Anodic stripping voltammetry of arsenic(III) using gold nanoparticle-modified electrodes

A novel method for the detection of arsenic(III) in 1 M HCl at a gold nanoparticle-modified glassy carbon electrode has been developed. The gold nanoparticles were electrodeposited onto the glassy carbon electrode via a potential step from +1.055 to -0.045 V vs SCE for 15 s from 0.5 M H2SO4 containing 0.1 mM HAuCl4. The resulting electrode surfaces were characterized with both AFM and cyclic voltammetry. Anodic stripping voltammetry of arsenic(III) on the modified electrode was performed. After optimization, a LOD of 0.0096 ppb was obtained with LSV.     

DNA sensing on a DNA probe-modified electrode using ferrocenylnaphthalene diimide as the electrochemically active ligand

Naphthalene diimide derivative 1 carrying ferrocenyl moieties at the termini of imide substituents binds intact calf thymus DNA 4 times more strongly than the denatured DNA, and its complex with the intact DNA dissociates 80 times more slowly than that with the denatured DNA. On the basis of these observations, ligand 1 was applied to a probe of electrochemical DNA sensing. A thiol-linked single-stranded DNA probe was immobilized through the S-Au bonding to 20-30 pmol/mm2 on a gold electrode. Following hybridization with the complementary DNA, the electrode was soaked in a solution containing 1 (intercalation step) and then washed with buffer for 5 s. The cyclic voltammogram and differential pulse voltammogram for this electrode gave an electrochemical signal due to the redox reaction of 1 that was bound to the double-stranded DNA on the electrode. Thus, dA20 and the yeast choline transport gene were quantitated at the subpicomole level. The sensitivity of DNA detection was improved to 10 zmol by reducing the amount of immobilized DNA probe and protecting the uncovered surface of the electrode with 2-mercaptoethanol.     

Introduction of gold nanoparticles into myoglobin-Nafion film for direct electrochemistry application

An effective myoglobin-Nafion film is prepared by introducing gold nanoparticles in through a simple procedure by ion-exchange combined with electrochemical reduction. Gold nanoparticles are highly dispersed in myoglobin-Nafion film with an average size of 2.3 +/- 0.2 nm. The electrochemical behavior of myoglobin entrapped in the film has been carefully investigated with cyclic voltammetry. The results show that the introduction of gold nanoparticles into myoglobin-Nafion film makes the direct electron transfer of myoglobin efficient. A pair of well-defined redox peaks for myoglobin heme Fe(II)/Fe(III) is observed with a formal potential of -0.150 V in 0.1 M phosphate buffer (pH 7.0). The electrochemical parameters of myoglobin in the composite film are further calculated with the results of the electron-transfer rate constant (k(s)) as 0.93 s(-1) and the charge transfer coefficient (alpha) as 0.69. The experimental results also demonstrate that the immobilized myoglobin retains its electrocatalytic activity for the reduction of hydrogen peroxide and the catalytic reduction peak of myoglobin appear in a linear relationship with H2O2 concentration in the range of 10.0-235.0 microM with correlation coefficient of 0.9970. Thus fabricated Au/Mb/Nafion electrode should give a new approach for developing redox protein or enzyme-based biosensors.     

Amperometric determination of hydrazine at manganese hexacyanoferrate modified graphite-wax composite electrode

Fabrication, characterization and application of a manganese hexacyanoferrate (MnHCF) modified graphite-wax composite electrode are described. The MnHCF mixed with graphite powder was dispersed into molten paraffin wax to yield a conductive composite, which was used as electrode material to construct a renewable three-dimensional MnHCF modified electrode. The characterization of the modified electrode has been studied by electrochemical techniques. The cyclic voltammogram of the MnHCF modified graphite-wax composite electrode prepared under optimum composition, showed a well-defined redox couple due to Fe(CN)(6)(4-)/Fe(CN)(6)(3-) system. The electrocatalytic oxidation of hydrazine by MnHCF modified graphite-wax composite electrode has been investigated in an attempt to develop a new sensor for its determination. It was found that the mediator catalyzed the oxidation of hydrazine. The electrocatalytic oxidation of hydrazine was also studied under hydrodynamic and chronoamperometric conditions. The anodic current increases linearly with increase in the concentration of hydrazine in the range of 3.33x10(-5)M to 8.18x10(-3)M. The detection limit was found to be 6.65x10(-6)M (S/N=3). The modified electrode can also be used for on-line detection of hydrazine. The proposed method has also been applied for the determination of hydrazine in photographic developer solution.     

