Redox Properties of Ferricyanide Ion on Layer‐by‐Layer Thin Film‐Coated Gold Electrodes; Effects of Type of Polycationic Components in the Film

The surface of a gold (Au) electrode was coated with layer‐by‐layer (LbL) thin films composed of poly(vinyl sulfate) (PVS) and different type of poly(amine)s including poly(allylamine) (PAH), poly(ethyleneimine) (PEI) and poly(diallyldimethylammonium chloride) (PDDA) and redox properties of ferricyanide ion ([Fe(CN)₆]^3?) on the LbL film‐coated Au electrodes were studied. The LbL film‐coated electrodes exhibited redox response to [Fe(CN)₆]^3? ion when the outermost surface of the LbL film was covered with the cationic poly(amine)s while virtually no response was observed on the LbL film‐coated electrodes whose outermost surface was covered with PVS due to an electrostatic repulsion between [Fe(CN)₆]^3? ion and the negatively‐charged PVS layer. The redox properties of [Fe(CN)₆]^3? ion on the LbL film‐coated electrodes significantly depended on the type of polycationic materials in the LbL film. The LbL film‐coated electrodes which had been immersed in the [Fe(CN)₆]^3? solution for 15 min exhibited redox response even in a [Fe(CN)₆]^3? ion‐free buffer solution, suggesting that [Fe(CN)₆]^3? ion is confined in the films. In the buffer solution, redox peaks were observed between +0.1 and 0.4 V depending on the type of polycations in the film. Thus, [Fe(CN)₆]^3? ion can be confined in the film and the redox potential is polycation‐dependent.     

Micropatterning and Impedance Characterization of an Electrically Percolating Layer‐by‐Layer Assembly

Micropatterned layer‐by‐layer (LbL) assemblies were studied as a potential platform for sensor applications by performing impedance characterization throughout a range of electrolyte concentrations. Conductive LbL thin films were prepared with carbon black nanoparticles dispersed in the polymer matrix to provide an electrically conductive network. LbL assemblies were micropatterned using a photolithographic lift‐off method, and a test circuit was constructed as multiple interdigitating coplanar electrodes. Impedance spectra were collected between 10⁴ and 10⁶ Hz within a flow cell containing NaCl solutions ranging from 0.001–1.0 M. These preliminary results demonstrate the ability to pattern conductive LbL composites and underscore the potential utility and shortcomings of their use in sensor applications.     

Picomolar Detection of Melamine Using Molecularly Imprinted Polymer‐Based Electrochemical Sensors Prepared by UV‐Graft Photopolymerization

Molecularly imprinted polymer (MIP) films of melamine were prepared by photopolymerization of vinylic monomers on diazonium‐modified gold electrodes. The gold‐grafted MIPs are specific and selective for melamine in either organic or aqueous media. The interferent molecules cyromazine and cyanuric acid were not recognized by the MIPs. The limit of detection was as low as 1.75×10^?12 mol L^?1 at S/N=3. Efficiency of melamine rebinding is related to the solubility parameter of the organic solvent or pH and ionic strength of the aqueous medium. It is concluded that diazonium salts permit to design robust electrochemical MIP sensors.     

Electropolymerization of iron tetra(<Emphasis Type="Italic">o</Emphasis>-aminophenyl)porphyrin from aqueous solution and the electrocatalytic behavior of modified electrode

