Insights into Structural Behaviors of Thiolated and Aminated Reduced Graphene Oxide Supports to Understand Their Effect on MOR Efficiency.

It is essential to develop novel catalysts with high catalytic activity, strong durability, and good stability for further application in methanol fuel cells. In this work, we present for the first time the effect of the chemical functional groups (thiol and amine) with different electron affinity in reduced graphene oxide supports on the morphology and catalytic activity of platinum nanoparticles for the methanol oxidation reaction. Hydroxyl groups on graphene oxide were initially brominated and then transformed to the desired functional groups. The good dispersion of metal nanoparticles over functionalized carbon substrates (particle size less than 5 nm) with good durability, even at a limited functionalization degree (less than 7%) has been demonstrated by morphological and structural studies. The durability of the catalysts was much improved via strong coordination between the metal and nitrogen or sulfur atoms. Impressively, the catalytic activity of platinum nanoparticles on aminated reduced graphene oxide was found to be much better than that on thiolated graphene oxide despite the weaker affinity between amine and noble metals. These findings support further developing new graphene derivatives with the desired functionalization for electronics and energy applications..

Electrochemical interface based on polydopamine and gold nanoparticles/reduced graphene oxide for impedimetric detection of lung cancer cells.

The use of non-invasive approaches for monitoring therapy processes in cancer patients at late stages is truly needed. In this work, we aim to develop an electrochemical interface based on polydopamine combined with gold nanoparticles and reduced graphene oxide for impedimetric detection of lung cancer cells. Gold nanoparticles (around 75 nm) were dispersed onto reduced graphene oxide material pre-electrodeposited onto disposable fluorine doped tin oxide electrodes. The coordination between gold and carbonaceous material has somehow improved the mechanical stability of this electrochemical interface. Polydopamine was later introduced onto modified electrodes via self-polymerization of dopamine in an alkaline solution. The result has demonstrated the good adhesion and biocompatibility of polydopamine towards A-549 lung cancer cells. The presence of the two conductive materials (gold nanoparticles and reduced graphene oxide) has led to a six-times decrease in charge transfer resistance of polydopamine film. Finally, the as-prepared electrochemical interface was employed for impedimetric detection of A-549 cells. The detection limit was estimated to be only 2 cells per mL. These findings have proved the possibilities to use advanced electrochemical interfaces for point-of-care applications.

An Electrolyte-Gated Graphene Field-Effect Transistor for Detection of Gadolinium(III) in Aqueous Media.

In this work, an electrolyte-gated graphene field-effect transistor is developed for Gd3+ ion detection in water. The source and drain electrodes of the transistor are fabricated by photolithography on polyimide, while the graphene channel is obtained by inkjet-printing a graphene oxide ink subsequently electro-reduced to give reduced graphene oxide. The Gd3+-selective ligand DOTA is functionalized by an alkyne linker to be grafted by click chemistry on a gold electrode without losing its affinity for Gd3+. The synthesis route is fully described, and the ligand, the linker and the functionalized surface are characterized by electrochemical analysis and spectroscopy. The as functionalized electrode is used as gate in the graphene transistor so to modulate the source-drain current as a function of its potential, which is itself modulated by the concentration of Gd3+captured on the gate surface. The obtained sensor is able to quantify Gd3+ even in a sample containing several other potentially interfering ions such as Ni2+, Ca2+, Na+ and In3+. The quantification range is from 1 pM to 10 mM, with a sensitivity of 20 mV dec-1 expected for a trivalent ion. This paves the way for Gd3+ quantification in hospital or industrial wastewater.

Challenges, Prospects, and Emerging Applications of Inkjet-Printed Electronics: A Chemist's Point of View.

Driven by the development of new functional inks, inkjet-printed electronics has achieved several milestones upon moving from the integration of simple electronic elements (e.g., temperature and pressure sensors, RFID antennas, etc.) to high-tech applications (e.g. in optoelectronics, energy storage and harvesting, medical diagnosis). Currently, inkjet printing techniques are limited by spatial resolution higher than several micrometers, which sets a redhibitorythreshold for miniaturization and for many applications that require the controlled organization of constituents at the nanometer scale. In this Review, we present the physico-chemical concepts and the equipment constraints underpinning the resolution limit of inkjet printing and describe the contributions from molecular, supramolecular, and nanomaterials-based approaches for their circumvention. Based on these considerations, we propose future trajectories for improving inkjet-printing resolution that will be driven and supported by breakthroughs coming from chemistry. Please check all text carefully as extensive language polishing was necessary. Title ok? Yes.

