Electrochemical characterization of cetyltrimethyl ammonium bromide modified carbon paste electrode and the application in the immobilization of DNA

A cetyltrimethyl ammonium bromide modified carbon paste electrode (CTAB/CPE) was developed in this work based on the surface modification method. The improved electrochemical response of K₄Fe(CN)₆ at this electrode indicated that CTAB could change the surface property of carbon paste electrodes (CPEs), which was demonstrated by the electrochemical impedance spectroscopy (EIS). In 0.1 mM [Fe(CN)₆]^3−/4−, a low exchange current (i₀) of 2.72×10⁻⁷ A at bare CPE was observed while that at CTAB/CPE was 6.79×10⁻⁵ A. The effect of CTAB concentration on the electrode quality revealed that CTAB formed a compact monolayer on the electrode surface with high density of positive charges directed outside the electrode. This electrode showed strong accumulation ability toward Fe(CN)₆⁴⁻ and can also accumulate Co(phen)₃²⁺ by the adsorption of the organic ligands in the hydrophobic area of the monolayer. The electrode was applied to the immobilization of DNA, which was characterized by the isotherm adsorption of Co(phen)₃²⁺.     

Electrooxidation of DNA at glassy carbon electrodes modified with multiwall carbon nanotubes dispersed in polyethylenimine

This work reports the electrochemical response of the complex between dsDNA and PEI formed in solution and at the surface of glassy carbon electrodes (GCE) modified with a dispersion of multi-walled carbon nanotubes in polyethylenimine (CNT-PEI). Scanning Electron Microscopy and Scanning Electrochemical Microscopy demonstrate that the dispersion covers the whole surface of the electrode although there are areas with higher density of CNT and, consequently, with higher electrochemical reactivity. The adsorption of DNA at GCE/CNT-PEI is fast and it is mainly driven by electrostatic forces. A clear oxidation signal is obtained either for dsDNA or a heterooligonucleotide of 21 bases (oligoY) at potentials smaller than those for the oxidation at bare GCE. The comparison of the behavior of DNA before and after thermal treatment demonstrated that the electrochemical response highly depends on the 3D structure of the nucleic acid.     

Tritium redistribution between water and clay minerals

Hydrogen-isotope exchange between clay minerals and tritiated water was studied with kaolinite, montmorillonite and palygorskite. At all possible positions, tritium accumulated most intensively during the initial stage (10 to 20 days) but further increase of tritium concentration in experimental systems was much less intensive. Interaction of tritiated water with clay minerals decreased in a similar manner. In all samples, the highest amounts of tritium atoms and the maximum accumulation rates (V) were observed in the surface-adsorbed water (V_surf) over the complete study period. The modes of tritium accumulation in the interlayer space (montmorillonite) and in the channels (palygorskite) (V_inter) are quite similar and both types of structures are very suitable for hydrogen-isotope exchange. Availability of well-developed paths for the access of T⁺ ions to structural OH-groups (V_struct) enables intense tritium accumulation at these positions in montmorillonite and palygorskite (V_inter  V_struct). In kaolinite the access of T⁺ ions to structural OH-groups is more difficult, in spite of the considerable number of potential exchange positions in its structure, therefore resulting in lower tritium adsorption in comparison with the other two clay minerals.     

Corrosion protection mechanisms of carbon steel by an epoxy resin containing indole-3 butyric acid modified clay

This work is an extension of studies into the mechanisms of corrosion protection of mild steel by an epoxy resin containing organically modified clay (Hang et al. [1]; Truc et al. [2]). In a previous study (Truc et al. [2]), it was shown that indole-3 butyric acid (IBA)-modified clay improved the corrosion performance of epoxy. In the present study, it was shown that the IBA is an anodic inhibitor and its efficiency was about 93%. Exfoliation and dispersion of the IBA-modified clay in the epoxy coating were checked by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The improvement of the corrosion performance of the epoxy coating containing IBA-modified clay by comparison with pure epoxy coating was confirmed for a low film thickness (10 μm). Local electrochemical impedance measurements performed on scratched samples revealed the inhibitive action of IBA at the carbon steel/coating interface. It was shown that the inhibitor release from the IBA-modified clay was favoured for high pH values. Thus, in neutral media, the corrosion process which induces a local increase of pH will increase the self-healing performance.     