Stable electroactive iron tetra(o-aminophenyl)porphyrin (FeTAPP) films are prepared by electropolymerization from aqueous solution by cycling the electrode potential between −0.4 and 1.0 V vs Ag/AgCl at 0.1 V s⁻¹. The cyclic voltammetric response indicates that polymerization takes place after the oxidation of amino groups, and the films could be produced on glassy carbon (GC) and gold electrodes. The film growth of poly(FeTAPP) was monitored by using cyclic voltammetry and electrochemical quartz crystal microbalance. The cyclic voltammetric features of Fe(III)/Fe(II) redox couple in the film resembles that of surface confined redox species. The electrochemical response of the modified electrode was found to be dependent on the pH of the contacting solution with a negative shift of 57 mV/pH. The electrocatalytic behavior of poly(FeTAPP) film-modified electrode was investigated towards reduction of hydrogen peroxide, molecular oxygen, and chloroacetic acids (mono-, di-, and tri-). The reduction of hydrogen peroxide, molecular oxygen, and dichloroacetic acid occurred at less negative potential on poly(FeTAPP) film compared to bare GC electrode. Particularly, the overpotential of hydrogen peroxide was reduced substantially. The O₂ reduction proceeds through direct four-electron reduction mechanism.     

Electrogenerated Chemiluminescence of Tris(2,2′‐bipyridyl)ruthenium(II) Immobilized in Humic Acid‐Silica‐Poly(vinyl alcohol) Composite Films

In this paper, we report the first attempt to use humic acid (HA) as modifiers to prepare the organic‐inorganic hybrid modified glassy carbon electrodes based on HA‐silica‐PVA (poly(vinyl alcohol)) sol‐gel composite. Electroactive species of tris(2,2′‐bipyridyl)ruthenium(II) (Ru(bpy) ) can easily incorporate into the HA‐silica‐PVA films to form Ru(bpy) modified electrodes. The amount of Ru(bpy) incorporated in the composite films strongly depends on the amount of HA in the hybrid sol. Electrochemical and electrogenerated chemiluminescence (ECL) of Ru(bpy) immobilized in HA‐silica composite films coated on a glassy carbon electrode have been studied with tripropylamine (TPA) as the coreactant. The analytical performance of this modified electrode was evaluated in a flow injection analysis (FIA) system with a homemade flow cell. The as‐prepared electrode showed good stability and high sensitivity. The detection limits (S/N=3) were 0.050 μmol L^?1 for TPA and 0.20 μmol L^?1 for oxalate, and the linear ranges were from 0.10 μmol L^?1 to 1.0 mmol L^?1 for TPA and from 1.0 μmol L^?1 to 1.0 mmol L^?1 for oxalate, respectively. The resulting electrodes were stable over two months.     

Ascorbic Acid Oxidation at Nonmodified and Copper‐Modified Polyaniline and Poly‐ortho‐methoxyaniline Coated Electrodes

The electrochemical oxidation of ascorbate ions is comparatively studied at polyaniline (PANI) and poly‐ortho‐methoxyaniline (POMA) layers in absence and presence of electrodeposited copper species. In comparison to PANI, POMA layers allow decreasing the overpotential necessary for driving the ascorbate oxidation reaction. A nonlinear dependence of the ascorbate oxidation current on the polymer layer redox charge is found. Copper electrodeposited in PANI and POMA layers is electrocatalytically active for the investigated reaction. Two separate oxidation waves are observed in the case of Cu‐PANI whereas a single ascorbate oxidation wave and enhanced currents are found in the Cu‐POMA case.     

Long Distance Electron Transfer Across >100 nm Thick Au Nanoparticle/Polyion Films to a Surface Redox Protein

Glutathione‐decorated 5 nm gold nanoparticles (AuNPs) and oppositely charged poly(allylamine hydrochloride) (PAH) were assembled into {PAH/AuNP}_n films fabricated layer‐by‐layer (LbL) on pyrolytic graphite (PG) electrodes. These AuNP/polyion films utilized the AuNPs as electron hopping relays to achieve direct electron transfer between underlying electrodes and redox proteins on the outer film surface across unprecedented distances >100 nm for the first time. As film thickness increased, voltammetric peak currents for surface myoglobin (Mb) on these films decreased but the electron transfer rate was relatively constant, consistent with a AuNP‐mediated electron hopping mechanism.     

