Electrocatalytic miRNA detection using cobalt porphyrin-modified reduced graphene oxide.

Metalated porphyrins have been described to bind nucleic acids. Additionally, cobalt porphyrins present catalytic properties towards oxygen reduction. In this work, a carboxylic acid-functionalized cobalt porphyrin was physisorbed on reduced graphene oxide, then immobilized on glassy carbon electrodes. The carboxylic groups were used to covalently graft amino-terminated oligonucleotide probes which are complementary to a short microRNA target. It was shown that the catalytic oxygen electroreduction on cobalt porphyrin increases upon hybridization of miRNA strand ("signal-on" response). Current changes are amplified compared to non-catalytic amperometric system. Apart from oxygen, no added reagent is necessary. A limit of detection in the sub-nanomolar range was reached. This approach has never been described in the literature.

Detection of glutamate and acetylcholine with organic electrochemical transistors based on conducting polymer/platinum nanoparticle composites.

The aim of the study is to open a new scope for organic electrochemical transistors based on PEDOT:PSS, a material blend known for its stability and reliability. These devices can leverage molecular electrocatalysis by incorporating small amounts of nano-catalyst during the transistor manufacturing (spin coating). This methodology is very simple to implement using the know-how of nanochemistry and results in efficient enzymatic activity transduction, in this case utilizing choline oxidase and glutamate oxidase.

Copolythiophene-based water-gated organic field-effect transistors for biosensing.

This paper reports on the sensing of proteins using water-gated organic field-effect transistors. As a proof-of-concept, streptavidin and avidin were used, with a biotinylated polymer as the active sensing material. The latter is a copolythiophene modified to graft biotin by peptidic coupling. After characterization of its structure, it was integrated as the channel material into transistors and its interactions with several proteins were investigated. Non-specific interactions were reduced when the polymer surface was pretreated with 1-octanol. In this case, human serum albumin had no effect on the transistor characteristics whereas avidin and streptavidin led to a decrease of the drain current.

Quinone-based polymers for label-free and reagentless electrochemical immunosensors: application to proteins, antibodies and pesticides detection.

Polyquinone derivatives are widely recognized in the literature for their remarkable properties, their biocompatibility, simple synthesis, and easy bio-functionalization. We have shown that polyquinones present very stable electroactivity in neutral aqueous medium within the cathodic potential domain avoiding side oxidation of interfering species. Besides, they can act as immobilized redox transducers for probing biomolecular interactions in sensors. Our group has been working on devices based on such modified electrodes with a view to applications for proteins, antibodies and organic pollutants using a reagentless label-free electrochemical immunosensor format. Herein, these developments are briefly reviewed and put into perspective.

Tuning the threshold voltage in electrolyte-gated organic field-effect transistors.

Low-voltage organic field-effect transistors (OFETs) promise for low power consumption logic circuits. To enhance the efficiency of the logic circuits, the control of the threshold voltage of the transistors are based on is crucial. We report the systematic control of the threshold voltage of electrolyte-gated OFETs by using various gate metals. The influence of the work function of the metal is investigated in metal-electrolyte-organic semiconductor diodes and electrolyte-gated OFETs. A good correlation is found between the flat-band potential and the threshold voltage. The possibility to tune the threshold voltage over half the potential range applied and to obtain depletion-like (positive threshold voltage) and enhancement (negative threshold voltage) transistors is of great interest when integrating these transistors in logic circuits. The combination of a depletion-like and enhancement transistor leads to a clear improvement of the noise margins in depleted-load unipolar inverters.

Advances in organic transistor-based biosensors: from organic electrochemical transistors to electrolyte-gated organic field-effect transistors.

Organic electronics have, over the past two decades, developed into an exciting area of research and technology to replace classic inorganic semiconductors. Organic photovoltaics, light-emitting diodes, and thin-film transistors are already well developed and are currently being commercialized for a variety of applications. More recently, organic transistors have found new applications in the field of biosensors. The progress made in this direction is the topic of this review. Various configurations are presented, with their detection principle, and illustrated by examples from the literature.

Functionalization of single-walled carbon nanotubes for direct and selective electrochemical detection of DNA.

