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

Reduced‐Graphene‐Oxide‐Based Needle‐Type Field‐Effect Transistor for Dopamine Sensing

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Selective detection of dopamine with an all PEDOT:PSS Organic Electrochemical Transistor

open6noAn all PEDOT:PSS Organic Electrochemical Transistor (OECT) has been developed and used for the selective detection of dopamine (DA) in the presence of interfering compounds (ascorbic acid, AA and uric acid, UA). The selective response has been implemented using a potentiodynamic approach, by varying the operating gate bias voltage and the scan rate. The trans-conductance curves allow to obtain a linear calibration plot for AA, UA and DA and to separate the redox waves associated to each compound; for this purpose, the scan rate is an important parameter to achieve a good resolution. The sensitivities and limits of detection obtained with the OECT have been compared with those obtained by potential step amperometric techniques (cyclic voltammetry and differential pulse voltammetry), employing a PEDOT:PSS working electrode: our results prove that the all-PEDOT:PSS OECT sensitivities and limits of detection are comparable or even better than those obtained by DPV, a technique that employs a sophisticate potential wave and read-out system in order to maximize the performance of electrochemical sensors and that can hardly be considered a viable readout method in practical applications.openGualandi, Isacco; Tonelli, Domenica; Mariani, Federica; Scavetta, Erika; Marzocchi, Marco; Fraboni, BeatriceGualandi, Isacco; Tonelli, Domenica; Mariani, Federica; Scavetta, Erika; Marzocchi, Marco; Fraboni, Beatric

Design of an electrochemically gated organic semiconductor for pH sensing

Since the development of potentiometric ion-selective electrodes, remarkable steps have been taken towards progressive simplification and improved robustness of pH sensing probes. In particular, the design of compact sensing architectures using solid-state components holds great potential for portable and wearable applications. Here we report the development of an electrochemically gated device for pH detection, combining the robustness of potentiometric-like transduction with an extremely simple and integrated geometry requiring no reference. The sensor is a two-point probe device comprising two thin polymeric films, i.e. a charge transport layer and a pH-sensitive layer, and exhibits a sensitivity of (8.3 ± 0.2) × 10−3 pH unit−1 in the pH range from 2 to 7. Thanks to the versatility and robustness of the optimised design, a textile pH sensor was fabricated whose performance is comparable with that of glass sensors

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

open8noOxygen 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.The work was supported by the European Union FESR FSE, PON Research and Innovation 2014-2020 and FSC, project number ARS01-00996 "TEXT-STYLENuovi tessuti intelligenti e sostenibilimultisettoriali per il design creative e stileMade-in-Italy" and by the Italian Ministry of Economic Development 2020-Project "AlmaMater patents-Monitoraggio in continuo di pH e idratazione-MIRAGE".openFrancesco Decataldo, Filippo Bonafè, Federica Mariani, Martina Serafini, Marta Tessarolo, Isacco Gualandi, Erika Scavetta, Beatrice FraboniFrancesco Decataldo, Filippo Bonafè, Federica Mariani, Martina Serafini, Marta Tessarolo, Isacco Gualandi, Erika Scavetta, Beatrice Frabon

Nanoporous Ge electrode as a template for nano-sized (<5 nm) Au aggregates

none8In this paper we present the extremely peculiar electrical properties of nanoporous Ge. A full and accurate electrical characterization showed an unexpected and extremely high concentration of positive carriers. Electrochemical analyses showed that nanoporous Ge has improved charge transfer properties with respect to bulk Ge. The electrode behavior, together with the large surface-to-volume ratio, make nanoporous Ge an efficient nanostructured template for the realization of other porous materials by electrodeposition. The pores were efficiently decorated by Au nanoparticles of diameter as low as 1–5 nm, prepared by electrochemical deposition. These new results demonstrate the potential and efficient use of nanoporous Ge as a nanostructured template for nano-sized Au aggregates, opening the way for the realization of innovative sensor devices.openG.Impellizzeri; L.Romano; B.Fraboni; E. Scavetta; F.Ruffino; C.Bongiorno; V. Privitera; M.G.GrimaldiG.Impellizzeri; L.Romano; B.Fraboni; E. Scavetta; F.Ruffino; C.Bongiorno; V. Privitera; M.G.Grimald

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