Nanoelectrode Ensembles Research Articles

Direct determination of pesticides in vegetable samples using gold nanoelectrode ensembles

Gold nanowires were produced by electrodeposition in polycarbonate membrane, with an average diameter of 200 nm and a height of about 2 μm. The nanowire array prepared by the proposed method can be considered as nanoelectrode ensembles (NEEs). An amperometric pesticides sensor based on gold NEEs has been developed and used for determination of phoxim and dimethoate in vegetable samples. The electrochemical performance of the gold NEEs has also been studied by the amperometric method. The electrode provided a linear response over a concentration range of 5.9 × 10−5 to 1.2 × 10−2 M for phoxim with a detection limit of 4.8 × 10−6 M and 6.3 × 10−5 to 1.1 × 10−2 M for dimethoate. This sensor displayed high sensitivity and selectivity, long-term stability and wide linear range. In addition, the ellipsis of enzyme and the reactivation of enzyme make the operation simple. This sensor has been used to determine pesticides in a real vegetable sample.

Tailor-made gold brush nanoelectrode ensembles modified with l-cysteine for the detection of daunorubicine

A new functionalized l-cysteine surface modified 3D gold brush nanoelectrode assembly BNEE ( l-cys/BNEEs) was prepared. The BNEEs consisted of gold nanowires 100 nm in diameter and up to 400 nm in length fabricated by template synthesis in track etched polycarbonate membranes. The nanowires were exposed by controlled chemical etching of the membrane and were then modified by coating l-cys on the surface of the exposed gold nanowires. The morphology of the BNEEs was imaged by scanning electron microscopy and the real active area of BNEEs was determined by electrochemical impedance spectroscopy. The redox of daunorubicine (DNR) at the l-cys/BNEEs exhibited absorption-controlled characteristics and higher current activity than that at l-cys surface modified 2D disk NEEs ( l-cys/DNEEs). The square wave voltammetry technique was employed to detect DNR. The detection limit was 1.0 × 10 −8 M (s/n = 3). The linear detection concentration range of DNR was from 2.5 × 10 −8 to 4.0 × 10 −7 M.

Gold Nanoelectrode Ensembles for the Simultaneous Electrochemical Detection of Ultratrace Arsenic, Mercury, and Copper

ADVERTISEMENT RETURN TO ISSUEPREVAddition/CorrectionORIGINAL ARTICLEThis notice is a correctionGold Nanoelectrode Ensembles for the Simultaneous Electrochemical Detection of Ultratrace Arsenic, Mercury, and CopperBikash Kumar Jena and C. Retna RajCite this: Anal. Chem. 2008, 80, 14, 5671Publication Date (Web):June 20, 2008Publication History Received5 May 2008Accepted5 May 2008Published online20 June 2008Published inissue 1 July 2008https://doi.org/10.1021/ac8009214Copyright © 2008 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views1266Altmetric-Citations15LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (27 KB) Get e-AlertsSUBJECTS:Arsenic,Copper,Gold,Mercury,Voltammetry Get e-Alerts

Gold Nanoelectrode Ensembles for the Simultaneous Electrochemical Detection of Ultratrace Arsenic, Mercury, and Copper

Simultaneous electrochemical detection of As(III), Hg(II), and Cu(II) using a highly sensitive platform based on gold nanoelectrode ensembles (GNEEs) is described. GNEEs were grown by colloidal chemical approach on thiol-functionalized solgel derived three-dimensional silicate network preassembled on a polycrystalline gold (Au) electrode. GNEEs on the silicate network have been characterized by field emission scanning electron microscopy, X-ray diffraction, diffuse reflectance spectroscopy, and electrochemical measurements. Square wave anodic stripping voltammetry (SWASV) has been used for the detection of As(III) and Hg(II) without any interference from Cu(II) at the potentials of 0.06 and 0.53 V, respectively. The GNEE electrode is highly sensitive, and it shows linear response for As(III) and Hg(II) up to 15 ppb. The detection limit (signal-to-noise ratio = 4) of the GNEE electrode toward As(III) and Hg(II) is 0.02 ppb, which is well below the guideline value given by the World Health Organization (WHO). The potential application of the GNEE electrode for the detection of As(III) in a real sample collected from the arsenic-contaminated water in 24 North Parganas, West Bengal is demonstrated. The GNEE electrode has been successfully used for the simultaneous detection of As(III), Cu(II), and Hg(II) at sub-part-per-billion level without any interference for the first time. The nanostructured electrode shows individual voltammetric peaks for As(III), Cu(II), and Hg(II) at 0.06, 0.35, and 0.53 V, respectively. The analytical performance of the GNEE electrode is superior to the existing electrodes.

