The most commonly used methods to electrodeposit nanomaterials on conductive supports or to obtain electrosynthesis nanomaterials are described. Au, layered double hydroxides (LDHs), metal oxides, and polymers are the classes of compounds taken into account. The electrochemical approach for the synthesis allows one to obtain nanostructures with well-defined morphologies, even without the use of a template, and of variable sizes simply by controlling the experimental synthesis conditions. In fact, parameters such as current density, applied potential (constant, pulsed or ramp) and duration of the synthesis play a key role in determining the shape and size of the resulting nanostructures. This review aims to describe the most recent applications in the field of electrochemical sensors of the considered nanomaterials and special attention is devoted to the analytical figures of merit of the devices.

The development of wearable chemical sensors is receiving a great deal of attention in view of non-invasive and continuous monitoring of physiological parameters in healthcare applications. This paper describes the development of a fully textile, wearable chemical sensor based on an organic electrochemical transistor (OECT) entirely made of conductive polymer (PEDOT:PSS). The active polymer patterns are deposited into the fabric by screen printing processes, thus allowing the device to actually “disappear” into it. We demonstrate the reliability of the proposed textile OECTs as a platform for developing chemical sensors capable to detect in real-time various redox active molecules (adrenaline, dopamine and ascorbic acid), by assessing their performance in two different experimental contexts: i) ideal operation conditions (i.e. totally dipped in an electrolyte solution); ii) real-life operation conditions (i.e. by sequentially adding few drops of electrolyte solution onto only one side of the textile sensor). The OECTs response has also been measured in artificial sweat, assessing how these sensors can be reliably used for the detection of biomarkers in body fluids. Finally, the very low operating potentials (<1 V) and absorbed power (~10⁻⁴W) make the here described textile OECTs very appealing for portable and wearable applications.

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.

An ascorbic acid (AA) sensor was developed by employing an organic electrochemical transistor (OECT) based only on PEDOT:PSS as a conductive material. The device was prepared by spin coating using the CLEVIOS™ PH 1000 suspension (PEDOT:PSS) masking the gate and the channel areas with tape. The device was electrically characterized while the doping level of the PEDOT:PSS in the channel was controlled using both the gate electrode and the potentiostat. It was demonstrated that the current that flows in channel (I_d) is controlled by the concentration of oxidized sites in the examined potential range. AA reacts with the conductive polymer leading to the extraction of charge carriers from the channel, and thus resulting in a decrease of the absolute value of I_d. It was observed that I_d linearly depends on the logarithm of the AA concentration between 10⁻⁶ and 10⁻³ M. The OECT response to AA was studied by varying the gate voltage or the PEDOT:PSS thickness. The performance of the device for optimized conditions shows a limit of detection equal to 10⁻⁸ M and a sensitivity of 4.5 ± 0.1 × 10⁻⁶ A decade⁻¹.

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.

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. Graphical Abstract