Electrochemical behavior of carbon paste electrodes modified with methylene green immobilized on two different X type zeolites

Two new modified carbon paste electrodes (CPEs) based on two different X type zeolites, a natural zeolitic volcanic tuff (NZ) and a NaX type synthetic zeolite (SZ), modified with methylene green (MG) were developed. Cyclic voltammetry measurements revealed a reasonably fast electron transfer rate and a good stability for both investigated electrodes. The observed differences between the electrochemical behavior of MG-NZ-CPEs and MG-SZ-CPEs (the effect of pH on the formal standard potential, the magnitude of the rate constants for heterogeneous electron transfer and electrode response decay) were explained in terms of zeolites structure. The modified electrodes showed moderate electrocatalytic effect towards H₂O₂ reduction and a relatively low limit of detection (0.5 mM for MG-NZ-CPEs).     

碳糊电极和化学修饰碳糊电极制备及应用综述

综述了碳糊电极及化学修饰碳糊电极的发展、制备及表征,概括了近年来化学修饰碳糊电极在食品分析、药物分析、环境监测等领域的应用,并展望了其发展前景。     

Electrokinetic DNA transport in a nanopore membrane

There is tremendous current interest in transporting DNA molecules through nanopores. This interest stems from the possibility of using nanopores for characterization/sequencing, separation, and sensing of DNA. In the presence of a transmembrane electric field, typically used in such applications, DNA chains can be driven through the nanopore via the electrokinetic transport processes of electrophoresis and electroosmotic flow, as well as by diffusion. To our knowledge there have been no quantitative studies of the relative importance of the electrokinetic and diffusive components for DNA transport in a nanopore system. We describe such quantitative studies here. We report on the transport of a series of single-stranded homo-oligonucleotides made of thymidine bases through nanopores in a polycarbonate filter membrane. We show that when an ionic current is passed through the nanopores, transmembrane DNA electrophoresis is the dominant transport process. Finally, the pores in these membranes have conical constrictions at both membrane faces. The effect of this interesting pore geometry on DNA transport is also discussed.     

Electrochemical characterization of screen-printed and conventional carbon paste electrodes

This work compares the electroactivity of a conventional carbon paste electrode and non-pretreated commercially available screen-printed carbon electrodes (from Alderon Biosciences, University of Florence and DropSens) towards some benchmark redox couples like hexaammineruthenium (III), ferricyanide, p-aminophenol and hydroquinone. While cyclic voltammograms of Ru³⁺ did not show significative electron transfer reactivity differences between the electrodes tested, the other redox systems exhibited higher reversible behaviours on DropSens electrodes. Scanning electron microscopy and roughness analysis with a profilometer were applied to detect the surface morphology of the working electrodes. The roughness evaluated of the screen-printed carbon working electrodes increased in this order Alderon < University of Florence < DropSens. Finally, the most electrochemically active and rough unpretreated electrode (DropSens commercial screen-printed electrode) was used to study the electrochemical-chemical reaction mechanism of indigo carmine oxidation in 0.1 M sulphuric acid. This study showed that the adsorption of the oxidation product of indigo carmine is stabilized when it is adsorbed on the surface of the electrode.     

Zinc ion-imprinted polymer based on silica particles modified carbon paste electrodes for highly selective electrochemical determination of zinc ions

ABSTRACT

In this study, Zn(II) ion-imprinted polymer was prepared on the surface of vinyl silica particles and applied for detection of Zn(II) ions using differential pulse voltametry. The ion- imprinted polymer particles were prepared by free radical polymerization. The prepared particles were characterized by different morphological and elemental techniques. The ion-imprinted particles were used to fabricate the carbon paste electrode as a zinc ions sensor. The modified zinc sensor showed linear response in the concentration range 6.12 × 10^?9 to 4.59 × 10^?8 mol L^?1. The limit of detection and limit of quantification of the electrode were 1.351 × 10^?8 and 4.094 × 10^?8 mol L^?1, respectively.     

