Nicola Coppedè

New opportunities for organic electronics and bioelectronics: ions in action

This perspective deals with the coupling of ionic and electronic transport in organic electronic devices, focusing on electrolyte-gated transistors. These include electrolyte-gated organic field-effect transistors (EG-OFETs) and organic electrochemical transistors (OECTs). EG-OFETs, based on molecules and polymers, can be operated at low electrical bias (about 1 V or below) and permit unprecedented charge carrier densities within the transistor channel. OECTs can be operated in aqueous environment as efficient ion-to-electron converters, thus providing an interface between the worlds of biology and electronics. The exploration and the exploitation of coupled ionic and electronic transport in organic materials brings together different disciplines such as materials science, physics, chemistry, electrochemistry, organic electronics and biology.

Superhydrophobic Surfaces as Smart Platforms for the Analysis of Diluted Biological Solutions

The aim of this paper is to expound on the rational design, fabrication and development of superhydrophobic surfaces (SHSs) for the manipulation and analysis of diluted biological solutions. SHSs typically feature a periodic array or pattern of micropillars; here, those pillars were modified to incorporate on the head, at the smallest scales, silver nanoparticles aggregates. These metal nanoclusters guarantee superior optical properties and especially SERS (surface enhanced Raman scattering) effects, whereby a molecule, adsorbed on the surface, would reveal an increased spectroscopy signal. On account of their two scale-hybrid nature, these systems are capable of multiple functions which are (i) to concentrate a solution, (ii) to vehicle the analytes of interest to the active areas of the substrate and, therefore, (iii) to measure the analytes with exceptional sensitivity and very low detection limits. Forasmuch, combining different technologies, these devices would augment the performance of conventional SERS substrates and would offer the possibility of revealing a single molecule. In this work, similar SHSs were used to detect Rhodamine molecules in the fairly low atto molar range. The major application of this novel family of devices would be the early detection of tumors or other important pathologies, with incredible advances in medicine.

Ambipolar copper phthalocyanine transistors with carbon nanotube array electrodes

We report on organic thin film transistors (OTFTs) based on copper phthalocyanine (CuPc) having electrodes consisting of isolated carbon nanotube (CNT) arrays embedded in the organic layer. CuPc OTFT with CNT array electrodes show p-type behavior with Ohmic hole injection, high hole mobility, and enhanced switching characteristics at low voltage. The p-type devices are converted to ambipolar OTFT by vacuum annealing. Despite the large offset between the CNT work function and the CuPc energy levels, electron injection characteristics are also Ohmic. The extension of CNT electrodes to the phthalocyanine family confirms the validity of this contact approach for organic electronic devices.

A single cotton fiber organic electrochemical transistor for liquid electrolyte saline sensing

A single natural cotton fiber has been functionalized with poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonate) (PEDOT:PSS) conductive polymer by a simple soaking process and used as a channel of an organic electrochemical transistor (OECT), directly interfaced with a liquid electrolyte in contact with an Ag wire gate. The device shows a stable and reproducible current modulation and has been demonstrated to be very effective for electrochemical sensing of NaCl concentration in water. The single wire cotton fiber OECT results to be a simple and low cost device, which is very attractive for wearable electronics in fitness and healthcare.

Organic electrochemical transistors monitoring micelle formation

Organic electrochemical transistors (OECTs) exploit electrolyte gating to achieve the transduction of ionic currents. Therefore, they are ideally suitable to sense different chemo/bio species dissolved in the electrolyte. Current modulation in OECTs relies on doping or dedoping of the OECT channel by electrolyte ions. Nevertheless the role played by the specific physicochemical properties of an electrolyte on OECT operation is largely unknown. Here we investigate OECTs, making use of aqueous solutions of the micelle-forming cationic surfactant cetyltrimethylammonium bromide (CTAB) as the electrolyte. Micelle-forming salts are remarkable model systems to study the doping and dedoping mechanism of OECTs, because the aggregation of dissociated ions into micelles at the critical micelle concentration permits to modify the size and the type of the species that dope or dedope the OECT channel in situ. The current modulation of OECTs using a CTAB electrolyte shows a marked increase close to the critical micellar concentration. The measurement of the transistors drain current as a function of CTAB concentration provides a simple, fast method to detect the formation of micelles from dissociated ions.

Controlling field-effect mobility in pentacene-based transistors by supersonic molecular-beam deposition

We show that pentacene field-effect transistors, fabricated by supersonic molecular beams, have a performance strongly depending on the precursor’s kinetic energy (KE). The major role played by KE is in achieving highly ordered and flat films. In the range KE≈3.5–6.5eV, the organic field effect transistor linear mobility increases of a factor ∼5. The highest value (1.0cm2V−1s−1) corresponds to very uniform and flat films (layer-by-layer type growth). The temperature dependence of mobility for films grown at KE>6eV recalls that of single crystals (bandlike) and shows an opposite trend for films grown at KE⩽5.5eV.

