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The next generation of brain-machine interfaces are envisioned to couple signal transduction, filtering, and sorting on board with minimum power consumption and maximum bio-integrability. These functional needs shall be mandatorily met in order to design efficient closed-loop brain-machine interfaces aimed at treating and monitoring various disorders of the central and peripheral nervous system. Here, we highlight the pivotal role organic bioelectronics may have in the contextual development of all these three desiderata, by demonstrating a modular organic-electronics circuit towards real-time signal filtering. The inherent filtering capabilities of electrolyte-gated organic transistor are tuned via adjustment of operational conditions and benchmarked in an electromyography experiment. Additionally, a whole-organic signal processing circuitry is presented, coupling such transistors with ad hoc designed organic passive components. This provides the possibility to sort complex signals into their constitutive frequency components in real time, thereby delineating innovative strategies to devise organic-based functional building-blocks for brain-machine interfaces.

Reversibly tunable short-term plasticity (STP) of the channel current in organic neuromorphic devices is demonstrated with a three-terminal architecture. Electrolyte-gated organic transistors--EGOTs--are driven with square voltage pulses at the drain electrodes, while the gate bias enables the modulation of the amplitude and characteristic time scale of the depressive STP spiking response up to 1 order of magnitude. The gate potential sets the baseline and the steady-state current, preluding multilevel memory writing. The fine-tuning of the STP response, which is not possible with two-electrode organic neuromorphic devices, is reversible and does not imply chemical modifications of the active layer.

Advanced materials interfaces 9(25), 2200709 (2022). doi:10.1002/admi.202200709, Published by Wiley-VCH, Weinheim

This is a Review paper on the use of conductive polymers in neural interfaces aimed at bidirectional communication with the brain.

Poly(3,4-ethylentedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is one of the most studied materials for organic bioelectronics, supercapacitors and organic photovoltaics. Its low impedance is ascribed to the so-called volumetric capacitance, a property that phenomenologically correlates the capacitive coupling/charge storage in devices to the PEDOT:PSS volume/thickness. Here we investigate the correlation between the capacitance and the electroactive surface area (ESA) for large-volume spin-cast PEDOT:PSS electrodes. We measure the capacitance with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), and characterize the surface morphology by atomic force microscopy and X-ray photoelectron spectroscopy. Capacitance of PEDOT:PSS films scales with volume up to ~5 × 106 ?m3 but is saturated at larger volumes. This scaling behavior is paralleled by the scaling of the ESA, hence the ratio between the effective capacitance and ESA remains constant across the whole data set, thus showing that the specific areal capacitance is indeed the relevant material property of PEDOT:PSS. EIS data fit supports the experimental evidence obtained by CV, further revealing that the diffusion time constant is also saturated at high volumes. This supports the scenario where the effective capacitance relates to the ion accessible ESA, and shows that the saturation of the capacitance arises from a change of ion penetration from a diffusive (at small volumes) to a non-diffusive regime at large volumes.

Plum Pox Virus (PPV) is the pathogen responsible for Sharka, a highly infectious disease affecting stone fruit trees and causing severe economic damages, which can be only contained through early-detection and frequent monitoring. We propose a bioelectronic PPV biosensor, based on a electrolyte-gated organic field-effect transistor (EGOFET), for the specific detection of PPV in plant extracts with a sub ng/ml detection limit. The sensing unit of the biosensor is based on anti-PPV antibodies, uniformly oriented on the gold gate electrode by using a sub-monolayer of Protein G. The sensitivity and dynamic range of the EGOFET-based biosensor are comparable to those of commercially available platforms for detection of plant pathogens. This novel electronic immunosensor is compatible with low-cost fabrication procedures and can be easily reconfigured into a fully portable device to be operated in greenhouse and in the field orchards.

Specific detection of dopamine (DA) is achieved with organic neuromorphic devices with no specific recognition function in an electrolyte solution. The response to voltage pulses consists of amplitude-depressed current spiking mimicking the short-term plasticity (STP) of synapses. An equivalent circuit hints that the STP timescale of the device arises from the capacitance and resistance of the poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) in series with the electrolyte resistance. Both the capacitance and resistance of PEDOT:PSS change with solution compositions. Dose curves are constructed from the STP timescale for each DA metabolite from pM to mM range of concentrations. The STP response of DA is distinctive from the other metabolites even when differences are by one functional group. Both STP and sensitivity to DA are larger across the patho-physiological range with respect to those to DA metabolites. Density functional theory calculations hint to a stronger hydrogen bond pattern of DA ammonium compared to cationic metabolites. The exponential correlation between STP and the binding energy of DA metabolites interacting with PEDOT:PSS indicates that the slow dynamics of ionic species in and out PEDOT:PSS is the origin of the neuromorphic STP. The sensing framework discriminates differences of nonspecific interactions of few kcal mol(-1), corresponding to one functional group in the molecule. Life Science Department Biomedical, Metabolic and Neural Sciences Department of University of Modena and Reggio Emilia through "FAR 2018" Dipartimenti di eccellenza 2018-2022, MIUR, Italy Regione Emilia-Romagna through "Percorso co-finanziato con risorse del Fondo Sociale Europeo Programma Operativo 2014/2020" Biomedical, Metabolic and Neural Sciences Department of University of Modena and Reggio Emilia through "FAR 2015" info:eu-repo/semantics/publishedVersion