Electrochemical surface plasmon resonance measurement based on gold nanohole array fabricated by nanoimprinting technique

In this paper, we describe our development of an electrochemical surface plasmon resonance (EC-SPR) measurement device based on a bottom-filled gold nanohole array. The polymer based gold nanohole array was fabricated with a UV nanoimprint technique and electron beam gold deposition. Direct reflection mode measurement was used to monitor the SPR dip in the reflection spectra. A cyclic voltammogram was also operated by using the standard three electrodes containing working electrode having a gold nanohole array and counter and reference electrodes. The gold nanohole array was modified with an osmium-poly(vinylpyridine)-wired horseradish peroxidase (Os-gel-HRP) film, and its redox state induced by the change in potential was monitored simultaneously. The redox state of the local film was obtained simply by scanning the sample substrate stage. The substrate modified with Os-gel-HRP film was incorporated in a microfluidic chip, and then the hydrogen peroxide was determined in terms of the redox change in the Os complex mediator from the slope of the SPR dip shift. The linear relation of hydrogen peroxide from 10 to 250 μM was successfully monitored, and a high conversion efficiency was realized.     

Electrochemical fabrication of polyaniline films containing gold nanoparticles deposited on titanium electrode for electro-oxidation of ascorbic acid

Polyaniline films prepared on titanium were employed as substrate for the electrodeposition of gold. The modified electrode was used as anode for the electro-oxidation of ascorbic acid. The electrochemical behavior and electro-catalytic activity of Au/PAni/Ti electrode were characterized by cyclic voltammetry. The morphology of the polyaniline film and gold coating on PAni/Ti electrode were characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) techniques, respectively. Results indicated that gold nanoparticles were homogeneously dispersed on the surface of polyaniline film. The electro-oxidation of ascorbic acid is found to proceed more facile on Au/PAni/Ti electrode than on bare gold electrode. The irreversible oxidation current of ascorbic acid exhibits a linear dependence on the ascorbic acid concentration in the range of 1–5 mM.     

Synthesis and enhanced electrochemical properties of pod-shaped gold/silica nanoparticles

Pod-shaped gold/silica nanoparticles (PGSNPs) were prepared using perfluorooctanoic acid (PFOA) and cetyltrimethylammonium bromide (CTAB) as cotemplates. The PGSNPs were utilized to explore a novel biosensor through coupling myoglobin (Mb) with chitosan (Chi). Compared with Mb-Chi-PSNPs (pod-shaped silica nanoparticles)/GC modified electrode, Mb-Chi-PGSNPs/GC electrode exhibited a pair of much stronger redox peaks at − 0.28 V (vs. Ag/AgCl). Moreover, facilitated direct electron transfer of the metalloenzymes with smaller peak-to-peak separation (ΔEp) of about 46 mV was acquired on the PGSNPs-based enzyme electrode. The PGSNPs-based biosensor demonstrated significant electrocatalytic activity for the reduction of hydrogen peroxide with a wide linear range (1-540 µM) and high sensitivity (661 mA cm^− 2 M^− 1). Together, the Mb-Chi-PGSNPs film is one of ideal candidate materials for direct electrochemistry of redox proteins, and may find potential applications in biomedical, food, and environmental analysis and detection.     