Computational Studies of a DNA-Based Aptasensor: toward Theory-Driven Transduction Improvement.

Aptamers are a class of bioreceptors intensively used in current analytical tools dedicated to molecular diagnostics due to their ability to perform large structural reorganization upon target binding. However, there is a lack of methodologies allowing us to rationalize their structure in order to improve the transduction efficiency in aptamer sensors. We choose here, as a model system, a three-strand DNA structure as the probe, composed of two DNA strands anchored on a gold surface and partially hybridized with an aptamer sequence sensitive to ampicillin (AMP). The DNA structure has been designed to show strong structural change upon AMP binding to its aptamer. Using a set of computational techniques including molecular dynamics simulations, we deeply investigated the structure change upon analyte binding, taking into account the grafting on the surface. Original analyses of ion distributions along the trajectories unveil a distinct pattern between both states which can be related to changes in capacitance of the interface between these states. To our knowledge, this work demonstrates the ability of computational investigations for the first time to drive, in silico, the design of aptasensors.

Recent trends in application of nanomaterials for the development of electrochemical microRNA biosensors.

The biology of the late twentieth century was marked by the discovery in 1993 of a new class of small non-coding ribonucleic acids (RNAs) which play major roles in regulating the translation and degradation of messenger RNAs. These small RNAs (18-25 nucleotides), called microRNAs (miRNAs), are implied in several biological processes such as differentiation, metabolic homeostasis, or cellular apoptosis and proliferation. The discovery in 2008 that the presence of miRNAs in body fluids could be correlated with cancer (prostate, breast, colon, lung, etc.) or other diseases (diabetes, heart diseases, etc.) has made them new key players as biomarkers. Therefore, miRNA detection is of considerable significance in both disease diagnosis and in the study of miRNA function. Until these days, more than 1200 miRNAs have been identified. However, traditional methods developed for conventional DNA does not apply satisfactorily for miRNA, in particular due to the low expression level of these miRNA in biofluids, and because they are very short strands. Electrochemical biosensors can provide this sensitivity and also offer the advantages of mass fabrication, low-cost, and potential decentralized analysis, which has wide application for microRNAs sensing, with many promising results already reported. The present review summarizes some newly developed electrochemical miRNA detection methods.

Sensors Made of Natural Renewable Materials: Efficiency, Recyclability or Biodegradability-The Green Electronics.

Nowadays, sensor devices are developing fast. It is therefore critical, at a time when the availability and recyclability of materials are, along with acceptability from the consumers, among the most important criteria used by industrials before pushing a device to market, to review the most recent advances related to functional electronic materials, substrates or packaging materials with natural origins and/or presenting good recyclability. This review proposes, in the first section, passive materials used as substrates, supporting matrixes or packaging, whether organic or inorganic, then active materials such as conductors or semiconductors. The last section is dedicated to the review of pertinent sensors and devices integrated in sensors, along with their fabrication methods.

Designing a magnetic inductive micro-electrode for virus monitoring: modelling and feasibility for hepatitis B virus.

A simple model is designed for an inductive immunosensor in which the magnetic particles are attached to the bioreceptors to form a sandwich on the surface of an inductor. The inductor consists of a coil covered on a silicon oxide wafer. The coil comprises 250 turns of a planar gold wire, which is approximately 200 nm thick and 392 mm long, placed in a circle with a diameter of 2 mm. The model is well characterised by controlling the geometrical and electrical parameters and also the permeability of the magnetic material. To evaluate the feasibility of the model for virus monitoring, a novel inductive immunosensor is designed and for the first time applied for the detection of hepatitis B surface antigen (HBsAg). At first, Fab' segment of primary anti-HBsAg is immobilised on the coil. Then, the coil is exposed to HBsAg and the complex is introduced to a secondary antibody conjugated with magnetic particles to form an immune-sandwich. Finally, the influence of magnetic particles on the coil inductance is recorded and used as a signal for HBsAg detection. The magnetic inductive immunosensor showed specific responses toward HBsAg with the detection limit of 1 ng mL-1, linear range of 1 to 200 ng mL-1, and a sensitivity of 6 × 10-4 mL ng-1. The experimental results showed a very good agreement with simulation data indicating the compatibility of sensor sensitivity to the expected theoretical values. Graphical abstract.