The water dispersion of the conductive polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) is one of the most used material precursors in organic electronics also thanks to its industrial production. There is a growing interest for conductive polymers that could be alternative surrogates or replace PEDOT:PSS in some applications. A recent study by our group compared electrodeposited PEDOT:Nafion vs PEDOT:PSS in the use for neural recordings. Here, we introduce an easy and reproducible synthetic protocol to prepare a water dispersion of PEDOT:Nafion. The conductivity of the pristine material is on the order of 2 S cm-1 and was improved up to ≈6 S cm-1 upon treatment with ethylene glycol. Faster ion transfer was assessed by electrochemical impedance spectroscopy (EIS), and, interestingly, an improved adhesion was observed for coatings of the new PEDOT:Nafion dispersion on glass substrates, even without the addition of the silane cross-linker needed for PEDOT:PSS. As proof of concept, we demonstrate the use of this novel water dispersion of PEDOT:Nafion in three different organic electronic device architectures, namely, an organic electrochemical transistor (OECT), a memristor, and an artificial synapse.

The photochemical core of every photosynthetic apparatus is the reaction center, a transmembrane enzyme that converts photons into charge-separated states across the biological membrane with an almost unitary quantum yield. We present a light-driven organic transistor architecture, which converts light into electrical current by exploiting the efficiency of this biological machinery. Proper surface tailoring enables the integration of the bacterial reaction center as photoactive element in organic transistors, allowing the transduction of its photogenerated voltage into photomodulation of the output current up to two orders of magnitude. The device architecture, termed Light-driven Electrolyte-Gated Organic Transistor (LEGOT), is the prototype of a new generation of low-power hybrid bio-optoelectronic organic devices.

Most of the photochemical activity of bacterial photosynthetic apparatuses occurs in the reaction center, a transmembrane protein complex which converts photons into chargeseparated states across the membrane with a quantum yield close to unity, fuelling the metabolism of the organism. Integrating the reaction center from the bacterium Rhodobacter sphaeroides onto electroactive surfaces, it is possible to technologically exploit the efficiency of this natural machinery to generate a photovoltage upon Near Infra-Red illumination, which can be used in electronic architectures working in the electrolytic environment such as electrolyte-gated organic transistors and bio-photonic power cells. Here, photovoltage generation in reaction center-based bio-hybrid architectures is investigated by means of chronopotentiometry, isolating the contribution of the functionalisation layers and defining novel surface functionalization strategies for photovoltage tuning.

Microelectrode arrays are used for recording and stimulation in neurosciences both in vitro and in vivo. The electrodeposition of conductive polymers, such as poly(3,4-ethylene dioxythiophene) (PEDOT), is widely adopted to improve both the in vivo recording and the charge injection limit of metallic microelectrodes. The workhorse of conductive polymers in the neurosciences is PEDOT:PSS, where PSS represents polystyrene-sulfonate. In this paper, the counterion is the fluorinated polymer Nafion, so the composite PEDOT:Nafion is deposited onto a flexible neural microelectrode array. PEDOT:Nafion coated electrodes exhibit comparable in vivo recording capability to the reference PEDOT:PSS, providing a large signal-to-noise ratio in a murine animal model. Importantly, PEDOT:Nafion exhibits a minimized polarization during electrical stimulation, thereby resulting in an improved charge injection limit equal to 4.4 mC cm-2 , almost 80% larger than the 2.5 mC cm-2 that is observed for PEDOT:PSS.