Oxidation-state speciation of

The analytical utility of chemically modified microelectrodes for oxidation-state speciation of redox couples by cyclic voltammetry has been explored. [Re(I)(DMPE)3]+/[Re(II)(DMPE)3]2+, where DMPE = 1,2-bis(dimethylphosphino)ethane, was studied at carbon-fiber microelectrodes of approximately 5 microm in radius coated with Nafion-entrapped solgel-derived silica (Nafion-silica) composite. The results are compared with cyclic voltammetry of [Fe(CN)6]3-/[Fe(CN)6]4- at bare carbon-fiber microelectrodes. At both microelectrodes, the cathodic and anodic limiting currents are linearly proportional to the concentrations of the reducible and oxidizable species of a redox couple, respectively. The shape of the cyclic voltammogram and the magnitude of the steady-state limiting current are not affected by the potential at which the scan starts. Speciation of both forms of a redox couple could be achieved voltammetrically at the microelectrodes. However, a considerably slower scan rate was required to achieve steady state at the modified electrode because of the smaller diffusion coefficients of [Re(I)(DMPE)3]+ and [Re(II)(DMPE)3]2+ in the Nafion-silica composite. The detection limit at the modified electrode was considerably lower (5 x 10(-9) M for [Re(I)(DMPE)3]+) than at the bare electrode (6 x 10(-5) M for [Fe(CN)6]3- and [Fe(CN)6]4-) because of the substantial preconcentration of [Re(I)(DMPE)3]+ by the Nafion-silica composite.     

介孔氧化镍微球的水热-热分解法制备及其在血红蛋白直接电化学检测中的应用

以聚乙二醇-6000为模板剂,Ni(NO3)2.6H2O为镍源,通过微波水热法合成了Ni(OH)2前驱体微球,再采用热分解法最终获得介孔氧化镍微球,并对样品XRD、SEM、TEM和N2吸-脱附等结构表征。利用涂布法以离子液体为粘合剂,制备了固定血红蛋白(Hb)的复合工作电极,并对吸附于膜内的Hb电化学行为进行了研究。结果表明采用水热-热分解法可以获得直径为2.0μm颗粒堆积介孔氧化镍微球,该氧化镍微球具有高的比表面积(234m2/g)和窄的孔径分布(3.25nm)。循环伏安实验表明,在pH值=7.0的磷酸缓冲溶液中,Hb表现出一对峰型良好的准可逆氧化还原峰,为Hb Fe(Ⅲ)/Fe(Ⅱ)电对的特征峰,对其直接电化学行为进行了研究,求出电位为-0.278V(vs Ag/AgCl),电子转移数为1.104,电荷传递系数为0.476,表观异相电子转移速率常数为0.775s-1。     

Multichannel electrochemiluminescence of luminol in neutral and alkaline aqueous solutions on a gold nanoparticle self-assembled electrode

The electrochemiluminescence (ECL) behavior of luminol on a gold nanoparticle self-assembled electrode in neutral and alkaline pH conditions was studied under conventional cyclic voltammetry (CV). The gold nanoparticle self-assembled electrode exhibited excellent electrocatalytic property and redox reactivity to the luminol ECL system. In neutral solution, four ECL peaks were observed at 0.69, 1.03, -0.45, and -1.22 V (vs SCE) on the curve of ECL intensity versus potential. Compared with a bulk gold electrode, two anodic and one cathodic ECL peaks were greatly enhanced, and one new cathodic ECL peak appeared. In alkaline solution, two anodic ECL peaks were obtained at 0.69 and 1.03 V, which were much stronger than those on a bulk gold electrode. These ECL peaks were found to depend on gold nanoparticles on the surface of the electrode, potential scan direction and range, the presence of O(2) or N(2), the pH and concentration of luminol solution, NaBr concentration, and scan rate. The emitter of all ECL peaks was identified as 3-aminophthalate by analyzing the ECL spectra. The spatial distribution of the luminol ECL peaks on the gold nanoparticle self-assembled electrode was studied by CCD. The surface state of the gold nanoparticle self-assembled electrode was characterized by scanning electron microscopy (SEM) and UV-visible reflection spectra. The mechanism for the formation of these ECL peaks has been proposed. The results indicate that the gold nanoparticle self-assembled electrode could lead to novel ECL properties, and strong luminol ECL in neutral and alkaline solutions could be obtained on such an electrode, which is of great analytical potential.     