Performance evaluation of a capillary electrophoresis electrochemical chip integrated with gold nanoelectrode ensemble working and decoupler electrodes

This paper presents a capillary electrophoresis poly(methyl methacrylate) (PMMA) based microchip for electrochemical detection applications featuring embedded gold nanoelectrode ensemble (GNEE) working and decoupler electrodes. In fabricating the microchip, the GNEE films are pressed directly onto the metallic electrode structures using a hot embossing technique, and the microfluidic channels are then sealed using a low-temperature azeotropic solvent bonding method. The detection performance of the microchip is evaluated using dopamine and catechol analytes for illustration purposes. The experimental results show that the GNEE working electrode provides a significantly higher signal response than that obtained from a bulk gold electrode when applied to the detection of dopamine analyte. Compared to a conventional bulk palladium decoupler electrode, the GNEE decoupler electrode reduces both the amplitude of the charge current (3.5 nA vs. 18.7 nA) and the baseline drift at higher separation voltages. The measured baseline current drift for the microchip equipped the proposed GNEE decoupler electrode is around three times smaller than the microchip with the palladium decoupler electrode under the applied separation electric field from 40 V/cm to 240 V/cm. Finally, when detecting a mixture of 1 mM dopamine and 1 mM catechol, the calculated signal response of the microchip with a GNEE decoupler electrode is approximately five times higher than that obtained from a microchip with a bulk Pd decoupler electrode, resulting in the detection limit of 1 μM for the proposed GNEE-based microchip device. Overall, the results indicate that the proposed capillary electrophoresis-electrochemical detection (CE-ED) microchip with embedded GNEE working and decoupler electrodes provides an ideal solution for sample detection in lab-on-a-chip and micro total analysis applications.

Nanoelectrode ensembles as recognition platform for electrochemical immunosensors

In this study we demonstrate the possibility to prepare highly sensitive nanostructured electrochemical immunosensors by immobilizing biorecognition elements on nanoelectrode ensembles (NEEs) prepared in track-etch polycarbonate membranes. The gold nanodisk electrodes act as electrochemical transducers while the surrounding polycarbonate binds the antibody-based biorecognition layer. The interaction between target protein and antibody is detected by suitable secondary antibodies labelled with a redox enzyme. A redox mediator, added to the sample solution, shuttles electrons from the nanoelectrodes to the biorecognition layer, so generating an electrocatalytic signal. This allows one to fully exploit the highly improved signal-to-background current ratio, typical of NEEs. In particular, the receptor protein HER2 was studied as the target analyte. HER2 detection allows the identification of breast cancer that can be treated with the monoclonal antibody trastuzumab. NEEs were functionalized with trastuzumab which interacts specifically with HER2. The biorecognition process was completed by adding a primary antibody and a secondary antibody labelled with horseradish peroxidase. Hydrogen peroxide was added to modulate the label electroactivity; methylene blue was the redox mediator generating voltammetric signals. NEEs functionalized with trastuzumab were tested to detect small amounts of HER2 in diluted cell lysates and tumour lysates.

Development and Evaluation of Gold 3D Cylindrical Nanoelectrode Ensembles

AbstractGold 3D cylindrical nanoelectrode ensembles (NEEs), 100 nm in diameter and 500 nm in length were prepared by electroless template synthesis in polycarbonate filter membranes, followed by selective controlled chemical etching. The morphology of the nanowires and cylindrical NEEs was imaged by scanning electron microscopy. The protruding nanoelectrodes were in good parallel order. EDX study showed that the nanoelectrode elements consisted of pure gold. The electrochemical evaluation of the 3D electrodes was conducted using the well known [Fe(CN)6]3−/[Fe(CN)6]4− couple. Cyclic voltammgrams (CV) show a very low double layer charging current and a higher ratio of signal to background current than 2D disc NEEs. Electrochemical impedance spectroscopy (EIS) indicates that the 3D cylindrical NEEs effectively accelerate the charge transfer process, which is in consistent with the results of CV. The linear relationship with a slope of 0.5 between lg Ipc and lg v shows that linear diffusion is dominant on the 3D cylindrical NEEs at conventional scan rates.