Our purpose was to study the tribological effects of surface texturing at the mesoscale, generally disregarded. We realized hemispherical dimples on 100Cr6 steel pins using a ns-pulsed Nd:YAG laser. Both radius and depth of the patterns fall in the very-low part of the micrometric scale, ranging respectively from 10 to 13 μm and from 4 to 6.5 μm. To map Stribeck curves, we used a pin-on-disk apparatus and a commercial motor oil as lubricant. The results confirm that the post-texturing lapping process is crucial to achieve a reduction in the coefficient of friction. These patterns show a tribological effect mainly in mixed lubrication regime, and partially in hydrodynamic regime. Even very small differences in radius and depth may induce very different response, evidencing the need of very fine tuning of the geometrical characteristics of the patterns. The lower friction was recorded for larger and deeper dimples. Friction reduction for increasing dimples density has been found as well. Endurance tests in boundary lubrication regime show a more stable coefficient of friction and a larger mean lifetime of patterned surfaces with respect to polished one. Furthermore, water-contact-angle tests show a weak hydrophobic effect for high aspect ratio patterns. However, no correlation was observed between wettability and tribological response.

The quantification of urea is of the utmost importance not only in medical diagnosis, where it serves as a potential indicator of kidney and liver disfunction, but also in food safety and environme ...

A novel fully organic bioelectronic device is presented and validated as electronic transducer and current stimulator for brain implants. The device integrates polymeric electrodes made of poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) on paper thin foils, resulting in a high surface-to-volume ratio architecture that exhibits high sensitivity to interfacial ionic transport phenomena. The prototyping technique herein presented yields devices for the bidirectional communication with biological systems whose dimensionality can be controlled according to the desired application. Transduction of ultra-low local-field potentials and delivery of voltage pulse-trains alike those used in deep-brain stimulation are herein assessed, paving the way towards novel theranostic strategies for the treatment of Parkinson’s Disease and other severe neurodegenerative and/or traumatic pathologies of the central nervous system.

Cytokines are small proteins that play fundamental roles in inflammatory processes in the human body. In particular, interleukin (IL)-6 is a multifunctional cytokine, whose increased levels are associated with infection, cancer, and inflammation. The quantification of IL-6 is therefore of primary importance in early stages of inflammation and in chronic diseases, but standard techniques are expensive, time-consuming, and usually rely on fluorescent or radioactive labels. Organic electronic devices and, in particular, organic field-effect transistors (OFETs) have been proposed in the recent years as novel platforms for label-free protein detection, exploiting as sensing unit surface-immobilized antibodies or aptamers. Here, the authors report two electrolyte-gated OFETs biosensors for IL-6 detection, featuring monoclonal antibodies and peptide aptamers adsorbed at the gate. Both strategies yield biosensors that can work on a wide range of IL-6 concentrations and exhibit a remarkable limit of detection of 1 pM. Eventually, electrolyte gated OFETs responses have been used to extract and compare the binding thermodynamics between the sensing moiety, immobilized at the gate electrode, and IL-6. (C) 2017 American Vacuum Society. Funding Agencies|IT MIUR Bilateral Project Italy/Sweden "Poincare"; joint INFM-CNR Project; Life Science Department; "Fondazione di Vignola"

In this work, we demonstrate the ultrasensitive and selective detection of dopamine by means of a neuro-inspired device platform without the need of a specific recognition moiety. The sensor is a whole organic device featuring two electrodes made of poly(3,4-ethylenedioxythiophene):polystyrenesulfonate—PEDOT:PSS—patterned on a polydymethylsiloxane—PDMS—flexible substrate. One electrode is pulsed with a train of voltage square waves, to mimic the presynaptic neuron behavior, while the other is used to record the displacement current, mimicking the postsynaptic neuron. The current response exhibits the features of synaptic Short-Term Plasticity (STP) with facilitating or depressing response according to the stimulus frequency. We found that the response characteristic time υSTP depends on dopamine (DA) concentration in solution. The dose curve exhibits superexponential sensitivity at the lowest concentrations below 1 nM. The sensor detects [DA] down to 1 pM range. We assess the sensor also in the presence o...

Organic field effect transistors (OFET) operated in aqueous environments are emerging as ultra-sensitive biosensors and transducers of electrical and electrochemical signals from a biological environment. Their applications range from detection of biomarkers in bodily fluids to implants for bidirectional communication with the central nervous system. They can be used in diagnostics, advanced treatments and theranostics. Several OFET layouts have been demonstrated to be effective in aqueous operations, which are distinguished either by their architecture or by the respective mechanism of doping by the ions in the electrolyte solution. In this work we discuss the unification of the seemingly different architectures, such as electrolyte-gated OFET (EGOFET), organic electrochemical transistor (OECT) and dual-gate ion-sensing FET. We first demonstrate that these architectures give rise to the frequency-dependent response of a synapstor (synapse-like transistor), with enhanced or depressed modulation of the output current depending on the frequency of the time-dependent gate voltage. This behavior that was reported for OFETs with embedded metal nanoparticles shows the existence of a capacitive coupling through an equivalent network of RC elements. Upon the systematic change of ions in the electrolyte and the morphology of the charge transport layer, we show how the time scale of the synapstor is changed. We finally show how the substrate plays effectively the role of a second bottom gate, whose potential is actually fixed by the pH/composition of the electrolyte and the gate voltage applied.