Graphene/zinc bismuthate nanorods composites and their electrochemical sensing performance for ascorbic acid

Graphene/zinc bismuthate nanorods composites have been prepared using graphene and zinc bismuthate nanorods as the raw materials. The composites are composed of graphene nanosheets with folds and wrinkles and zinc bismuthate nanorods which possesses cubic ZnBi₃₈O₅₈ and hexagonal graphite phases. The zinc bismuthate nanorods are dispersed on the graphene nanosheets. A pair of quasi-reversible redox cyclic voltammogram (CV) peaks exist at the graphene/zinc bismuthate nanorods composites modified glassy carbon electrode. The CV peak current linearly increases with the scan rate from 25?mV?s^?1 to 200?mV?s^?1. The electrochemical response is linear in the ascorbic acid concentration range of 0.0001-2?mM and the detection limit is 0.07?μM. The graphene/zinc bismuthate nanorods composites can be considered as a promising electrode materials to be utilized as the electrochemical sensor.     

Gold/silicon nanocomposites: synthesis,characterization, and application in detection of dopamine

Silicon nanowires (SiNWs) with the length of several hundreds of micrometers and an average diameter of 15 nm were successfully synthesized via a thermal-evaporation oxide-assisted process. Then, a convenient method was applied to metallize the SiNWs just by dipping them into an aqueous deposition solution. During the metallization process, which is a redox reaction, gold nanoparticles (NPs) were prepared on SiNWs surface to confine the particle size and prevent agglomeration during the preparation and utilization of gold NPs. The synthesized SiNWs decorated with gold NPs were utilized to modify the glassy carbon electrode. Electrochemical measurements displayed that the modified electrode showed high sensitivity for dopamine (DA) detection.     

Electrochemically prepared poly(o-phenylenediamine) — Prussian blue composite film for a three-colour expressible ECD material

Both Prussian blue (PB) and poly(o-phenylenediamine) (PoPD) were easily electrodeposited as stable films onto a transparent indium tin oxide (ITO) electrode. The voltammogram of the PB film showed a reversible sharp redox peak current at about 0.25 V. Although the colour change was caused by altering the applied potentials, no colour change was seen after about 10⁴ repetitions. The PoPD film also showed a reversible redox peak current at about –0.05 V. The redox reaction was accompanied by a readily observable colour change between nearly red (vermilion) and colourless. The PoPD film was electrodeposited onto the PB coated electrode to obtain a PB/PoPD composite film. The voltammogram of the film was comprised of the two redox waves of the individual components. The film retained the electrochromic properties of each component and there was no undesirable interference. By changing the potentials, the film exhibited a continuous variety of colours: colourless (-0.2 V), vermilion (0.1 V) and emerald green (0.6 V). The switching time of the colour change was found to be <600 ms. Compared with the PB film, the composite film lasted longer. About 60% of the colouration remained after 10⁵ repetitions since the PoPD worked as a binder which enhanced the adhesion of PB to the electrode surface.     

Preconcentration of f-elements from aqueous solution utilizing a modified carbon paste electrode

An evaluation using paraffin oil based, Acheson 38 carbon paste electrodes modified with α-hydroxyisobutyric acid (HIBA) to preconcentrate f-elements cathodically is described. The modified paste was made by directly mixing solid HIBA into the carbon paste. A chemically reversible cyclic voltammogram for HIBA was observed on this modified carbon paste, which was found to be a non-Nerstian, single electron transfer process. Lanthanides (less promethium) were found to accumulate onto the electrode surface during a 30 s electrodeposition step at -0.4 V vs Ag/AgCl from 0.1 M LiCl. The elements were then stripped off into a 2% HNO(3) solution by an oxidative step at +0.8 V vs Ag/AgCl; quantitative removal from the electrode was confirmed by ICPMS. Ultratrace solutions with initial concentrations down to 5 parts per quadrillion (ppq) were preconcentrated in 5 min above our instrumental limit of detection (LOD) of around 1 ppt for lanthanides.     

