We propose a new facile electrochemical sensing platform for determination of urea, based on a glassy carbon electrode (GCE) modified with nickel cobalt oxide (NiCo 2 O 4 ) nanoneedles. These nanoneedles are used for the first time for highly sensitive determination of urea with the lowest detection limit (1 μM) ever reported for the non-enzymatic approach. The nanoneedles were grown through a simple and low-temperature aqueous chemical method. We characterized the structural and morphological properties of the NiCo 2 O 4 nanoneedles by TEM, SEM, XPS and XRD. The bimetallic nickel cobalt oxide exhibits nanoneedle morphology, which results from the self-assembly of nanoparticles. The NiCo 2 O 4 nanoneedles are exclusively composed of Ni, Co, and O and exhibit a cubic crystalline phase. Cyclic voltammetry was used to study the enhanced electrochemical properties of a NiCo 2 O 4 nanoneedle-modified GCE by overcoming the typical poor conductivity of bare NiO and Co 3 O 4 . The GCE-modified electrode is highly sensitive towards urea, with a linear response (R 2 = 0.99) over the concentration range 0.01-5 mM and with a detection limit of 1.0 μM. The proposed non-enzymatic urea sensor is highly selective even in the presence of common interferents such as glucose, uric acid, and ascorbic acid. This new urea sensor has good viability for urea analysis in urine samples and can represent a significant advancement in the field, owing to the simple and cost-effective fabrication of electrodes, which can be used as a promising analytical tool for urea estimation.

Biological systems use a large variety of ions and molecules of different sizes for signaling. Precise electronic regulation of biological systems therefore requires an interface which translates the electronic signals into chemically specific biological signals. One technology for this purpose that has been developed during the last decade is the organic electronic ion pump (OEIP). To date, OEIPs have been fabricated by micropatterning and labor-intensive manual techniques, hindering the potential application areas of this promising technology. Here we show, for the first time, fully screen-printed OEIPs. We demonstrate a large-area printed design with manufacturing yield >90%. Screen-printed cation- and anion-exchange membranes are both demonstrated with promising ion selectivity and performance, with transport verified for both small ions (Na⁺, K⁺, Cl^–) and biologically-relevant molecules (the cationic neurotransmitter acetylcholine, and the anionic anti-inflammatory salicylic acid). These advances open the 'iontronics' toolbox to the world of printed electronics, paving the way for a broader arena for applications.

Organic electrochemical transistors (OECTs) operated in the faradic regime were shown as outperforming transducers of bioelectric signals in vitro and in vivo. Fabrication by additive manufacturing techniques fosters OECTs as ideal candidates for point-of-care applications, as well as imposes limitations on the choice of materials and their processing conditions. Here, we address the question of how the response of fully printed OECTs depends on gate electrode material. Toward this end, we investigate the redox processes underlying the operation of OECTs under faradic regime, to show OECTs with carbon gate (C-gate) that exhibit no current modulation gate voltages <1.2 V. This is a hallmark that no interference with the faradic operation of the device enabled by redox processes occurs when operating C-gate OECTs in the low-voltage range as label-free biosensors for the detection of electroactive (bio)molecules. To tune the faradic response of the device, we electrodeposited Au on the carbon gate (Au-C-gate), obtaining a device that operates at lower gate voltage values than C-gate OECT. The presence of gold on the gate allowed further modification of the electrical performances by functionalization of the Au-C-gate with different self-assembled monolayers by fast potential-pulse-assisted method. Moreover, we show that the presence in the electrolyte solution of an external redox probe can be used to drive the faradic response of both C- and Au-C-gate OECTs, impacting on the gate potential window that yields effective drain current modulation. The results presented here suggest possible new strategies for controlling the faradic operation regime of OECTs sensors by chemical modification of the gate surface.

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 environmental control. Here, we describe a urea biosensor based on urease entrapped in a crosslinked gelatin hydrogel, deposited onto a fully printed PEDOT:PSS-based organic electrochemical transistor (OECT). The device response is based on the modulation of the channel conductivity by the ionic species produced upon urea hydrolysis catalyzed by the entrapped urease. The biosensor shows excellent reproducibility, a limit of detection as low as 1 μM and a response time of a few minutes. The fabrication of the OECTs by screen-printing on flexible substrates ensures a significant reduction in manufacturing time and costs. The low dimensionality and operational voltages (0.5 V or below) of these devices contribute to make these enzymatic OECT-based biosensors as appealing candidates for high-throughput monitoring of urea levels at the point-of-care or in the field.