A whole organic artificial synapse has been fabricated by patterning PEDOT:PSS electrodes on PDMS that are biased in frequency to yield a STP response. The timescale of the STP response is shown to be sensitive to the concentration of dopamine, DA, a neurotransmitter relevant for monitoring the development of Parkinson's disease and potential locoregional therapies. The sensitivity of the sensor towards DA has been validated comparing signal variation in the presence of DA and its principal interfering agent, ascorbic acid, AA. The whole organic synapse is biocompatible, soft and flexible, and is attractive for implantable devices aimed to real-time monitoring of DA concentration in bodily fluids. This may open applications in chronic neurodegenerative diseases such as Parkinson's disease. EU 7th Framework Programme [FP7/2007–2013]; Grant Agreement No. 280772; IT MIUR Bilateral Project IT/SE “Poincaré”

The bis(dansylated) polyoxometalate (nBu4N)4[γ-SiW10O36{(Me2N)C10H6SO2NH(CH2)3Si}2O] has been investigated to establish the impact of the inorganic polyanionic domain on the photophysical behaviour of the appended dansyl chromophore. The interactions of this molecular hybrid with Lewis acids (lanthanide cations) and with an aromatic cationic molecule (N,N′-2,7-didecyldiazapyrenium) have also been monitored by multiple techniques, including spectrofluorimetry, Z-potential, 1H NMR spectroscopy, transmission electron microscopy. The different spectral behaviour, coupled with the morphological evolution of the resulting nanostructures, highlights the capability of the hybrid polyoxometalate to interact, acting as a ditopic receptor, with different chemical substrates.

none 14 si Biorecognition is a central event in biological processes in the living systems that is also widely exploited in technological and health applications. We demonstrate that the Electrolyte Gated Organic Field Effect Transistor (EGOFET) is an ultrasensitive and specific device that allows us to quantitatively assess the thermodynamics of biomolecular recognition between a human antibody and its antigen, namely, the inflammatory cytokine TNFα at the solid/liquid interface. The EGOFET biosensor exhibits a superexponential response at TNFα concentration below 1 nM with a minimum detection level of 100 pM. The sensitivity of the device depends on the analyte concentration, reaching a maximum in the range of clinically relevant TNFα concentrations when the EGOFET is operated in the subthreshold regime. At concentrations greater than 1 nM the response scales linearly with the concentration. The sensitivity and the dynamic range are both modulated by the gate voltage. These results are explained by establishing the correlation between the sensitivity and the density of states (DOS) of the organic semiconductor. Then, the superexponential response arises from the energy-dependence of the tail of the DOS of the HOMO level. From the gate voltage-dependent response, we extract the binding constant, as well as the changes of the surface charge and the effective capacitance accompanying biorecognition at the electrode surface. Finally, we demonstrate the detection of TNFα in human-plasma derived samples as an example for point-of-care application. Berto, Marcello; Casalini, Stefano; Di Lauro, Michele; Marasso, Simone L; Cocuzza, Matteo; Perrone, Denis; Pinti, Marcello; Cossarizza, Andrea; Pirri, Candido F; Simon, Daniel T; Berggren, Magnus; Zerbetto, Francesco; Bortolotti, Carlo A; Biscarini, Fabio Berto, Marcello; Casalini, Stefano; Di Lauro, Michele; Marasso, Simone L; Cocuzza, Matteo; Perrone, Denis; Pinti, Marcello; Cossarizza, Andrea; Pirri, Candido F; Simon, Daniel T; Berggren, Magnus; Zerbetto, Francesco; Bortolotti, Carlo A; Biscarini, Fabio

Electrolyte-gated organic field-effect transistors (EGOFETs), based on ultrathin pentacene films on quartz, were operated with electrolyte solutions whose pH was systematically changed. Transistor parameters exhibit nonmonotonic variation versus pH, which cannot be accounted for by capacitive coupling through the Debye–Helmholtz layer. The data were fitted with an analytical model of the accumulated charge in the EGOFET, where Langmuir adsorption was introduced to describe the pH-dependent charge buildup at the quartz surface. The model provides an excellent fit to the threshold voltage and transfer characteristics as a function of the pH, which demonstrates that quartz acts as a second gate controlled by pH and is mostly effective from neutral to alkaline pH. The effective capacitance of the device is always greater than the capacitance of the electrolyte, thus highlighting the role of the substrate as an important active element for amplification of the transistor response.

