Functional Enhancement and Characterization of an Electrophysiological Mapping Electrode Probe with Carbonic, Directional Macrocontacts.

Electrophysiological mapping (EM) using acute electrode probes is a common procedure performed during functional neurosurgery. Due to their constructive specificities, the EM probes are lagging in innovative enhancements. This work addressed complementing a clinically employed EM probe with carbonic and circumferentially segmented macrocontacts that are operable both for neurophysiological sensing ("recording") of local field potentials (LFP) and for test stimulation. This paper illustrates in-depth the development that is based on the direct writing of functional materials. The unconventional fabrication processes were optimized on planar geometry and then transferred to the cylindrically thin probe body. We report and discuss the constructive concept and architecture of the probe, characteristics of the electrochemical interface deduced from voltammetry and chronopotentiometry, and the results of in vitro and in vivo recording and pulse stimulation tests. Two- and three-directional macrocontacts were added on probes having shanks of 550 and 770 µm diameters and 10-23 cm lengths. The graphitic material presents a ~2.7 V wide, almost symmetric water electrolysis window, and an ultra-capacitive charge transfer. When tested with clinically relevant 150 µs biphasic current pulses, the interfacial polarization stayed safely away from the water window for pulse amplitudes up to 9 mA (135 µC/cm2). The in vivo experiments on adult rat models confirmed the high-quality sensing of LFPs. Additionally, the in vivo-prevailing increase in the electrode impedance and overpotential are discussed and modeled by an ionic mobility-reducing spongiform structure; this restricted diffusion model gives new applicative insight into the in vivo-uprisen stimulation overpotential.

Plasmon-Enhanced Photoresponse of Self-Powered Si Nanoholes Photodetector by Metal Nanowires.

In this work, we report the development of self-powered photodetectors that integrate silicon nanoholes (SiNHs) and four different types of metal nanowires (AgNWs, AuNWs, NiNWs, PtNWs) applied on the SiNHs' surface using the solution processing method. The effectiveness of the proposed architectures is evidenced through extensive experimental and simulation analysis. The AgNWs/SiNHs device showed the highest photo-to-dark current ratio of 2.1 × 10-4, responsivity of 30 mA/W and detectivity of 2 × 1011 Jones along with the lowest noise equivalent power (NEP) parameter of 2.4 × 10-12 WHz-1/2 in the blue light region. Compared to the bare SiNHs device, the AuNWs/SiNHs device had significantly enhanced responsivity up to 15 mA/W, especially in the red and near-infrared spectral region. Intensity-modulated photovoltage spectroscopy (IMVS) measurements revealed that the AgNWs/SiNHs device generated the longest charge carrier lifetime at 470 nm, whereas the AuNWs/SiNHs showed the slowest recombination rate at 627 nm. Furthermore, numerical simulation confirmed the local field enhancement effects at the MeNWs and SiNHs interface. The study demonstrates a cost-efficient and scalable strategy to combine the superior light harvesting properties of SiNHs with the plasmonic absorption of metallic nanowires (MeNWs) towards enhanced sensitivity and spectral-selective photodetection induced by the local surface plasmon resonance effects.

Two-Dimensional Nanostructures for Electrochemical Biosensor.

Current advancements in the development of functional nanomaterials and precisely designed nanostructures have created new opportunities for the fabrication of practical biosensors for field analysis. Two-dimensional (2D) and three-dimensional (3D) nanomaterials provide unique hierarchical structures, high surface area, and layered configurations with multiple length scales and porosity, and the possibility to create functionalities for targeted recognition at their surface. Such hierarchical structures offer prospects to tune the characteristics of materials-e.g., the electronic properties, performance, and mechanical flexibility-and they provide additional functions such as structural color, organized morphological features, and the ability to recognize and respond to external stimuli. Combining these unique features of the different types of nanostructures and using them as support for bimolecular assemblies can provide biosensing platforms with targeted recognition and transduction properties, and increased robustness, sensitivity, and selectivity for detection of a variety of analytes that can positively impact many fields. Herein, we first provide an overview of the recently developed 2D nanostructures focusing on the characteristics that are most relevant for the design of practical biosensors. Then, we discuss the integration of these materials with bio-elements such as bacteriophages, antibodies, nucleic acids, enzymes, and proteins, and we provide examples of applications in the environmental, food, and clinical fields. We conclude with a discussion of the manufacturing challenges of these devices and opportunities for the future development and exploration of these nanomaterials to design field-deployable biosensors.