Towards a Better Understanding of Gold Electroless Deposition in Track-Etched Templates

The template method for preparing nanomaterials entails synthesis of tubular or fibrillar nanostructures within the pores of a microporous membrane. If the holes are completely filled, solid nanowires result, while a partial filling with a continuous coating gives rise to nanotubes. This paper focused on the study of the parameters controlling electroless gold deposition in track-etched polycarbonate membranes. The structure and morphology of the obtained nanomaterials are examined and compared by a variety of electron microscopies and atomic force microscopy and examined in relation to electrochemical and spectrophotometric results. As far as nanotubes are concerned, problems with obtaining such a nanostructure are observed, in particular when membranes with pore diameters equal to or smaller than 30 nm are used. In the case of nanowires, defects related to fabrication problems are evidenced when they are used to prepare nanoelectrode ensembles (NEEs), because defects dramatically influence their voltamm...

Part I: Recent Developments in Nanoelectrodes for Biological Measurements

Biosensors are a type of analytical device that use biological molecules to monitor biorecognition events and interactions. Coupled with the progress in nanotechnologies over recent years, the development of a nanobiosensor based on individual nanoelectrodes and nanoelectrode arrays or nanoelectrode ensembles offers unprecedented avenues for screening and detection at ultrahigh sensitivities. These capabilities provide the basis for a paradigmatic change in biomedical diagnostics and treatment. In this review, we highlight recent developments in nanoelectrode platforms and their suitability for integrating with biological components for the fabrication of ultrasensitive nanobiosensors.

Biosensors based on gold nanoelectrode ensembles and screen printed electrodes

Gold nanowires were synthesized within polycarbonate membranes according to an electroless deposition method, obtaining nanoelectrode ensembles (NEEs) with special electrochemical features. NEEs were coupled with home-produced carbon graphite screen printed electrodes and the electrochemical properties of the original nanoelectrode ensemble on screen printed substrate (NEE/SPS) assembly has been tested for sensors application. Glucose oxidase has been used as model enzyme in order to verify the feasibility of disposable gold NEE/SPS biosensors. Finally, different immobilisation and electrochemical deposition techniques based on either self assembled monolayers of cysteamine (CYS) or amino-propyl-triethoxysilane (APTES) and conductive polyaniline (PANI) molecular wires were used. Spatial patterning of the enzyme on the polycarbonate surface and of PANI wires on gold nanoelectrodes was obtained. Possible direct electron transfer between the enzyme and the PANI modified gold nanoelectrodes has been evaluated.

Poly(methyl methacrylate) microchip device integrated with gold nanoelectrode ensemble for in-column biochemical reaction and electrochemical detection

This paper proposes a poly(methyl methacrylate) (PMMA) based microchip with an integrated gold nanoelectrode ensemble (GNEE) and a quartet-T loading channel for in-column urea/urease reactions and electrochemical detections. The on-chip GNEE electrode is fabricated using an electrodeless deposition process on a thin polycarbonate (PC) film and bonded directly onto a PMMA substrate to carry out high-performance electrochemical detections. The in-column bio-catalytic reaction of urea/urease is successfully demonstrated utilizing a novel approach based on the different electrokinetic mobilities of urea and urease in capillary electrophoresis (CE) channel. The experimental results significantly show that the GNEE electrode provides a better detection response for the reaction product of ammonia (NH 4 +) than a conventional planar gold electrode. The detection results demonstrate a satisfactory determination coefficient ( R 2 value) and high reproducibility with a detection limit of 14.8 and 62.8 μM while detecting standard ammonia solution and the urea/urease reaction product of NH 4 +, respectively. These results confirm the capability of the proposed device for the high-resolution CE-electrochemical detection (CE-ED) of bioanalytical reactions.

Rapid analysis of l-dopa in urine samples using gold nanoelectrode ensembles

This work describes the application of a three-dimensional gold nanoelectrode ensembles (GNEE) for monitoring l-dopa in standards and human urine samples using flow injection analysis (FIA) with amperometric detection. Analytical results reveal that the GNEE exhibited better electrocatalytic activity than a gold disk or glassy carbon electrode. Under optimal conditions of l-dopa analysis at GNEE, the calibration plot has a linear range of 5–300 ng/mL with a coefficient of variation (CV) of 3.1% in pH 7.0 phosphate buffer saline (PBS, pH 7.0). The detection limit was 3.0 ng/mL for FIA. The high precision and sensitivity of GNEE provides a feasible means of directly determining l-dopa in urine samples.

