for the photostability of the resulting solar cell. While devices based on undoped ZnO were particularly affected by degradation, we found that using AZO nanoparticles the losses in performance, due to the presence of oxygen, were partially or totally prevented depending on the Al doping level.