Selective Electroanalysis of Ascorbic Acid Using a Nickel Hexacyanoferrate and Poly(3,4‐ethylenedioxythiophene) Hybrid Film Modified Electrode

The mixed‐valent nickel hexacyanoferrate (NiHCF) and poly(3,4‐ethylenedioxythiophene) (PEDOT) hybrid film (NiHCF‐PEDOT) was prepared on a glassy carbon electrode (GCE) by multiple scan cyclic voltammetry. The films were characterized using atomic force microscopy, field emission scanning electron microscopy, energy dispersive spectroscopy, X‐ray diffraction, and electrochemical impedance spectroscopy (AC impedance). The advantages of these films were demonstrated for the detection of ascorbic acid (AA) using cyclic voltammetry and amperometric techniques. The electrocatalytic oxidation of AA at different electrode surfaces, such as the bare GCE, the NiHCF/GCE, and the NiHCF‐PEDOT/GCE modified electrodes, was determined in phosphate buffer solution (pH 7). The AA electrochemical sensor exhibited a linear response from 5×10⁻⁶ to 1.5×10⁻⁴ M (R²=0.9973) and from 1.55×10⁻⁴ to 3×10⁻⁴ M (R²=0.9983), detection limit=1×10⁻⁶ M, with a fast response time (3 s) for AA determination. In addition, the NiHCF‐PEDOT/GCE was advantageous in terms of its simple preparation, specificity, stability and reproducibility.     

Nickel,copper and manganese hexacyanoferrate with poly(3,4-ethylenedioxythiophene) hybrid film modified electrode for selectively determination of ascorbic acid

The NiHCF-PEDOT, CuHCF-PEDOT and MnHCF-PEDOT films were prepared on glassy carbon electrode (GCE) by multiple scan cyclic voltammetry and characterized using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscope (SEM) techniques. The advantages of these films are demonstrated for selectivity detection of ascorbic acid using cyclic voltammetry and amperometric method. Interestingly, the NiHCF-PEDOT and CuHCF-PEDOT modified electrodes exhibited a wide linear response range (5 × 10⁻⁶−3 × 10⁻⁴ M, R ² = 0.9973 and 1.8 × 10⁻³−1.8 × 10⁻² M, R ² = 0.9924). The electrochemical sensors facilitated the oxidation of AA but not responded to other electroactive biomolecules such as dopamine, uric acid, H₂O₂, glucose. The difference is MnHCF-PEDOT/GCE that no response to AA. In addition, the NiHCF-PEDOT and CuHCF-PEDOT modified electrodes exhibited a distinct advantage of simple preparation, specificity, stability and reproducibility.     

Electron transfer through single-crystal silver electrode/<Emphasis Type="Italic">n</Emphasis>-decanthiol monolayer/NaNO<Subscript>3</Subscript> solution interfaces

The kinetics of Ru[(NH₃)₆]³⁺ reduction in 1 M NaNO₃ solution at Ag(210) and Ag(111) singlecrystal electrodes modified by n-decanthiol monolayer is studied by electrochemical impedance spectroscopy and cyclic voltammetry. By using these two methods, standard rate constants of the redox reaction involving Ru[(NH₃)₆]^3+/2+ redox couple in the absence and in the presence of the n-decanthiol film were estimated. The equivalent circuit describing the experimental data in the presence of the self-assembled organic monolayer and in the absence of redox reaction is an electrical circuit comprising a large resistance (∼10⁶ Ω) connected in parallel with a capacitance (∼10⁻⁸ F). Analysis of kinetic data and extrapolation of Tafel lines resulted in the determination of the rate constant at unmodified Ag-electrode, which is characteristic of very fast heterogeneous electron transfer. The calculated rate constants for n-decanthiol-modified silver singlecrystal faces (210) and (111) in 1 M NaNO₃ solution (pH 6.3) equal 4.63 × 10⁻⁵ and 3.05 × 10⁻⁵ cm/s, respectively. The results are compared with the data at hand reported by different authors for gold electrodes in indifferent electrolyte solution in the absence and in the presence of self-assembled monolayer.     