Electrochemical sensor array made from bisphthalocyanine modified carbon paste electrodes for discrimination of red wines

A new sensor system devoted to the discrimination of red wines is presented. It consists of an array of electrochemical sensors made from carbon paste electrodes modified with three rare-earth bisphthalocyaninate compounds, including lutetium(III), gadolinium(III) and praseodymium(III) bisphthalocyaninates. The sensor responses have been evaluated either by cyclic voltammetry or by square wave voltammetry, and demonstrate that such voltammetric sensors show a rich response when immersed in red wines. In addition, this response can be tuned by changing the central metal atom of the double-decker complexes, obtaining sensing units with high cross-selectivity.

The sensor array is exposed to six Spanish red wines made from the same grape variety, prepared using a similar vinification method, but belonging to three different geographic origins and ageing stages. The voltammograms indicate that each sensing unit provides a particular response to each class of wine.

Finally, the signals coming from each sensor are combined and the system’s discrimination capability is evaluated by using principal component analysis (PCA), where a windowed slicing pre-processing method has been developed to capture the information throughout the global response. The PCA score plots of the obtained data show the discrimination of the tested wines with a good-quality performance.     

Zinc(II) modified carbon paste electrodes based on self-assembled mercapto compounds-gold-nanoparticles for its determination in water samples

In the present study newly developed potentiometric sensors for determination of zinc(II) are presented. The proposed potentiometric method was based on the fabrication of modified carbon paste (MCPE; electrode X) and modified gold nanoparticles-carbon paste (GNPs-CPE; electrode IX) sensors. A mercapto compound of 1,4-bis(5-mercaptopentyloxy)-benzene (BMPB) alone or self-assembled on gold nanoparticles was used as modifier to construct electrode (X) and electrode (IX) sensors, respectively. The prepared electrodes exhibit Nernstian slope of 29.93 ± 0.4 and 26.0 ± 1.02 mV decade⁻¹ towards Zn(II) ion over a wide concentration range of 6.8 × 10⁻¹⁰ to 2.9 × 10⁻² and 1.0 × 10⁻⁷ to 1.0 × 10⁻² mol L⁻¹ for electrode (IX) and electrode (X) sensors, respectively. The limit of detection of the electrode (IX) and electrode (X) sensors was found to be 6.8 × 10⁻¹⁰ and 1.0 × 10⁻⁷ mol L⁻¹, respectively. The potentiometric response of the electrode (IX) and electrode (X) based on GNPs-BMPB and BMPB are independent of pH of test solution in the pH range of 2.5–8.1 and 3–7 with a response time of 6 and 8 s for electrode (IX) and electrode (X) sensors, respectively. The proposed sensors showed fairly good discriminating ability towards Zn(II) ion in comparison with many hard and soft metal ions. Finally, the proposed electrodes were successfully used as indicator electrodes in potentiometric titration of zinc ion with sodium tetraphenylborate (NaTPB) and in direct determination of Zn(II) ion in some water samples. The results obtained compared well with those obtained using atomic absorption spectrometry.     

Powdered activated carbon and carbon paste electrodes: comparison of electrochemical behaviour

Commercial activated carbon (Norit R3ex), de-mineralised with conc. HF and HCl, was oxidised (conc. HNO₃) and heat-treated at various temperatures (180, 300 and 420 °C). The physicochemical properties of the samples obtained were characterised by selective neutralisation and pH-metric titration of surface functional groups (acid–base properties), thermogravimetry (thermal stability—TG), FTIR spectroscopy (chemical structure) and low-temperature nitrogen adsorption (BET surface area). Thermal treatment of the carbon materials caused the surface functional groups to decompose; in consequence, the chemical properties of the carbon surfaces changed. Cyclic voltammetric studies were carried out on all samples using a powdered activated carbon electrode (PACE) and a carbon paste electrode (CPE), as were electrochemical measurements in aqueous electrolyte solutions (0.1 M HNO₃ or NaNO₃) in the presence of Cu²⁺ ions acting as a depolariser. The shapes of the cyclic voltammograms varied according to the form of the electrodes (powder or paste) and to the changes in the surface chemical structure of the carbons. The electrochemical behaviour of the carbons depended on the presence of oxygen-containing surface functional groups. The peak potentials and their charge for the redox reactions of copper ions depended on their interaction with the carbon surface.     