The key step in the construction of efficient and selective analytical separations or sensors is the design of the recognition interface. Biomimicry of the recognition features typically found in biological molecules, using amino acids, peptides and nucleic acids, provides plausible opportunities to integrate biological molecules or their active sites into a synthetic polymeric backbone. Given the basic role of functional amino acids in biorecognition, we focused on the synthesis of polymerizable amino acid derivatives and their incorporation into a polymer-based biohybrid interface to construct generic bioinspired analytical tools. We also utilized polyvinyl alcohol (PVA) as a sacrificial polymer to adjust the porosity of these biohybrid interfaces. The surface morphologies of the interfaces on gold electrodes were characterized by using scanning electron (SEM) and atomic force (AFM) microscopies. The electrochemical behavior of the polymeric films was systematically investigated using differential pulse voltammetry (DPV) to demonstrate the high affinity of the biohybrid interfaces for Cu(II) ions. The presence of macropores also significantly improved the recognition performance of the interfaces while enhancing interactions between the target [Cu(II) ions] and the functional groups. As a final step, we showed the applicability of the proposed analytical platform to create a Cu(II) ion-mediated supramolecular self-assembly on a quartz crystal microbalance (QCM) electrode surface in real time.

Redox labeled DNAs are of increasing interest for the fabrication of next generation molecular tools. In the present work we are investigating the use of various redox labeled dNTPs, ddNTPs and DNA primers for use in detection of diseases. We have reported the use of Polyoxometalate (POM) labeled DNA primers and dNTPs for use in PCR and subsequently used for direct electrochemical detection of PCR products. The use of POM labeled DNAs in PCR enabled us to check the compatibility with polymerases and PCR incorporability of the modified DNAs. Furthermore we have investigated the solid-phase array based primer extension (é-PEX) with redox labelled ddNTPs (ferrocene (Fc), anthraquinone (AQ) phenothiazine (PTZ) and methylene blue (MB)) to prove the strategy of detection of single nucleotide polymorphisms using the labeled ddNTPs. This strategy will allow the development of cost-effective, rapid and user-friendly platform for the screening of known and unknown genetic mutations.

We describe a composite material for use in electrochemical oxygen reduction. A screen-printed electrode (SPE) was consecutively modified with electrodeposited copper, a Nafion membrane and electropolymerized polyaniline (PANi) to give an electrocatalytic composite of type PANi/Nafion/Cu2O/SPE that displays good electrical conductivity at neutral pH values. It is found that the presence of ammonia causes complex formation with Cu(I), and this causes electroreduction of oxygen to result in an increased cathodic current. The finding was applied to the quantification of ammonium ions in the 1 to 1000 μM concentration range by amperometry at −0.45 V (vs. Ag/AgCl). This Faradaic phenomenon offers the advantage of direct voltammetric detection, one of the lowest known limits of detection (0.5 μM), and high sensitivity (250 mA∙M−1∙cm−2). It was applied to the determination of ammonium ion in human serum where it compared well with the photometric routine approach for clinical analysis using glutamate dehydrogenase. [Figure not available: see fulltext.]

Here we demonstrate the use of a functional dopant as a fast and simple way to tune the chemical affinity and selectivity of polypyrrole films. More specifically, a boronic-functionalised dopant, 4-N-Pentylphenylboronic Acid (PBA), was used to provide to polypyrrole films with enhanced affinity towards diols. In order to prove the proposed concept, two model systems were explored: (i) the capture and the electrochemical detection of dopamine and (ii) the adhesion of bacteria onto surfaces. The chemisensor, based on overoxidised polypyrrole boronic doped film, was shown to have the ability to capture and retain dopamine, thus improving its detection; furthermore the chemisensor showed better sensitivity in comparison with overoxidised perchlorate doped films. The adhesion of bacteria, Deinococcus proteolyticus, Escherichia coli, Streptococcus pneumoniae and Klebsiella pneumoniae, onto the boric doped polypyrrole film was also tested. The presence of the boronic group in the polypyrrole film was shown to favour the adhesion of sugar-rich bacterial cells when compared with a control film (Dodecyl benzenesulfonate (DBS) doped film) with similar morphological and physical properties. The presented single step synthesis approach is simple and fast, does not require the development and synthesis of functional monomers, and can be easily expanded to the electrochemical, and possibly chemical, fabrication of novel functional surfaces and interfaces with inherent pre-defined sensing and chemical properties.

Mobile diagnostics for healthcare, food safety and environmental monitoring, demand a new generation of inexpensive sensing systems suitable for production in high volume. Herein we report on the development of a new disposable electrochemical instrument exploiting the latest advances in printed electronics and printed biosensors. The current system is manufactured under ambient conditions with all interconnections printed; electrochemical measurements and data elaboration are realized by the integration onto the platform of two chips: a MICROCHIP-PIC24F16KA101 and a Texas Instrument's LMP91000. A PEDOT.PSS vertical electrochromic display (VECD) is also incorporated into the system to visualize the data. A printed Enfucell 3V manganese dioxide battery was used to deliver the required power. Finally, in order to demonstrate the utility of the system, screen-printed sensors for the detection of glucose were added and the performance of the overall system was evaluated.