Pulse voltammetric and ac impedance spectroscopic studies on lithium ion transfer at an electrolyte/Li4/3Ti5/3O4 electrode interface

Pulse voltammetry and ac impedance spectroscopy were used to study the lithium ion kinetics at a lithium ion insertion electrode consisting of Li4/3Ti5/3O4 thin films in an organic electrolyte. In the cyclic voltammogram, two redox peaks appeared at around 1.56 V vs Li/Li+ due to the insertion and extraction of lithium ion at the electrode. Differential pulse voltammetry gave a large reduction current at approximately 1.56 V during a cathodic scan due to lithium ion insertion into the electrode. From the peak current and potential, the charge-transfer resistance was evaluated by quantitative analysis using approximate equations for irreversible reactions. In the Nyquist plot, one semicircle was observed at 1.56 V, which was assigned to the charge-transfer resistance due to lithium ion transfer at the electrode/electrolyte interface. The value of the charge-transfer resistance at 1.56 V was almost identical to that evaluated by differential pulse voltammetry with an identical characteristic relaxation time. This result shows that both dc differential pulse voltammetry and ac impedance spectroscopy are useful for elucidating the phase transfer kinetics of lithium ion at insertion electrodes.     

泡沫镍负载石墨烯/钯复合电极催化H2O2电还原研究

采用简单的一步浸渍法制备了还原氧化石墨烯-贵金属Pd复合改性的泡沫镍电极,采用X射线衍射和扫描电镜对复合电极的微观结构和表面形貌进行分析,通过循环伏安法、线性伏安法、计时电流法对H₂O₂还原反应的催化活性及稳定性进行了测试。结果表明,石墨烯包覆在泡沫镍骨架表面,在石墨烯内均匀分散着贵金属Pd纳米颗粒,直径约为100nm。该复合电极对H₂O₂电还原表现出较好的催化性能。在1mol/L NaOH+0.5mol/L H₂O₂混合溶液中,电位为-0.5V时,电流密度可达164mA/cm²,同时表现出较好的稳定性。     

Effect of processable polyindole and nanostructured domain on the selective sensing of dopamine

The effect of carboxylic acid functionality present in polymer backbone is reported on electrochemical sensing of dopamine (DA). The electropolymerized conducting polymers made from carboxylic acid substituted indole at positions − 5 and − 6 are found processable in aqueous medium and are compatible with suitable additives/precursors for fabricating polymer modified electrodes (PMEs). The modified electrodes are fabricated following two methods, i.e.: (1) the processable polymers are cast over glassy carbon electrode (GCE) using Nafion® followed by chemical modification using hydrophobic organic redox mediators and (2) the processable polymers are encapsulated within organically modified silicate (Ormosil) matrix along with the hydrophilic redox mediator followed by incorporation of silver and gold nanoparticles. The electrochemical performances of these modified electrodes show selective sensing of DA with major findings: (i) both polymers introduced selectivity in electrochemical sensing of DA with analogous sensitivity, (ii) sensitivity is enhanced when hydrophobic organic redox mediators are coupled with modified electrode matrix involving Nafion®, (iii) the polymers are suitable for encapsulation within ormosil matrix thus introducing nanostructured network for further improvement in sensitivity of DA analysis, (iv) the presence of gold and silver nanoparticles within ormosil matrix along with polymers caused > 100 fold increase in sensitivity of DA sensing with lowest detection limit to the order of 100 nM.     

