Direct electrochemistry and electrocatalytic activity of cytochrome c covalently immobilized on a boron-doped nanocrystalline diamond electrode

Cytochrome c (Cyt c) was covalently immobilized on a boron-doped nanocrystalline diamond (BDND) electrode via surface functionalization with undecylenic acid methyl ester and subsequent removal of the protecting ester groups to produce a carboxyl-terminated surface. Cyt c-modified BDND electrode exhibited a pair of quasi-reversible and well-defined redox peaks with a formal potential (E(0)) of 0.061 V (vs Ag/AgCl) in 0.1 M phosphate buffer solution (pH 7.0) and a surface-controlled process with a high electron transfer constant (ks) of 5.2 +/- 0.6 s(-1). The electrochemical properties of as-deposited and Cyt c-modified boron-doped microcrystalline diamond (BDMD) electrodes were also studied for comparison. Investigation of the electrocatalytic activity of the Cyt c-modified BDND electrode toward hydrogen peroxide (H2O2) revealed a rapid amperometric response (5 s). The linear range of response to H2O2 concentration was from 1 to 450 microM, and the detection limit was 0.7 microM at a signal-to-noise ratio of 3. The stability of the Cyt c-modified BDND electrode, in comparison with that of the BDMD and glassy carbon counterpart electrodes, was also evaluated.     

Electrochemical oxidation of pulp and paper making wastewater assisted by transition metal modified kaolin

The electrochemical oxidation of pulp and paper making wastewater assisted by transition metal (Co, Cu) modified kaolin in a 200 ml electrolytic batch reactor with graphite plate as electrodes was investigated. H(2)O(2), which produced on the surface of porous graphite cathode, would react with the catalysts to form strong oxidant (hydroxyl radicals) that can in turn destroy the pollutants adsorbed on the surface of kaolin. The transition metal (Co, Cu) modified kaolin was also characterized by XRD and SEM before and after the modification and the results showed that the transition metals were completely supported on kaolin and formed a porous structure with big BET surface. The mechanism was proposed on the basis of XPS analysis of the catalyst after the degradation process. Series of experiments were also done to prove the synergetic effect of the combined oxidation system and to find out the optimal operating parameters such as initial pH, current density and amount of catalyst. From the results it can be founded that when the initial pH was at 3, current density was 30 mA cm(-2); catalyst dose was 30 g dm(-3), COD (chemical oxygen demand) removal could reach up to 96.8% in 73 min.     

Remediation of metal-contaminated aqueous systems by electrochemical peroxidation: an experimental investigation

An innovative technology, electrochemical peroxidation (ECP), was investigated for remediation of mixed metal-contaminated aqueous systems by application of direct electric current to steel electrodes and of dilute H(2)O(2) solution to promote Fenton's reactions, forming sparingly soluble solid hydrous ferric oxides (HFO). Bench scale experiments evaluated the sorption and distribution of As, Be, Cd, Cr, Cs, Cu, Li, Ni, Pb, Se, V, and Zn among the soluble and solid state HFO formed as part of the ECP process. The effects of pH, hydrogen peroxide concentrations and electric current process times on the efficiency of metal removal were studied. The potential of this technology was demonstrated by effective removal at pH 3.5-4.6 and within 3 min of 0.25 A dc+100 mg H(2)O(2) l(-1), of As, Cr, Pb, Se and V with complete removal of As and Cr, >95.0%. On increasing the pH of the solution to 6.0, the retention of Be and Cu by HFO increased from 0.9-1.9% at pH 3.5 to 76.8-80.7% at pH 6.0 while concentrations of other metals, such as Pb, decreased due to precipitation of Pb hydroxy-complexes. Experiments in the absence of H(2)O(2) revealed that metals were adsorbed by HFO with the same order of affinity, As>Cr>Se>V>Be, as in the presence of H(2)O(2), but, with the exception of Cr, to a lesser extent. H(2)O(2) used in the ECP process was fundamental to increase the adsorption capacity of HFO for As, from 79.2 to 99.2%, due to the oxidation of As(III) to As(V), which has a stronger affinity for HFO. The reduced adsorption may be related to the formation of poorly ordered crystalline akaganeite, which has a lower surface area than ferrihydrite formed when H(2)O(2) was used. The optimal operating conditions were pH<6.0, an H(2)O(2) concentration of 100 mg l(-1) and a current process time not exceeding 3 min.     