Nanoelectrode ensembles based on semi-interpenetrating network of carbon nanotubes

A method for preparing nanoelectrode ensembles based on semi-interpenetrating network (SIN) of multi-walled carbon nanotubes (MWNTs) on gold electrode through phase-separation method is initially proposed. Individual nanoelectrode owns irregular three-dimensional MWNTs networks, which is denoted as SIN-MWNTs. On the as-prepared SIN-MWNTs nanoelectrode ensembles, the assembled MWNTs clusters in nanoscale serve as individual nanoelectrode and the electroinactive lipid networks located on the top of alkanethiol monolayer are used as a shielding layer. Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), tapping-mode atomic force microscopy (TM-AFM) and scanning electron microscopy (SEM) were used to characterize the as-prepared SIN-MWNT nanoelectrode ensembles. Experimental results indicate that the well-defined nanoelectrode ensembles were prepared through self-assembly technology. Meantime, sigmoid curves in a wide scanning range can be obtained in CV experiments. This study may pave the way for the construction of truly nanoscopic nanoelectrode arrays by bottom-up strategy.

Ultrasensitive Nanostructured Platform for the Electrochemical Sensing of Hydrazine

Ultrasensitive electrochemical detection of hydrazine using nanosized Au particles self-assembled on a sol−gel-derived 3D silicate network is described. The citrate-stabilized gold nanoseeds (GNSs) were self-assembled on the thiol groups of the silicate network, which was preassembled on a polycrystalline Au electrode. The size of the GNSs on the network was enlarged by a seed-mediated growth approach, and the GNSs were characterized by UV−visible spectroscopy, X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), and electrochemical measurements. The enlarged nanoparticles (GNEs) on the silicate network have a size distribution between 70 and 100 nm and behave as a nanoelectrode ensemble. This nanostructured platform is highly sensitive toward the electrochemical oxidation of hydrazine. A very large decrease in the overpotential (∼800 mV) and significant enhancement in the peak currents with respect to the bulk Au electrode were observed without using any redox mediator. The nanos...

Addressable Nanoelectrode Membrane Arrays: Fabrication and Steady-State Behavior

An addressable nanoelectrode membrane array (ANEMA) based on a Au-filled track-etched polycarbonate membrane was fabricated. The Au-filled membrane was secured to a lithographically fabricated addressable ultramicroelectrode (UME) array patterned with 25 regularly spaced (100 microm center to center spacing), 10 microm diameter recessed Pt UMEs to create 25 microregions of 10 microm diameter nanoelectrode ensembles (NEEs) on the membrane. The steady-state voltammetric behavior of 1.0 mM Ru(NH(3))(6)Cl(3) and 1.0 mM ferrocene methanol in 0.1 M KCl on each of the micro NEEs resulted in sigmoidal-shaped voltammograms which were reproducible across the ANEMA. This reproducibility of the steady-state current was attributed to the overlapping hemispherical diffusion layers at the Au-filled nanopores of each 10 microm diameter NEE of a ANEMA. The track-etched polycarbonate membranes were filled using a gold electroless deposition procedure into the 30 nm diameter pores in the membrane. Electrical connection between the Au-filled template array and the lithographic UME platform array was achieved by potentiostatic electrodeposition of Cu from an acidic copper solution into each of the 25 recessed Pt UMEs on the UME array platform. A multiplexer unit capable of addressing 64 individual micro NEEs on an ANEMA is described. ANEMAs have advantages of high reproducibility, facile fabrication, multitime reuse of lithographically fabricated UME arrays, and purely steady-state behavior.

Nanoelectrode ensembles based on conductive polyaniline/poly(acrylic acid) using porous sol–gel films as template

Porous sol–gel (PSG) film has been utilized as a template for the electrochemical polymerization of aniline in presence of poly(acrylic acid) (PAA). The presence of electroactive polyaniline (PAn)/PAA within the porous skeleton of the sol–gel films has been confirmed using cyclic voltammetry, UV–vis spectrometry and atomic force microscopic measurements. The densities and the sizes of the nanoelectrodes can be controlled easily using electrochemical methods. The conductive polymer “wires” of PAn/PAA formation in PSG matrix can behave as an ensemble of closely-spaced but isolated nanoelectrodes. Moreover, the nanoelectrode ensembles based on conductive PAn/PAA for glucose biosensing are fabricated by immobilization of glucose oxidase (GOx) and Nafion onto the surface of conductive polymer. Owing to the biocompatibility of PSG and electro-activity of PAn/PAA at neutral pH regions, the glucose biosensor shows excellent characteristics and performance, such as low detection limit and fast response time.