From Chip Size to Wafer-Scale Nanoporous Gold Reliable Fabrication Using Low Currents Electrochemical Etching.

We report a simple, scalable route to wafer-size processing for fabrication of tunable nanoporous gold (NPG) by the anodization process at low constant current in a solution of hydrofluoric acid and dimethylformamide. Microstructural, optical, and electrochemical investigations were employed for a systematic analysis of the sample porosity evolution while increasing the anodization duration, namely the small angle X-ray scattering (SAXS) technique and electrochemical impedance spectroscopy (EIS). Whereas the SAXS analysis practically completes the scanning electronic microscopy (SEM) investigations and provides data about the impact of the etching time on the nanoporous gold layers in terms of fractal dimension and average pore surface area, the EIS analysis was used to estimate the electroactive area, the associated roughness factor, as well as the heterogeneous electron transfer rate constant. The bridge between the analyses is made by the scanning electrochemical microscopy (SECM) survey, which practically correlates the surface morphology with the electrochemical activity. The results were correlated to endorse the control over the gold film nanostructuration process deposited directly on the substrate that can be further subjected to different technological processes, retaining its properties. The results show that the anodization duration influences the surface area, which subsequently modifies the properties of NPG, thus enabling tuning the samples for specific applications, either optical or chemical.

A polycarboxylic chelating ligand for efficient resin purification of His-tagged proteins expressed in mammalian systems.

We describe the synthesis of a novel polyamino polycarboxylic ligand, its ability to coordinate metal-ions and attachment to a solid support designed for protein purification through Immobilised Metal-ion Affinity Chromatography (IMAC). The resin was found to be highly efficient for purification of His-tagged HCV E2 glycoproteins expressed in 293T mammalian cells.

Comparative analysis of honey and citrate stabilized gold nanoparticles: In vitro interaction with proteins and toxicity studies.

Gold nanoparticles of comparable size were synthetized using honey mediated green method (AuNPs@honey) and citrate mediated Turkevich method (AuNPs@citrate). Their colloidal behavior in two cell media DMEM and RPMI, both supplemented with 10% FBS, was systematically investigated with different characterization techniques in order to evidence how the composition of the media influences their stability and the development of protein/NP complex. We revealed the formation of the protein corona which individually covers the nanoparticles in RPMI media, like a dielectric spacer according to UV-Vis spectroscopy, while DMEM promotes more abundant agglomerations, clustering together the nanoparticles, according to TEM investigations. In order to evaluate the biological impact of nanoparticles, B16 melanoma and L929 mouse fibroblasts cells were used to carry out the viability assays. Generally, the L929 cells were more sensitive than B16 cells to the presence of gold nanoparticles. Measurements of cell viability, proliferation and apoptotic activities of B16 cells indicated that the effects induced by AuNPs@honey were slightly similar to those induced by AuNPs@citrate, however, the toxic response improved in the L929 fibroblast cells following the treatment with AuNPs@honey within the same concentration range from 1 µg/ml to 15 µg/ml for 48 h. Results showed that honey mediated synthesis generates nanoparticles with reduced toxicity trends depending on the cell type, concentration of nanoparticles and exposure time toward various biomedical applications.

Dataset on large area nano-crystalline graphite film (NCG) grown on SiO2 using plasma-enhanced chemical vapour deposition.

A Si wafer coated with a low temperature oxide (LTO) was used as substrate (Si/SiO2) during the deposition of a thick nano-crystalline graphite (NCG) film by means of plasma-enhanced chemical vapour deposition (PECVD) procedure. The process parameters, the atomic force (AFM) and scanning electron (SEM) micrographs, Raman spectrum and X-ray diffraction (XRD) pattern are herein illustrated. The as deposited NCG film was electrochemically pretreated (3 mA applied current, during 240 s, in 10 mM phosphate buffer saline (PBS) solution containing 0.1 M KCl, pH 7) and thereafter used as electrode for sensing the caffeic acid content in lyophilised berries and dried chokeberries in "Nano-crystalline graphite film on SiO2: Electrochemistry and electro-analytical application" [1].