An Air‐breathing Carbon Cloth‐based Screen‐printed Electrode for Applications in Enzymatic Biofuel Cells

We report a prototype air‐breathing carbon cloth‐based electrode that was fabricated starting from a commercially available screen‐printed electrode equipped with a transparent ITO working electrode (DropSens, ref. ITO10). The fabrication of the air‐breathing electrodes is straightforward, shows satisfactory reproducibility and a good electrochemical response as evaluated by means of [Fe(CN)₆]^3?/4? voltammetry. The gas‐diffusion electrodes were successfully modified with the O₂ reducing enzyme bilirubin oxidase from Myrothecium verrucaria in a direct electron transfer regime. The enzyme modified electrodes showed a remarkable high current density for O₂ reduction in passive air‐breathing mode of up to 5 mA cm^?2. Moreover, the enzyme modified electrodes were applied as O₂ reducing biocathodes in a glucose/air enzymatic biofuel cell in combination with a high current density glucose oxidase/redox polymer bioanode. The biofuel cell provides a high maximum power density of (0.34±0.02) mW cm^?2 at 0.25 V. The straightforward design, low cost and the high reproducibility of these electrodes are considered as basis for standardized measurements under gas‐breathing conditions and for high throughput screening of gas converting (bio‐)catalysts.     

Fabrication of Chitosan‐Multiwall Carbon Nanotube Nanocomposite Containing Ferri/Ferrocyanide: Application for Simultaneous Detection of D‐Penicillamine and Tryptophan

We report a simple and effective strategy for fabrication of the nanocomposite containing chitosan (CS) and multiwall carbon nanotube (MWNT) coated on a glassy carbon electrode (GCE). The characterization of the modified electrode (CS‐MWNT/GC) was carried out using scanning electron microscopy (SEM) and UV–vis absorption spectroscopy. The electrochemical behavior of CS‐MWNT/GC electrode was investigated and compared with the electrochemical behavior of chitosan modified GC (CS/GC), multiwalled carbon nanotube modified GC (MWNT/GC) and unmodified GC using cyclic voltammetry (CV) and electron impedance spectroscopy (EIS). The chitosan films are electrochemically inactive; similar background charging currents are observed at bare GC. The chitosan films are permeable to anionic Fe(CN)₆^3?/4? (FC) redox couple. Electrochemical parameters, including apparent diffusion coefficient for the Fe(CN)₆^3?/4? redox probe at FC/CS‐MWNT/GC electrode is comparable to values reported for cast chitosan films. This modified electrode also showed electrocatalytic effect for the simultaneous determination of D‐penicillamine (D‐PA) and tryptophan (Trp). The detection limit of 0.9 μM and 4.0 μM for D‐PA and Trp, respectively, makes this nanocomposite very suitable for determination of them with good sensitivity.     

Study of the Electrochemical Behavior of Disperse Blue 1‐Modified Graphite Electrodes. Application to the Flow Determination of NADH

The preparation and the electrochemical study of Disperse Blue 1‐chemically modified electrodes (DB1‐CME), as well as their efficiency for the electrocatalytic oxidation of NADH is described. The proposed mediator was immobilized by physical adsorption onto graphite electrodes. The electrochemical behavior of DB1‐CME was studied with cyclic voltammetry. The electrochemical redox reaction of DB1 was found to be reversible, revealing two well‐shaped pair of peaks with formal potentials 152 and ?42 mV, respectively, (vs. Ag/AgCl/3M KCl) at pH 6.5. The current I_p has a linear relationship with the scan rate up to 800 mV s^?1, which is indicative for a fast electron transfer kinetics. The dissociation constants of the immobilized DB1 redox couple were calculated pK₁=4 and pK₂=5. The electrochemical rate constants of the immobilized DB1 were calculated k₁°=18 s^?1 and k₂°=23 s^?1 (Γ=2.36 nmol cm^?2). The modified electrodes were mounted in a flow injection manifold, poised at +150 mV (vs. Ag/AgCl/3M KCl) and a catalytic current due to the oxidation of NADH was measured. The reproducibility was 1.4% RSD (n=11 for 30 μM NADH) The behavior of the sensor towards different reducing compounds was investigated. The sensor exhibited good operational and storage stability.     