Electrochemical Biosensor Based on Integrated Assembly of Dehydrogenase Enzymes and Gold Nanoparticles

Development of a highly sensitive nanostructured electrochemical biosensor based on the integrated assembly of dehydrogenase enzymes and gold (Au) nanoparticle is described. The Au nanoparticles (AuNPs) have been self-assembled on a thiol-terminated, sol-gel-derived, 3-D, silicate network and enlarged by hydroxylamine seeding. The AuNPs on the silicate network efficiently catalyze the oxidation of NADH with a decrease in overpotential of approximately 915 mV in the absence of any redox mediator. The surface oxides of AuNP function as an excellent mediator, and a special inverted "V" shape voltammogram at less positive potential was observed for the oxidation of NADH. The AuNP self-assembled sol-gel network behaves like a nanoelectrode ensemble. The nanostructured electrode shows high sensitivity (0.056 +/- 0.001 nA/nM) toward NADH with an amperometric detection limit of 5 nM. The electrode displays excellent operational and storage stability. A novel methodology for the fabrication of a NADH-dependent dehydrogenase biosensor based on the integration of dehydrogenase enzyme and AuNPs with the silicate network is developed. The enzymatically generated NADH is, in turn, electrocatalytically detected by the AuNPs on the silicate network. The integrated assembly has been successfully used for the amperometric biosensing of lactate and ethanol at a potential of -5 mV. The biosensor is very stable and highly sensitive, and it has a fast response time. The excellent performance validates the integrated assembly as an attractive sensing element for the development of new dehydrogenase biosensors.

One step fabrication of nanoelectrode ensembles formed via amphiphilic block copolymers self-assembly and selective voltammetric detection of uric acid in the presence of high ascorbic acid content

A novel one-step approach to glassy carbon nanoelectrode ensembles (NEEs) with the pores of 20–120 nm in radii has been developed using an amphiphilic block copolymer [polystyrene-block-poly (acrylic acid)] self-assembly. This procedure is simple and fast, and requires only conventional, inexpensive electrochemical instrumentation. Electrochemical methods were used to characterize the NEEs prepared using this new procedure. The NEEs drastically suppressed the response of ascorbic acid (AA) and resolved the overlapping voltammetric response of uric acid (UA) and AA into two well-defined peaks with a large anodic peak difference (Δ E pa) of about 310 mV. The peak current obtained from differential pulse voltammetry (DPV) was linearly dependent on the UA concentration in the range of 0.25–50 μM at neutral pH (PBS, pH 6.86) with a correlation coefficient of 0.999, and the detection limit was 0.04 μM (S/N = 3). The NEEs has also been demonstrated to be applicable in the detection of UA in serum and urine samples with excellent sensitivity and selectivity. The NEEs will hopefully be of good application for further sensor development.

Detection of Glucose and Related Analytes by Biosensors: A Fractal Analysis

A fractal analysis is used to model the binding and dissociation kinetics of connective tissue interstitial glucose, adipose tissue interstitial glucose, insulin, and other related analytes on biosensor surfaces. The analysis provides insights into diffusion-limited analyte-receptor reactions occurring on heterogeneous biosensor surfaces. Numerical values obtained for the binding and the dissociation rate coefficients are linked to the degree of heterogeneity or roughness (fractal dimension, Df) present on the biosensor chip surface. The binding and dissociation rate coefficients are sensitive to the degree of heterogeneity on the surface. For example, for the binding of plasma insulin, as the fractal dimension value increases by a factor of 2.47 from Df1 equal to 0.6827 to Df2 equal to 1.6852, the binding rate coefficient increases by a factor of 4.92 from k1 equal to 1.0232 to k2 equal to 5.0388. An increase in the degree of heterogeneity on the probe surface leads to an increase in the binding rate coefficient. A dual-fractal analysis is required to fit the binding kinetics in most of the cases presented. A single fractal analysis is adequate to describe the dissociation kinetics. Affinity (ratio of the binding to the dissociation rate coefficient) values are also presented. Interferents for glucose such as uric acid and ascorbic acid were also detected using glucose biosensors based on carbon nanotube (CNT) nanoelectrode ensembles (NEEs) (29) (Lin, Y.; Lu, F.; Tu, Y.; Ren, Z. Nano Lett. 2004, 4 (2), 191-195). Attempts are made to standardize biosensor properties in terms of diffusion characteristics on in vivo responsiveness.

Nanoelectrode Ensembles Using Carbon Nanopipettes

We demonstrate a simple approach for fabricating nanoelectrode ensembles (NEEs) for nanostructures exhibiting conical morphologies. The fabrication concept utilizes the tapered geometries of carbon nanopipettes (CNPs) and entails one simple, dipcoating step with an insulating polymer to engineer their spatial distribution. After dip-coating, the CNPs in the NEE are separated by several micrometers. Uncoated CNP arrays exhibit peak-shaped behavior in cyclic voltammetry, whereas polymer-coated NEEs yield steady-state, sigmoidal voltammograms over a wide range of scan rates. As-synthesized CNPs could also be employed as templates for synthesizing conical morphologies of other materials to be incorporated into NEEs.