Tunable photoluminescence from interconnected graphene network with potential to enhance the efficiency of a hybrid Si nanowire solar cell.

An interconnected graphene network (IGN) structure with excellent photoluminescence (PL) properties was synthesized using a one-pot microwave-assisted hydrothermal carbonization route. The material exhibited intense and excitation-wavelength dependent PL emission located mainly in the UV-blue light range (300-450 nm). The result demonstrates that graphene networks could also be included in the emerging class of tunable PL carbon nanomaterials. Furthermore, we have taken a first step towards their incorporation into solar cell devices by fabricating IGN/p-SiNWs radial heterojunctions using the versatile potentiostatic electrodeposition technique. The IGN modified p-SiNW solar cell showed the best performance with an overall enhancement of power conversion efficiency of 7.5 times higher than the reference cell. We emphasize that the structural and electronic characteristics of the as-prepared IGN combined with tapering effects are directly responsible for the tripled short circuit current density and 9% improvement of open circuit voltage with respect to the reference cell. Finally, we have demonstrated that the IGN successfully passivated the Si nanowires' surface using intensity modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS). These promising findings indicate that further IGN exploitation may help to gain efficiency in future energy conversion applications.

High-performance solid state supercapacitors assembling graphene interconnected networks in porous silicon electrode by electrochemical methods using 2,6-dihydroxynaphthalen.

The challenge for conformal modification of the ultra-high internal surface of nanoporous silicon was tackled by electrochemical polymerisation of 2,6-dihydroxynaphthalene using cyclic voltammetry or potentiometry and, notably, after the thermal treatment (800 °C, N2, 4 h) an assembly of interconnected networks of graphene strongly adhering to nanoporous silicon matrix resulted. Herein we demonstrate the achievement of an easy scalable technology for solid state supercapacitors on silicon, with excellent electrochemical properties. Accordingly, our symmetric supercapacitors (SSC) showed remarkable performance characteristics, comparable to many of the best high-power and/or high-energy carbon-based supercapacitors, their figures of merit matching under battery-like supercapacitor behaviour. Furthermore, the devices displayed high specific capacity values along with enhanced capacity retention even at ultra-high rates for voltage sweep, 5 V/s, or discharge current density, 100 A/g, respectively. The cycling stability tests performed at relatively high discharge current density of 10 A/g indicated good capacity retention, with a superior performance demonstrated for the electrodes obtained under cyclic voltammetry approach, which may be ascribed on the one hand to a better coverage of the porous silicon substrate and, on the other hand, to an improved resilience of the hybrid electrode to pore clogging.

Engineering Graphene Quantum Dots for Enhanced Ultraviolet and Visible Light p-Si Nanowire-Based Photodetector.

In this work, a significant improvement of the classical silicon nanowire (SiNW)-based photodetector was achieved through the realization of core-shell structures using newly designed GQDPEIs via simple solution processing. The poly(ethyleneimine) (PEI)-assisted synthesis successfully tuned both optical and electrical properties of graphene quantum dots (GQDs) to fulfill the requirements for strong yellow photoluminescence emission along with large band gap formation and the introduction of electronic states inside the band gap. The fabrication of a GQDPEI-based device was followed by systematic structural and photoelectronic investigation. Thus, the GQDPEI/SiNW photodetector exhibited a large photocurrent to dark current ratio (Iph/Idark up to ∼0.9 × 102 under 4 V bias) and a remarkable improvement of the external quantum efficiency values that far exceed 100%. In this frame, GQDPEIs demonstrate the ability to arbitrate both charge-carrier photogeneration and transport inside a heterojunction, leading to simultaneous attendance of various mechanisms: (i) efficient suppression of the dark current governed by the type I alignment in energy levels, (ii) charge photomultiplication determined by the presence of the PEI-induced electron trap levels, and (iii) broadband ultraviolet-to-visible downconversion effects.