Liposome sensing and monitoring by organic electrochemical transistors integrated in microfluidics

BACKGROUND Organic electrochemical transistors (OECTs), which are becoming more and more promising devices for applications in bioelectronics and nanomedicine, are proposed here as ideally suitable for sensing and real time monitoring of liposome-based structures. This is quite relevant since, currently, the techniques used to investigate liposomal structures, their stability in different environments as well as drug loading and delivery mechanisms, operate basically off-line and/or with pre-prepared sampling. METHODS OECTs, based on the PEDOT:PSS conductive polymer, have been employed as sensors of liposome-based nanoparticles in electrolyte solutions to assess sensitivity and monitoring capabilities based on ion-to-electron amplified transduction. RESULTS We demonstrate that OECTs are very efficient, reliable and sensitive devices for detecting liposome-based nanoparticles on a wide dynamic range down to 10(-5)mg/ml (with a lowest detection limit, assessed in real-time monitoring, of 10(-7)mg/ml), thus matching the needs of typical drug loading/drug delivery conditions. They are hence particularly well suited for real-time monitoring of liposomes in solution. Furthermore, OECTs are shown to sense and discriminate successive injection of different liposomes, so that they could be good candidates in quality-control assays or in the pharmaceutical industry. GENERAL SIGNIFICANCE Drug loading and delivery by liposome-based structures is a fast growing and very promising field that will strongly benefit from real-time, highly sensitive and low cost monitoring of their dynamics in different pharma and biomedical environments, with a particular reference to the pharmaceutical and production processes, where a major issue is monitoring and measuring the formation and concentration of liposomes and the relative drug load. The demonstrated ability to sense and monitor complex bio-structures, such as liposomes, paves the way for very promising developments in biosensing and nanomedicine. This article is part of a Special Issue entitled Organic Bioelectronics-Novel Applications in Biomedicine.

Human stress monitoring through an organic cotton-fiber biosensor

Selective detection of bioanalytes in physiological fluids, such as blood, sweat or saliva, by means of low-cost and non-invasive devices, is of crucial importance to improve diagnosis and prevention in healthcare. To be really useful in everyday life a sensing system needs to be handy, non-invasive, easy to read and possibly wearable. Only a sensor that satisfies these requirements could be eligible for applications in healthcare and physiological condition monitoring. Herein an organic electrochemical transistor has been investigated as a simple, low-cost and e-textile biosensor, fully integrated on a single cotton yarn. The biosensor has been used for real-time detection of adrenaline, selectively compared to the saline content in human physiological fluids. The sensing mechanism is based on the oxidation of adrenaline at the Pt-gate electrode surface, with the formation of adrenaline-quinone and adrenochrome. Two independent organic electrochemical transistors, characterized by different gate-electrode materials, detect saline and adrenaline concentrations, respectively, in real human sweat. Measurements performed in real-time mode show the complete independence of adrenaline detection from NaCl and, hence, guarantee the simultaneous monitoring of both concentrations. The oxidation of adrenaline has been studied by means of absorption spectroscopy in air, with either silver or platinum working electrodes. Our results confirm that the oxidation reaction driven by the Pt-electrode leads to the formation of adrenochrome, while with the Ag-electrode the oxidation is similar to the spontaneous one occurring in air. The cotton-based biosensor shows the possibility of monitoring human performances (hydration and stress) in situ and using a non-invasive approach, opening new unexplored opportunities in healthcare, fitness and work safety.

Irreversible evolution of eumelanin redox states detected by an organic electrochemical transistor: en route to bioelectronics and biosensing

Organic electrochemical transistors (OECTs) are currently emerging as powerful tools for biosensing, bioelectronics and nanomedical applications owing to their ability to operate under liquid phase conditions optimally integrating electronic and biological systems. Herein we disclose the unique potential of OECTs for detecting and investigating the electrical properties of insoluble eumelanin biopolymers. Gate current measurements on fine aqueous suspensions of a synthetic eumelanin sample from 5,6-dihydroxyindole (DHI) revealed a well detectable hysteretic response similar to that of the pure monomer in solution, with the formal concentration of the polymer as low as 10-6 M. Induction of the gate current would reflect electron transfer from solid eumelanin to the Pt-electrode sustained by redox active catechol/quinone components of the polymer. A gradual decrease in gate current and areas subtended by hysteretic loops were observed over 5 cycles both in the eumelanin- and DHI-based devices, suggesting evolution of the polymer from a far-from-the-equilibrium redox state toward a more stable electronic arrangement promoted by redox exchange with the gate electrode. OECTs are thus proposed as valuable tools for the efficient heterogeneous-phase sensing of eumelanins and to gauge their peculiar electrical and redox behaviour.

Microtexturing of the conductive PEDOT:PSS Polymer for superhydrophobic organic electrochemical transistors

Superhydrophobic surfaces are bioinspired, nanotechnology artifacts, which feature a reduced friction coefficient, whereby they can be used for a number of very practical applications including, on the medical side, the manipulation of biological solutions. In this work, we integrated superhydrophobic patterns with the conducting polymer PEDOT:PSS, one of the most used polymers in organic electronics because highly sensitive to ionized species in solution. In doing so, we combined geometry and materials science to obtain an advanced device where, on account of the superhydrophobicity of the system, the solutions of interest can be manipulated and, on account of the conductive PEDOT:PSS polymer, the charged molecules dispersed inside can be quantitatively measured. This original substrate preparation allowed to perform electrochemical measurements on ionized species in solution with decreasing concentration down to 10−7 molar. Moreover, it was demonstrated the ability of the device of realizing specific, combined time and space resolved analysis of the sample. Collectively, these results demonstrate how a tight, interweaving integration of different disciplines can provide realistic tools for the detection of pathologies. The scheme here introduced offers breakthrough capabilities that are expected to radically improve both the pace and the productivity of biomedical research, creating an access revolution.