Standard electrochemical behavior of high-quality, boron-doped polycrystalline diamond thin-film electrodes

Standard electrochemical data for high-quality, boron-doped diamond thin-film electrodes are presented. Films from two different sources were compared (NRL and USU) and both were highly conductive, hydrogen-terminated, and polycrystalline. The films are acid washed and hydrogen plasma treated prior to use to remove nondiamond carbon impurity phases and to hydrogen terminate the surface. The boron-doping level of the NRL film was estimated to be in the mid 1019 B/cm3 range, and the boron-doping level of the USU films was approximately 5 x 10(20) B/cm(-3) based on boron nuclear reaction analysis. The electrochemical response was evaluated using Fe-(CN)6(3-/4-), Ru(NH3)6(3+/2+), IrCl6(2-/3-), methyl viologen, dopamine, ascorbic acid, Fe(3+/2+), and chlorpromazine. Comparisons are made between the apparent heterogeneous electron-transfer rate constants, k0(app), observed at these high-quality diamond films and the rate constants reported in the literature for freshly activated glassy carbon. Ru(NH3)6(3+/2+), IrCl6(2-/3-), methyl viologen, and chlorpromazine all involve electron transfer that is insensitive to the diamond surface microstructure and chemistry with k0(app) in the 10(-2)-10(-1) cm/s range. The rate constants are mainly influenced by the electronic properites of the films. Fe(CN)6(3-/4-) undergoes electron transfer that is extremely sensitive to the surface chemistry with k0(app) in the range of 10(-2)-10(-1) cm/s at the hydrogen-terminated surface. An oxygen surface termination severely inhibits the rate of electron transfer. Fe(3+/2+) undergoes slow electron transfer at the hydrogen-terminated surface with k0(app) near 10(-5) cm/s. The rate of electron transfer at sp2 carbon electrodes is known to be mediated by surface carbonyl functionalities; however, this inner-sphere, catalytic pathway is absent on diamond due to the hydrogen termination. Dopamine, like other catechol and catecholamines, undergoes sluggish electron transfer with k0(app) between 10(-4) and 10(-5) cm/s. Converting the surface to an oxygen termination has little effect on k0(app). The slow kinetics may be related to weak adsorption of these analytes on the diamond surface. Ascorbic acid oxidation is very sensitive to the surface termination with the most negative Ep(ox) observed at the hydrogen-terminated surface. An oxygen surface termination shifts Ep(ox) positive by some 250 mV or more. An interfacial energy diagram is proposed to explain the electron transfer whereby the midgap density of states results primarily from the boron doping level and the lattice hydrogen. The films were additionally characterized by scanning electron microscopy and micro-Raman imaging spectroscopy. The cyclic voltammetric and kinetic data presented can serve as a benchmark for research groups evaluating the electrochemical properties of semimetallic (i.e., conductive), hydrogen-terminated, polycrystalline diamond.     

Electrochemical behavior of L-cysteine and its detection at ordered mesoporous carbon-modified glassy carbon electrode

In this paper, the electrochemical behavior of L-cysteine (CySH) was investigated thoroughly at an ordered mesoporous carbon-modified glassy carbon (OMC/GC) electrode. The voltammetric studies showed there were three anodic peaks for the electrooxidation of CySH in the pH range of 2.00-5.00; however, one peak disappeared above pH 5.00. This behavior has never been reported before. Through the studies of the effect of pH on the distribution fractions (delta) of the four chemical species of CySH, we conclude only CySH2+ (H3A+) and CyS- (HA-) are the electroactive substances and should be responsible for the electrooxidation of CySH. And for the first time, we successfully established the exact and systemic mechanisms based on the electroactive species to explain CySH oxidation at different pH values. On the other hand, a sensitive CySH sensor was developed based on an OMC/GC electrode, which shows a large determination range (18-2500 micromol L(-1)), a high sensitivity (23.6 microA mmol L(-1)), and a remarkably low detection limit (2.0 nmol L(-1), which is the lowest value ever reported for direct CySH determination on the electrodes) at pH 2.00. At pH 7.00, the modified electrode can be still used to readily detect CySH in the range of the physiological levels. These make OMC/GC electrode a promising candidate for efficient electrochemical sensors for the detection of CySH.     

孔结构对煤基活性炭电极材料电化学性能的影响(英文)

以太西无烟煤为前驱体,NaOH为活化剂制备电化学电容器电极材料。采用N2吸附法及电化学测试对活性炭的孔结构和电化学性能进行了表征。在1mol/L(C2H5)4NBF4/碳酸丙烯酯有机电解液体系中,研究了孔结构对活性炭电极材料的电化学性能的影响。结果表明:以NaOH为活化剂可制备出比表面积943mol/L～2479mol/L、比电容57F/g～167F/g的活性炭电极材料。活性炭电极材料的比电容不仅取决比表面积,而且与活性炭的孔径分布有关。孔径为2nm～3nm的中孔的存在可以有效降低电解液的扩散阻力,提高电极材料比表面积的利用率,从而使电容器的电化学性能得到增强。     

Poly-cobalt[tetrakis(o-aminophenyl)porphyrin] nanowire and single-walled carbon nanotube for the analysis of hydrogen peroxide

Nanowires of poly-cobalt[tetrakis(o-aminophenyl)porphyrin] (PCoTAPPNW) were fabricated by electrochemical polymerization by the cyclic voltammetric method in anodic aluminum oxide membranes. A glassy carbon electrode (GCE) modified by PCoTAPPNW and single-walled carbon nanotubes (SWNT) without any binder was investigated with voltammetric methods in phosphate buffer saline (PBS) at pH 7.4. The PCoTAPPNW + SWNT/GCE exhibited strongly enhanced voltammetric and amperometric sensitivity towards hydrogen peroxide (H2O2), which shortened the response time (< 5 seconds), showed detection limit of 1.0 microM and enhanced the sensitivity for H2O2 detection with 194 microA mM(-1) cm(-2). The PCoTAPPNW + SWNT/GCE can be used to monitor H2O2 at very low concentration in physiological pH as an efficient electrochemical H2O2 sensor.     