Molybdenum disulphide and graphene quantum dots as electrode modifiers for laccase biosensor.

A nanocomposite formed from molybdenum disulphide (MoS2) and graphene quantum dots (GQDs) was proposed as a novel and suitable support for enzyme immobilisation displaying interesting electrochemical properties. The conductivity of the carbon based screen-printed electrodes was highly improved after modification with MoS2 nanoflakes and GQDs, the nanocomposite also providing compatible matrix for laccase immobilisation. The influence of different modification steps on the final electroanalytical performances of the modified electrode were evaluated by UV-vis absorption and fluorescence spectroscopy, scanning electron microscopy, transmission electron microscopy, X ray diffraction, electrochemical impedance spectroscopy and cyclic voltammetry. The developed laccase biosensor has responded efficiently to caffeic acid over a concentration range of 0.38-100µM, had a detection limit of 0.32µM and a sensitivity of 17.92nAµM(-1). The proposed analytical tool was successfully applied for the determination of total polyphenolic content from red wine samples.

Determination of the antiradical properties of olive oils using an electrochemical method based on DPPH radical.

The present work describes the development of an electrochemical method based on the use of 2,2'-diphenyl-1-picrylhidrazyl free radical (DPPH) for the determination of the antiradical properties of several olive oils. Differential pulse voltammetry was used as measuring technique while the electrochemical process was recorded at a platinum screen-printed working electrode. The decrease in 2,2'-diphenyl-1-picrylhidrazyl peak current intensity was measured at a specific potential value of +160 mV vs. screen-printed pseudo-reference electrode, in the presence of α-, δ- and γ-tocopherol and olive oil samples, respectively. The obtained results using differential pulse voltammetry, as detection technique for real samples analysis, showed a satisfactory agreement with those obtained by high-performance liquid chromatography coupled with fluorescence detection. The reported electrochemical method is rapid and easy to use, feasible and accessible to be used as an alternative to 2,2'-diphenyl-1-picrylhidrazyl spectrophotometric based method.

Disposable biosensor based on platinum nanoparticles-reduced graphene oxide-laccase biocomposite for the determination of total polyphenolic content.

A disposable amperometric biosensor was developed for the detection of total polyphenolic compounds from tea infusions. The biosensor was designed by modifying the surface of a carbon screen-printed electrode with platinum nanoparticles and reduced graphene oxide, followed by the laccase drop-casting and stabilization in neutralised 1% Nafion solution. The obtained biosensor was investigated by scanning electron microscopy and electrochemical techniques. It was observed that platinum nanoparticles-reduced graphene oxide composite had synergistic effects on the electron transfer and increased the electroactive surface area of the carbon screen-printed electrode. The constructed analytical tool showed a good linearity in the range 0.2-2 µM for caffeic acid and a limit of detection of 0.09 µM. The value of Michaelis-Menten apparent constant was calculated from the electrochemical version of Lineweaver-Burk equation to be 2.75 µM. This disposable laccase biosensor could be a valuable tool for the estimation of total polyphenolic content from tea infusions.

Design, fabrication and characterization of a low-impedance 3D electrode array system for neuro-electrophysiology.

Recent progress in patterned microelectrode manufacturing technology and microfluidics has opened the way to a large variety of cellular and molecular biosensor-based applications. In this extremely diverse and rapidly expanding landscape, silicon-based technologies occupy a special position, given their statute of mature, consolidated, and highly accessible areas of development. Within the present work we report microfabrication procedures and workflows for 3D patterned gold-plated microelectrode arrays (MEA) of different shapes (pyramidal, conical and high aspect ratio), and we provide a detailed characterization of their physical features during all the fabrication steps to have in the end a reliable technology. Moreover, the electrical performances of MEA silicon chips mounted on standardized connector boards via ultrasound wire-bonding have been tested using non-destructive electrochemical methods: linear sweep and cyclic voltammetry, impedance spectroscopy. Further, an experimental recording chamber package suitable for in vitro electrophysiology experiments has been realized using custom-design electronics for electrical stimulus delivery and local field potential recording, included in a complete electrophysiology setup, and the experimental structures have been tested on newborn rat hippocampal slices, yielding similar performance compared to commercially available MEA equipments.