Ionic Liquids as Environmentally Benign Electrolytes for High-Performance Supercapacitors.

Electrochemical capacitors (ECs) are a vital class of electrical energy storage (EES) devices that display the capacity of rapid charging and provide high power density. In the current era, interest in using ionic liquids (ILs) in high-performance EES devices has grown exponentially, as this novel versatile electrolyte media is associated with high thermal stability, excellent ionic conductivity, and the capability to withstand high voltages without undergoing decomposition. ILs are therefore potentially useful materials for improving the energy/power performances of ECs without compromising on safety, cyclic stability, and power density. The current review article underscores the importance of ILs as sustainable and high-performance electrolytes for electrochemical capacitors.

Recent Advances in Skin Chemical Sensors.

This review summarizes the latest developments in the field of skin chemical sensors, in particular wearable ones. Five major applications are covered in the present work: (i) sweat analysis, (ii) skin hydration, (iii) skin wounds, (iv) perspiration of volatile organic compounds, and (v) general skin conditions. For each application, the detection of the most relevant analytes is described in terms of transduction principles and sensor performances. Special attention is paid to the biological fluid collection and storage and devices are also analyzed in terms of reusability and lifetime. This review highlights the existing gaps between current performances and those needed to promote effective commercialization of sensors; future developments are also proposed.

Transistors for Chemical Monitoring of Living Cells.

We review here the chemical sensors for pH, glucose, lactate, and neurotransmitters, such as acetylcholine or glutamate, made of organic thin-film transistors (OTFTs), including organic electrochemical transistors (OECTs) and electrolyte-gated OFETs (EGOFETs), for the monitoring of cell activity. First, the various chemicals that are produced by living cells and are susceptible to be sensed in-situ in a cell culture medium are reviewed. Then, we discuss the various materials used to make the substrate onto which cells can be grown, as well as the materials used for making the transistors. The main part of this review discusses the up-to-date transistor architectures that have been described for cell monitoring to date.

A nanocomposite prepared from FeOOH and N-doped carbon nanosheets as a peroxidase mimic, and its application to enzymatic sensing of glucose in human urine.

A method is described for the synthesis of a nanocomposite containing FeOOH and N-doped carbon nanosheets. The nanocomposite was synthesized by a hydrothermal method using a Fe3O4/chitosan nanocomposite as the precursor. The nanocomposite displays peroxidase-like activity and catalyzes the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2. This results in the formation of a blue colored product with an absorption maximum at 652 nm in the UV-vis spectra. Based on these findings, colorimetric assays were worked out for both hydrogen peroxide and glucose. The H2O2 assay works in the 5 to 19 µM concentration range, and the limit of detection is 5 nM. The glucose assay works in the 8 µM to 0.8 mM concentration range and has a 0.2 µM detection limit. The method was successfully applied to the determination of glucose in human urine. Graphical abstract Schematic of the hydrothermal synthesis of a FeOOH/N-doped carbon nanocomposite. It was used to replace peroxidase enzyme for the catalytic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) in a visual colorimetric test for glucose in human urine.

Switchable Hydrogel-Gated Organic Field-Effect Transistors.

Stimuli-responsive hydrogels represent a class of materials capable of reversibly switching their morphological and physicochemical characteristics. An ultrathin poly(acrylic acid) film (ca. 6 nm) grafted onto the gate of a p-type EGOFET is studied, and the correlation between the swelling state of the hydrogel and the transistor output characteristics is presented. The hydrogel-related swelling process occurring in basic medium causes an increase in threshold voltage due to the abrupt and intense increase of the negative charge density on the gate electrode. The variation of the drain current during the in situ modification of the pH electrolyte allows a quantitative analysis of the hydrogel switching kinetics. This work shows not only the relevance of EGOFET as an analytical tool in the broad sense, i.e., able to follow in real time phase transition processes of stimuli-responsive materials, but also the relevance of using a hydrogel for field-effect-based (bio)detection according to the ability of such material to overcome the well-known Debye length problematics.

Recent Advances in Electrochemical Immunosensors.