Layer-by-layer construction of protein architectures through avidin–biotin and lectin–sugar interactions for biosensor applications

In this review, the preparation and properties of protein architectures constructed by layer-by-layer (LbL) deposition through avidin–biotin and concanavalin A (Con A)–sugar interactions are discussed in relation to their use for optical and electrochemical biosensors. LbL films can be constructed through the alternate deposition of avidin and biotin-labeled enzymes on the surfaces of optical probes and electrodes. The enzymes retain their catalytic activity, resulting in the formation of optical and electrochemical biosensors. Alternatively, Con A can be used to construct enzyme-containing LbL films and microcapsules using sugar-labeled enzymes. Some enzymes such as glucose oxidase and horseradish peroxidase can be used for this purpose without labeling with sugar, because these enzymes contain intrinsic hydrocarbon chains on their molecular surfaces. The Con A/enzyme LbL architectures were successfully used to develop biosensors sensitive to specific substrates of the enzyme. In addition, Con A-based films can be used for the optical and electrochemical detection of sugars.     

Glutaraldehyde-modified electrode for nonlabeling voltammetric detection of <Emphasis Type="Italic">p16</Emphasis><Superscript><Emphasis Type="Italic">INK4A</Emphasis></Superscript> gene

A nonlabeling electrochemical detection method for analyzing the polymerase-chain-reaction-amplified sequence-specific p16 ^INK4A gene, in which the basis for the covalent immobilization of deoxyribonucleic acid (DNA) probe is described, has been developed. The self-assembly process was based on the covalent coupling of glutaraldehyde (GA) as an arm molecule onto an amino-functional surface. The p16 ^INK4A gene was used as the model target for the methylation detection of early cancer diagnosis. An amino-modified DNA probe was successfully assembled on the GA-coupling surface through the formation of Schiff base under potential control. The hybridization of amino-modified DNA probes with the target was investigated by means of electrochemical measurements, including cyclic voltammetry and square wave voltammetry. Furthermore, the functions of GA coupling for sequence-specific detection were compared with those obtained based on mercaptopropionic acid. Hybridization experiments indicated that the covalent coupling of GA was suitable for the immobilization of DNA probe and was sensitive to the electrochemical detection of single-base mismatches of label-free DNA targets in hybridization. Moreover, reported probe-modified surfaces exhibited excellent stability, and the hybridization reactions were found to be completely reversible and highly specific for recognition in subsequent hybridization processes. The strategy provided the potential for taking full advantage of existing modified electrode technologies and was verified in microarray technology, which could be applied as a useful and powerful tool in electrochemical biosensor and microarray technology.     

[SiCu(H2O)W11O39]6-在玻碳电极上的多层组装及电催化性能

The electrochemical behavior of SiCu W11 heteropolyacide in acidic aqueous solution was studied. The effect of solution pH on the electrochemical behavior of SiCu W11 was discussed and the mechanism was suggested. New electrode was modified by muhilayer films composed of heteropolyanion (SiCu W11 and cationic polymer poly (diallyldimethylammonium chloride). Cyclic vohammetry showed the uniform growth of the film. The modified electrodes exhibited some special electrochemical properties in the films, different from those in homogeneous aqueous solutions. The effect of pH on the redox behavior of SiCu W11 in the films was discussed in details. The muhilayer film electrodes have an excellent electrocatalytic response to the reduction of BrO3^- and NO2^-.     