Electrochemical sensing of sulphur dioxide: a comparison using dodecanethiol and citrate capped gold nanoclusters

A comparison of cyclic voltammograms of dodecanethiol (DDT) capped Au nanoclusters (5.0 0.5 nm) and trisodium citrate (Cit) capped Au nanoclusters (approximately 10-15 nm) modified glassy carbon electrode shows a dramatic variation in the current when exposed to a small amount of sulphur dioxide. This is explained using the electrocatalytic properties of Au nanoclusters towards the oxidation of SO2, thus facilitating the fabrication of electrochemical sensors for the detection of SO2. The intrinsic redox changes observed for gold nanocluster-modified glassy carbon electrodes disappear on passing SO2, despite a dramatic current increase, which indeed scales up with the amount of dissolved SO2. Interestingly, a complete rejuvenation of the redox behavior of gold is also observed on subsequent removal of SO2 from the solution by passing pure nitrogen for 15 minutes. Further, these nanoclusters when characterized with X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) after SO2 passage reveal a variety of SO2 adsorption modes on gold surface. XP spectra also show a shift of 1.03 eV towards higher binding energy indicating a strong adsorption of SO2 gas, while FTIR gives conclusive evidence for the interaction of SO2 with gold nanoparticles.     

Fabrication of a gold nanoparticles decorated carbon nanotubes based novel modified electrode for the electrochemical detection of glucose

A modified electrode based on gold nanoparticles decorated multiwall carbon nanotubes (MWNTs), MWNT-Au(nano)-ME is fabricated. MWNTs are functionalized with 4-aminothiophenol and coated over the glassy carbon electrode. Further, Au nanoparticles are deposited into MWNTs coated GC electrode by electrochemical reduction of HAuCl4. Field emission transmission electron microscope (FETEM) image shows the formation of approximately 5 nm sized Au nanoparticles without any agglomeration on the MWNTs surface. Further, the presence of Au nanoparticles is confirmed through X-ray photoelectron spectroscopic (XPS) studies. The electrocatalytic activity of the MWNT-Au(nano)-ME towards the detection of glucose is investigated. MWNT-Au(nano)-ME shows enhanced current response than pristine MWNT-ME over the entire (+0.05 to +0.80 V) potential range. The modified electrode shows linear response to current with the concentration of glucose between 1 and 20 mM. Larger current responses to glucose oxidation are witnessed at +0.60 V than at +0.05 V. However, a large interference signal, reflecting the accelerated oxidation of electroactive interference is observed at +0.60 V. No overlapping signal from the interferents such as ascorbic acid, acetaminophen, and dopamine are observed at the MWNT-Au(nano)-ME at +0.05 V. Further, the MWNT-Au(nano)-ME shows high resistance to the toxictiy of chloride ions.     

Electrochemical behavior of two and one electron redox systems adsorbed on to micro- and mesoporous silicate materials: Influence of the channels and the cationic environment of the host materials

Electrochemical behavior of two electron redox system, phenosafranine (PS⁺) adsorbed on to micro- and mesoporous materials is investigated by cyclic voltammetry and differential pulse voltammetry using modified micro- and mesoporous host electrodes. Two redox peaks were observed when phenosafranine is adsorbed on the surface of microporous materials zeolite-Y and ZSM-5. However, only a single redox peak was observed in the modified electrode with phenosafranine encapsulated into the mesoporous material MCM-41 and when adsorbed on the external surface of silica. The observed redox peaks for the modified electrodes with zeolite-Y and ZSM-5 host are suggested to be primarily due to consecutive two electron processes. The peak separation ΔE and peak potential of phenosafranine adsorbed on zeolite-Y and ZSM-5 were found to be influenced by the pH of the electrolyte solution. The variation of the peak current in the cyclic voltammogram and differential pulse voltammetry with scan rate shows that electrodic processes are controlled by the nature of the surface of the host material. The heterogeneous electron transfer rate constants for phenosafranine adsorbed on to micro- and mesoporous materials were calculated using the Laviron model. Higher rate constant observed for the dye encapsulated into the MCM-41 indicates that the one-dimensional channel of the mesoporous material provides a more facile micro-environment for phenosafranine for the electron transfer reaction as compared to the microporous silicate materials. The stability of the modified electrode surface was investigated by multisweep cyclic voltammetry.