Immunosensors have experienced a very significant growth in recent years, driven by the need for fast, sensitive, portable and easy-to-use devices to detect biomarkers for clinical diagnosis or to monitor organic pollutants in natural or industrial environments. Advances in the field of signal amplification using enzymatic reactions, nanomaterials such as carbon nanotubes, graphene and graphene derivatives, metallic nanoparticles (gold, silver, various oxides or metal complexes), or magnetic beads show how it is possible to improve collection, binding or transduction performances and reach the requirements for realistic clinical diagnostic or environmental control. This review presents these most recent advances; it focuses first on classical electrode substrates, then moves to carbon-based nanostructured ones including carbon nanotubes, graphene and other carbon materials, metal or metal-oxide nanoparticles, magnetic nanoparticles, dendrimers and, to finish, explore the use of ionic liquids. Analytical performances are systematically covered and compared, depending on the detection principle, but also from a chronological perspective, from 2012 to 2016 and early 2017.

Molecular Dynamics Simulation of a RNA Aptasensor.

Single-stranded RNA aptamers have emerged as novel biosensor tools. However, the immobilization procedure of the aptamer onto a surface generally induces a loss of affinity. To understand this molecular process, we conducted a complete simulation study for the Flavin mononucleotide aptamer for which experimental data are available. Several molecular dynamics simulations (MD) of the Flavin in complex with its RNA aptamer were conducted in solution, linked with six thymidines (T6) and, finally, immobilized on an hexanol-thiol-functionalized gold surface. First, we demonstrated that our MD computations were able to reproduce the experimental solution structure and to provide a meaningful estimation of the Flavin free energy of binding. We also demonstrated that the T6 linkage, by itself, does not generate a perturbation of the Flavin recognition process. From the simulation of the complete biosensor system, we observed that the aptamer stays oriented parallel to the surface at a distance around 36 Å avoiding, this way, interaction with the surface. We evidenced a structural reorganization of the Flavin aptamer binding mode related to the loss of affinity and induced by an anisotropic distribution of sodium cationic densities. This means that ionic diffusion is different between the surface and the aptamer than above this last one. We suggest that these findings might be extrapolated to other nucleic acids systems for the future design of biosensors with higher efficiency and selectivity.

Versatile transduction scheme based on electrolyte-gated organic field-effect transistor used as immunoassay readout system.

We report on an innovative heterogeneous bisphenol A (BPA) immunoassay based on an electrolyte-gated organic field-effect transistor whose organic semiconductor is poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) co-crystallized with an alkyl derivative of bisphenol A. A decrease of the transistor output current is first observed upon antibody specific binding onto the organic semiconductor. Upon bisphenol A addition, the competitive dissociation of the antibody from the semiconductor surface leads to an opposite increase of the output current. We present here a proof-of-concept for bisphenol A detection; the device could be readily adapted to other small organic molecules of interest and is a promising tool for simple, low-cost, portable and easy-to-use biosensors.

Comparison of Electrochemical Immunosensors and Aptasensors for Detection of Small Organic Molecules in Environment, Food Safety, Clinical and Public Security.

We review here the most frequently reported targets among the electrochemical immunosensors and aptasensors: antibiotics, bisphenol A, cocaine, ochratoxin A and estradiol. In each case, the immobilization procedures are described as well as the transduction schemes and the limits of detection. It is shown that limits of detections are generally two to three orders of magnitude lower for immunosensors than for aptasensors, due to the highest affinities of antibodies. No significant progresses have been made to improve these affinities, but transduction schemes were improved instead, which lead to a regular improvement of the limit of detections corresponding to ca. five orders of magnitude over these last 10 years. These progresses depend on the target, however.

Modified electrodes used for electrochemical detection of metal ions in environmental analysis.

Heavy metal pollution is one of the most serious environmental problems, and regulations are becoming stricter. Many efforts have been made to develop sensors for monitoring heavy metals in the environment. This review aims at presenting the different label-free strategies used to develop electrochemical sensors for the detection of heavy metals such as lead, cadmium, mercury, arsenic etc. The first part of this review will be dedicated to stripping voltammetry techniques, on unmodified electrodes (mercury, bismuth or noble metals in the bulk form), or electrodes modified at their surface by nanoparticles, nanostructures (CNT, graphene) or other innovative materials such as boron-doped diamond. The second part will be dedicated to chemically modified electrodes especially those with conducting polymers. The last part of this review will focus on bio-modified electrodes. Special attention will be paid to strategies using biomolecules (DNA, peptide or proteins), enzymes or whole cells.

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.

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.