Electrochemical determination of <Emphasis Type="Italic">p</Emphasis>-cresol using mesoporous TiO<Subscript>2</Subscript>-modified carbon paste electrode

A mesoporous TiO₂ (meso-TiO₂) was synthesized, and used to prepare modified carbon paste electrode (CPE). The electrochemical sensing properties were characterized using K₃[Fe(CN)₆], showing that meso-TiO₂ modified CPE possesses larger surface area and higher electron transfer rate. The electrochemical behavior of p-cresol was investigated. At the meso-TiO₂ modified CPE, the oxidation peak current of p-cresol remarkably increases, and the oxidation peak potential shifts negatively, suggesting that meso- TiO₂ exhibits highly efficient catalytic activity to the oxidation of p-cresol. Based on this, a sensitive, rapid and convenient electrochemical method was developed for the detection of p-cresol. The linear range is from 1.5 × 10⁻⁷ and 2.0 × 10⁻⁵ mol l⁻¹, and the limit of detection is as low as 8.0 × 10⁻⁸ mol l⁻¹. Finally, the new method was successfully used to determine p-cresol in water samples.     

Comparative studies of solid‐state synthesized poly(o‐methoxyaniline) and poly (o‐toluidine)

Poly(o‐methoxyaniline) (POMA) and poly(o‐toluidine) (POT) salts doped with different acids (methanesulphonic acid (MeSA), trifluoroacetic acid (TFA), and hydrochloric acid (HCl)) were synthesized by using solid‐state polymerization method. The polymers were characterized by Fourier transform infrared (FTIR) spectra, ultraviolet–visible (UV–Vis) spectrometry, X‐ray diffraction (XRD), cyclic voltammetry (CV), and conductivity measurements. Transmission electron microscopy (TEM) was done to study the morphologies of POMA and POT salts. The FTIR and UV‐Vis absorption spectra revealed that the reduced phase was predominant in POMA salts, and the pernigraniline phase was predominant in POT salts. It was found that POMA salts displayed higher doping level and conductivity. In contrast, POT salts were lower at doping levels and conductivity. In accordance with these results, the electrochemical activity was also found to be lower in POT salts. The XRD patterns showed that the POMA salts displayed higher crystallinity than POT salts. The results from TEM revealed that the morphologies of POMA salts were different from those of POT salts. Copyright © 2008 John Wiley & Sons, Ltd.     

Fabrication and the electrochemical activation of network-like MnO<Subscript>2</Subscript> nanoflakes as a flexible and large-area supercapacitor electrode

Porous network-like MnO₂ thick films are successfully synthesized on a flexible stainless steel (SS) mesh using a simple and low-cost electrodeposition method followed by an electrochemical activation process. Morphology, chemical composition, and crystal structure of the prepared electrodes before and after the activation process are determined and compared by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) analyses. The results show that the implementation of the electrochemical activation process does not change the chemical composition and crystal structure of the films, but it influences the surface morphology of the MnO₂ thick layer to a flaky nanostructure. Based on the electrochemical data analysis, the maximum specific capacitance of 1400 mF (381 F g^?1) and 3700 mF (352 F g^?1) are measured for small (2.6 cm²) and large (10 cm²) surface area electrodes, respectively. In addition, a flexible symmetric MnO₂//MnO₂ solid-state supercapacitor shows a capacitance of 0.3 F with about 98% retention at different bending angles from 0 to 360°.     

Modified electrodes with Keggin-type silicotungstates and poly(brilliant cresyl blue)

Electrosynthesis of poly(brilliant cresyl blue) in aqueous solution in the presence of Keggin-type polyoxotungstates, [SiW₁₁Fe(H₂O)O₃₉]^5? or [SiW₁₁Co(H₂O)O₃₉]^6?, was used to prepare modified glassy carbon electrodes. The deposited hybrid organic/inorganic films were studied and characterised by cyclic voltammetry and electrochemical impedance spectroscopy. Cyclic voltammetry showed that the electrochemical features of the polyoxoanions were maintained after immobilisation, with the first tungsten reduction peak involving the uptake of protons from the solution. The chemically modified electrodes were stable, and their preparation was easy to perform. The results provide valuable information for exploring future applications of these films in electrochemical sensors or electrocatalysis.