Four linear terarylene molecules (i) 4-nitro-terphenyl-4″-methanethiol (NTM), (ii) 4-nitro-terphenyl-3″,5″-dimethanethiol (NTD), (iii) ([1,1′;4′,1″] terphenyl-3,5-diyl)methanethiol (TM), and (iv) ([1,1′;4′,1″] terphenyl-3,5-diyl)dimethanethiol (TD) have been synthesized and their self-assembled monolayers (SAMs) have been obtained on polycrystalline gold. NTM and NTD SAMs have been characterized by X-ray photoelectron spectroscopy, Kelvin probe measurements, electrochemistry, and contact angle measurements. The terminal nitro group (−NO2) is irreversibly reduced to hydroxylamine (−NHOH), which can be reversibly turned into nitroso group (−NO). The direct comparison between NTM/NTD and TM/TD SAMs unambiguously shows the crucial influence of the nitro group on electrowetting properties of polycrystalline Au. The higher grade of surface tension related to NHOH has been successfully exploited for basic operations of digital μ-fluidics, such as droplets motion and merging.

Organic electronic transistors are rapidly emerging as ultrahigh sensitive label-free biosensors suited for point-of-care or in-field deployed applications. Most organic biosensors reported to date are based on immunorecognition between the relevant biomarkers and the immobilized antibodies, whose use is hindered by large dimensions, poor control of sequence, and relative instability. Here, an electrolyte-gated organic field effect transistor (EGOFET) biosensor where the recognition units are surface immobilized peptide aptamers (Affimer proteins) instead of antibodies is reported. Peptide aptasensor for the detection of the pro-inflammatory cytokine tumor necrosis factor alpha (TNF alpha) with a 1 x 10(-12) M limit of detection is demonstrated. Ultralow sensitivity is met even in complex solutions such as cell culture media containing 10% serum, demonstrating the remarkable ligand specificity of the device. The device performances, together with the simple one-step immobilization strategy of the recognition moieties and the low operational voltages, all prompt EGOFET peptide aptasensors as candidates for early diagnostics and monitoring at the point-of-care. Funding Agencies|IT MIUR Bilateral Project Italy/Sweden "Poincare"; INFM-CNR Project "EOS - Organic electronics for innovative measuring instruments"; Life Science Department through "FAR"; "Fondazione di Vignola"

High-mobility organic semiconductors such as [1]benzothieno[3,2-b]benzothiophene (BTBT) derivatives are potential candidates for ultrasensitive biosensors. Here 2,7-dioctyl BTBT (C8-BTBT-C8)-based liquid-gated organic electronic devices are demonstrated with two device architectures, viz. electrolyte-gated organic field-effect transistor (EGOFET) and electrolyte-gated organic synapstor (EGOS), and different electrode materials, viz. gold and poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS). EGOFETs exhibit a mean transconductance of about 45 µS, on a par with literature, and a max value up to 256 µS at the state-of-the-art in aqueous electrolyte, with a mean product of charge mobility and effective capacitance of about 0.112 and 0.044 µS V−1 for gold and PEDOT:PSS electrodes, respectively. EGOSs exhibit a dynamic response with 15 ms characteristic timescale with Au electrodes and about twice with PEDOT:PSS electrodes. These results demonstrate a promising route for sensing applications in physiological environment based on fully solution-processed whole-organic electronic devices featuring ultrahigh sensitivity and fast response.

International audience; Electrolyte gated organic transistors can operate as powerful ultrasensitive biosensors, and efforts are currently devoted to devising strategies for reducing the contribution of hardly avoidable, nonspecific interactions to their response, to ultimately harness selectivity in the detection process. We report a novel lab-on-a-chip device integrating a multigate electrolyte gated organic field-effect transistor (EGOFET) with a 6.5 μL microfluidics set up capable to provide an assessment of both the response reproducibility, by enabling measurement in triplicate, and of the device selectivity through the presence of an internal reference electrode. As proof-of-concept, we demonstrate the efficient operation of our pentacene based EGOFET sensing platform through the quantification of tumor necrosis factor alpha with a detection limit as low as 3 pM. Sensing of inflammatory cytokines, which also include TNFα, is of the outmost importance for monitoring a large number of diseases. The multiplexable organic electronic lab-on-chip provides a statistically solid, reliable, and selective response on microliters sample volumes on the minutes time scale, thus matching the relevant key-performance indicators required in point-of-care diagnostics.