Detection of human papilloma viruses using nanostructurated silicon support in microarray technology.

In a typical microarray experiment, DNA is arrayed on a solid substrate as spots, the array being probed with a sample or a capture molecule of interest and the interaction monitored through different detection methods. The present study evaluates the possibility to use micro-array technology to genotype samples with Human Papilloma Viruses (HPV). The performance of DNA microarrays strongly depend on their surface properties. The efficiency of DNA immobilization in terms of sensitivity and specificity is one of the most important step in obtaining a microarray chip for diagnosis of HPV family viruses. Here we report the preparation and evaluation of nano-porous silicon surfaces for HPV detection based on DNA micro-array technique. Two different surfaces based on similar porous structure chemically modified in order to efficiently immobilize ss-DNA specific for HPV viruses were investigate.

Development of an electrochemical biosensor for the detection of aflatoxin M1 in milk.

We have developed an electrochemical immunosensor for the detection of ultratrace amounts of aflatoxin M(1) (AFM(1)) in food products. The sensor was based on a competitive immunoassay using horseradish peroxidase (HRP) as a tag. Magnetic nanoparticles coated with antibody (anti-AFM(1)) were used to separate the bound and unbound fractions. The samples containing AFM(1) were incubated with a fixed amount of antibody and tracer [AFM(1) linked to HRP (conjugate)] until the system reached equilibrium. Competition occurs between the antigen (AFM(1)) and the conjugate for the antibody. Then, the mixture was deposited on the surface of screen-printed carbon electrodes, and the mediator [5-methylphenazinium methyl sulphate (MPMS)] was added. The enzymatic response was measured amperometrically. A standard range (0, 0.005, 0.01, 0.025, 0.05, 0.1, 0.25, 0.3, 0.4 and 0.5 ppb) of AFM(1)-contaminated milk from the ELISA kit was used to obtain a standard curve for AFM(1). To test the detection sensitivity of our sensor, samples of commercial milk were supplemented at 0.01, 0.025, 0.05 or 0.1 ppb with AFM(1). Our immunosensor has a low detection limit (0.01 ppb), which is under the recommended level of AFM(1) [0.05 µg L-1 (ppb)], and has good reproducibility.

Characterization of the gold-catalyzed deposition of silver on graphite screen-printed electrodes and their application to the development of impedimetric immunosensors.

This paper describes the characterization of the gold-catalyzed deposition of silver on graphite screen-printed electrodes (SPEs) using electrochemical impedance spectroscopy (EIS) and the application of this approach to the development of impedimetric immunosensors. After applying -0.1 V for 45 s, the amount of electrodeposited silver quantitatively changes the magnitude of two elements of the electrical equivalent circuit: the interface capacitance, Ci, and the charge-transfer resistance, R(CT). Better correlations have been found when considering the R(CT) since this parameter is almost exclusively dependent on the amount of deposited silver under these experimental conditions. This approach has been successfully applied to the development of an impedimetric immunosensor for aflatoxin M(1). The R(CT) magnitude shows good correlation with the amount of gold immobilized on the electrode surface after a competitive assay and thus, with the toxin concentration. This approach has been found sensitive in a wide range of concentrations, from 15 to 1000 free-AFM(1) ppt with a limit of detection of 12 ppt.

Recent advances in NADH electrochemical sensing design.

NADH electrochemical sensor development has been one of the most studied areas of bioelectroanalysis because of the ubiquity of NAD(P)H based enzymatic reactions in nature. The different solutions proposed are still far from the realisation of the "ideal" NADH sensor and the research area is still challenging. The principles and the recent approaches in NADH electrochemical sensing design are reported in this review. An overview of selected examples and novel sensor materials for the electrocatalysis of NADH is given with emphasis on the appropriate design to obtain improved performances. The literature data taken in consideration has been grouped depending on the strategy used in: surface modified electrodes for NADH sensing, surface redox mediated NADH probes, and bulk modified electrodes for the electrocatalytic oxidation of NADH. A list of already reported dehydrogenase-based biosensors is also given.