We report here a new strategy to graft both redox and DNA probes on carbon nanotubes to make a label-free DNA sensor. Oxidized single-walled carbon nanotubes are first immobilized on a self-assembled monolayer of cysteamine; then the redox probe, a quinone derivative 3-[(2-aminoethyl)sulfanyl-5-hydroxy-1,4-naphthoquinone], is grafted on the free carboxylic groups of the nanotubes. After that, for DNA probe grafting, new carboxylic sites are generated via an aryl diazonium route. After hybridization with a complementary sequence, the conformational changes of DNA could influence the redox kinetics of quinone, leading to a current increase of the redox signal, detected by square wave voltammetry. The system is selective, as it can discriminate a single mismatched sequence from the complementary one.

Hydroxynaphthoquinone ultrathin films obtained by diazonium electroreduction: toward design of biosensitive electroactive interfaces.

Electroactive 2-(phenylsulfanyl)-8-hydroxy-1,4-naphthoquinone has been electrodeposited via the reduction of the corresponding diazonium salt on Au electrodes. Surface characterizations by X-ray photoelectron spectroscopy (XPS) and infrared reflection-absorption spectroscopy (IRRAS) reveal that the mechanism of film deposition follows an aryl radical formation and its immobilization on the electrode surface. Electrochemical study shows that the surface coverage can be finely tuned (thickness between one and four layers) by adjusting the potential and the deposition time. By managing the potential applied when reducing diazonium in potentiostatic mode, the formed layer could mediate or not charge transfer. This is the first time that the films obtained by diazonium process are demonstrated to act as mediators in the growth process. Hence, with potentials higher than the formal potential of quinone group, very thin and homogeneous layers are obtained, whereas thicker films are formed when more cathodic potentials than that of quinone are applied. The possibility to manage the charge-transfer kinetics, the thickness, and the homogeneity of electroactive deposits is interesting in the scope of designing electrochemical transducers.

Nanometric layers for direct, signal-on, selective, and sensitive electrochemical detection of oligonucleotides hybridization.

We report a signal-on, reagentless electrochemical DNA biosensor, based on an electroactive self-assembled naphthoquinone derivative (JUG(thio)) monolayer. This system achieves highly sensitive (approximately 300 pM) and selective signal-on detection. Before hybridization, the single strand can interact with JUG(thio) and slow down the redox reaction. When the complementary target is added, the formation of the double helix eliminates the single strand/JUG(thio) interactions and the JUG(thio) redox rate, and hence the current increase.

Selectivity and sensitivity of a reagentless electrochemical DNA sensor studied by square wave voltammetry and fluorescence.

Poly(5-hydroxy-1,4-naphthoquinone-co-5-hydroxy-3-thioacetic acid-1,4-naphthoquinone)-modified electrode is used for the direct electrochemical detection of oligonucleotide hybridization. The polymer film presents well-defined electroactivity in the cathodic potential domain (between 0 and -0.8 V/SCE), due to the quinone group embedded into the polymer structure. The detection can be performed simply by square wave voltammetry. This sensor is a "signal-on" device and works with different oligonucleotide lengths, from 10 to 30 bases. Quantitative results from fluorescence are consistent with electrochemical data. It is confirmed that the signal increase in square wave voltammetry is unambiguously due to hybridization. The biosensor presents a detection limit of target of ca. 25 nM and is highly selective as it can discriminate single mismatch base.

DNA electrochemical sensor based on conducting polymer: dependence of the "signal-on" detection on the probe sequence localization.

We show in this work that it is possible to make selective direct electrochemical hybridization detection of a target strand onto a probe strand immobilized on a conducting polymer modified with a quinone group, which presents cation-exchange properties. This leads to a "signal-on"detection, a unique behavior in comparison to similar systems described in the literature. It is shown that this system is efficient for various probe and target lengths (10-30 bp) and can discriminate a single mismatch. To go further in comprehension of the detection mechanism, a systematic study of the electrochemical response versus the probe sequence localization onto the immobilized strand is performed. For example, a 30-bp target strand is divided into three shorter 10-bp sequences (A-C, respectively), and we investigate the successive hybridization of these 1/3 strands onto the 30-bp probe strand. It is shown that one probe strand can be used to address several shorter targets.