Covalent attachment of single-stranded DNA to carbon paste electrode modified by activated carboxyl groups

A new method of the electrode modification and DNA immobilization for a biosensor is reported. Outer layer of a conventional carbon paste electrode (CPE) was modified with carboxyl groups by mixing stearic acid with the paste. Single-stranded deoxyribonucleic acid was attached to the modified electrode through a linker - ethylenediamine. Immobilization process was performed in the presence of activators - water soluble 1-ethyl-3(3′-dimethylaminopropyl)-carbodiimide (EDC) and N-hydroxysulfosuccinimide (NHS). Stearic acid concentration and other experimental parameters of the procedure were optimized. Covalent immobilization of DNA on the electrode surface exhibits some advantages as compared to simple adsorption mainly due to the fact that nucleic acid chains are bound to an electrode surface by one end only and it ensures structural flexibility and increases hybridization without DNA leakage. Modified electrode with immobilized (21-mer) oligonucleotide as a specific probe was successfully applied in preliminary investigations for the detection of bar gene commonly used in genetically modified food.     

化学修饰碳糊电极的研究新进展

碳糊电极和化学修饰碳糊电极在电化学研究中起着非常重要的作用,综述了近年来化学修饰碳糊电极的优势及劣势、制备及应用,且分析了修饰剂的选择,最终对其进行了展望。     

Nickel-dimethylglyoxime complex modified graphite and carbon paste electrodes: preparation and catalytic activity towards methanol/ethanol oxidation

Nickel-dimethylglyoxime complex (abbreviated as Ni(II)(DMG)₂) modified carbon paste and graphite electrodes were prepared by mixing Ni(II)(DMG)₂ with graphite paste, and coating Ni(II)(DMG)₂ to the graphite surface. It is necessary to cycle the electrode potential to a high value (e.g. 0.8 V versus SCE) for the preparation of the modified electrodes. The electrochemical reaction was originally assumed to be a one-electron process converting Ni(II)(DMG)₂ to [(DMG)₂(H₂O)Ni(III)ONi(III)(OH)(DMG)₂]⁻. [(DMG)₂(H₂O)Ni(III)ONi(III)(OH)(DMG)₂]⁻ showed a strong catalytic activity toward electro-oxidation of methanol and ethanol. The electrocatalytic oxidation currents consistently increase with the increase in Ni(II)(DMG)₂ loading, OH⁻, and alcohol concentrations. Rotating disk electrode results obtained with a Ni(II)(DMG)₂ coated graphite disk electrode showed that the electrocatalytic oxidation of alcohol is a 4-electron process producing formate anion (methanol oxidation) or acetate anion (ethanol oxidation). A mechanism for the electrocatalytic oxidation of methanol/ethanol was proposed, and a rate-determining step was also discussed.     

Heterogeneous oligonucleotide-hybridization assay based on hot electron-induced electrochemiluminescence of a rhodamine label at oxide-coated aluminum and silicon electrodes

This paper describes a heterogeneous oligonucleotide-hybridization assay based on hot electron-induced electrochemiluminescence (HECL) of a rhodamine label. Thin oxide-film coated aluminum and silicon electrodes were modified with an aminosilane layer and derivatized with short, 15-mer oligonucleotides via diisothiocyanate coupling. Target oligonucleotides were conjugated with tetramethylrhodamine (TAMRA) dye at their amino modified 5′ end and hybridization was detected using HECL of TAMRA. Preliminary results indicate sensitivity down to picomolar level and low nonspecific adsorption. The sensitivity was better on oxide-coated silicon compared to oxide-coated aluminum electrodes and two-base pair mismatched hybrids were successfully discriminated. The experimental results presented here might be useful for the design of disposable electrochemiluminescent DNA biosensors.     

Comparative investigation on electrochemical behavior of hydroquinone at carbon ionic liquid electrode, ionic liquid modified carbon paste electrode and carbon paste electrode

Ionic liquid, 1-heptyl-3-methylimidazolium hexafluorophosphate (HMIMPF₆), has been used to fabricate two new electrodes, carbon ionic liquid electrode (CILE) and ionic liquid modified carbon paste electrode (IL/CPE), using graphite powder mixed with HMIMPF₆ or the mixture of HMIMPF₆/paraffin liquid as the binder, respectively. The electrochemical behaviors of hydroquinone at the CILE, the IL/CPE and the CPE were investigated in phosphate buffer solution. At all these electrodes, hydroquinone showed a pair of redox peaks. The order of the current response and the standard rate constant of hydroquinone at these electrodes were as follows: CILE > IL/CPE > CPE, while the peak-to-peak potential separation was in an opposite sequence: CILE < IL/CPE < CPE. The results show the superiority of CILE to IL/CPE and CPE, and IL/CPE to CPE in terms of promoting electron transfer, improving reversibility and enhancing sensitivity. The CILE was chosen as working electrode to determine hydroquinone by differential pulse voltammetry, which can be used for sensitive, simple and rapid determination of hydroquinone in medicated skin cosmetic cream.     

碳纳米管修饰电极的研究进展

化学修饰电极如今在电化学和电分析化学中应用极为广泛。综述了碳纳米管的结构和性能,介绍了碳纳米管修饰电极的制备及应用。     

The pH-dependence of oxygen reduction on multi-walled carbon nanotube modified glassy carbon electrodes

The pH-dependence of oxygen electroreduction has been investigated on multi-walled carbon nanotube (MWCNT) modified glassy carbon (GC) electrodes. Various surfactants were used in the electrode modification: dihexadecyl hydrogen phosphate, cetyltrimethylammonium bromide, sodium dodecyl sulfate and Triton X-100. Electrochemical experiments were carried out in 0.5 M H₂SO₄ solution, acetate buffer (pH 5), phosphate buffers (pH 6, 7 and 8), borate buffer (pH 10), 0.01 M KOH, 0.1 M KOH and in 1 M KOH solution, using the rotating disk electrode (RDE) method. The oxygen reduction behaviour of MWCNT-modified GC electrodes at different pHs was compared. The RDE results revealed that the half-wave potential (E_1/2) of oxygen reduction was higher in solutions of high pH. At lower pHs (pH < 10) the value of E_1/2 did not essentially depend on the solution pH. A comparison with previous studies on bare GC showed that the pH-dependence of the half-wave potential of oxygen reduction on MWCNT-modified GC electrodes follows a similar trend to that observed for bare GC.     

Enhanced electrochemical reduction of hydrogen peroxide on silver paste electrodes modified with surfactant and salt

The modification of silver paste electrodes with a combination of dodecylbenzenesulfonic acid and KCl has been shown to lead to significant enhancements of the electrochemical reduction of hydrogen peroxide. The catalytic enhancement was shown to be dependent on the concentration of the surfactant/salt solution, which resulted in increases of some 80-fold in amperometric response to hydrogen peroxide at −0.1 V vs Ag/AgCl, pH 6.8 over unmodified silver paste. Physical analysis showed modifications to both the surface morphology and chemical composition of the silver paste electrode surface. However, BET and electrochemical analysis revealed no significant change in surface area. It is suggested that the enhanced catalysis may result from the formation of stabilised surfactant/salt structures at the metal electrode surface. The electrode was also shown to be suitable for the amperometric detection of hydrogen peroxide with a limit of detection of 1.1 × 10⁻⁶ M (S/N = 3).