An Enzyme Switch Employing Direct Electrochemical Communication between Horseradish Peroxidase and a Poly(aniline) Film

An enzyme switch, or microelectrochemical enzyme transistor, responsive to hydrogen peroxide was made by connecting two carbon band electrodes (～10 μm wide, 4.5 mm long separated by a 20-μm gap) with an anodically grown film of poly(aniline). Horseradish peroxidase (EC 1.11.1.7) was either adsorbed onto the poly(aniline) film or immobilized in an insulating poly(1,2-diaminobenzene) polymer grown electrochemically on top of the poly(aniline) film to complete the device. In the completed device, the conductivity of the poly(aniline) film changes from conducting (between - 0.05 and + 0.3 V vs SCE at pH 5) to insulating (>+0.3 V vs SCE at pH 5) on addition of hydrogen peroxide. The change in conductivity is brought about by oxidation of the poly(aniline) film by direct electrochemical communication between the enzyme and the conducting polymer. This was confirmed by measuring the potential of the poly(aniline) film during switching of the conductivity in the presence of hydrogen peroxide. The devices can be reused by rereducing the poly(aniline) electrochemically to a potential below +0.3 V vs SCE. A blind test showed that the device can be used to determine unknown concentrations of H(2)O(2) in solution and that, when used with hydrogen peroxide concentrations below 0.5 mmol dm(-)(3), the same device maybe reused several times. The possible development of devices of this type for use in applications requiring the measurement of low levels of hydrogen peroxide or horseradish peroxidase is discussed.     

Thin films of polyelectrolyte-encapsulated catalase microcrystals for biosensing

Polyelectrolyte (PE)-encapsulated catalase microcrystals were assembled onto gold electrodes by their sequential deposition with oppositely charged PEs, utilizing electrostatic interactions to form enzyme thin films for biosensing. The PE coating around the microcrystals provided a regular surface charge, thus facilitating the stepwise film growth, and it effectively prevented catalase leakage from the assembled films. The encapsulated catalase was shown to retain both its biological and its electrochemical activity. Direct electron transfer between catalase molecules and the gold electrode was achieved without the aid of any electron mediator. In pH 5.0 phosphate buffer solution, the apparent formal potential (E(o)') of catalase was -0.131 V (vs Ag/AgCl). As a H2O2 biosensor, films consisting of one layer of the encapsulated catalase displayed considerably higher (approximately 5-fold) and more stable electrocatalytic responses to the reduction of H2O2 than did corresponding films made of one layer of nonencapsulated catalase or solubilized catalase. An increase in either the number of "precursor" PE layers between the gold electrodes and the catalase microcrystal layers in the film or the number of PE layers encapsulating the catalase microcrystals was found to decrease the electrocatalytic activity of the electrode. At low precursor PE layer numbers (approximately 2) and PE encapsulating layers (approximately 4), the current response was proportional to the H2O2 concentration in the range 3.0 x 10(-6) to 1.0 x 10(-2) M. The overall electroactivity of the multilayer film increased for the first two layers of encapsulated catalase, after which a plateau was observed. This was attributed to the increasing difficulty of electron transfer and substrate diffusion limitations. The current approach of using immobilized PE-encapsulated enzyme microcrystals for biosensing provides a versatile method to prepare high enzyme content films with high and tailored enzyme activities.     

Controlled synthesis of mesoporous hematite nanostructures and their application as electrochemical capacitor electrodes

In this work, iron oxalate (FeC?O?·2H?O) with different morphologies was synthesized through a simple solution-based direct precipitation process. Three samples with distinct morphologies, i.e., microrods with a parallelogram-like cross-section, nanorods, and multi-layered nanosheets, could be obtained in a selective manner. We found that the shapes of the iron oxalate could be controlled just through simply altering the solvents used. The one-dimensional (1D) characteristic of the infinite linear chains and the selective interaction between solvents and various crystallographic planes of FeC?O?·2H?O played an important role in the formation of FeC?O?·2H?O with different morphologies. Phase-pure hematite (α-Fe?O?) had be obtained by annealing these as-prepared FeC?O?·2H?O precursors without significant alterations in morphology. The as-obtained mesoporous α-Fe?O? products had high specific surface areas with narrow pore size distribution. The electrochemical properties of the α-Fe?O? electrodes were investigated using cyclic voltammetry (CV) and galvanostatic charge-discharge measurements by a three electrode system. The electrochemical experiments revealed that they showed a structure-dependence in their specific capacitances. The mesoporous multi-layered nanosheets exhibited a significant structurally induced enhancement of capacity properties associated with their novel structure characteristic in addition to the high specific surface area. They can present the highest specific capacitance value (116.25 F g?1) and excellent long cycle life within the voltage window from - 0.6 to 0 V. This method can be easily controlled and is expected to be extended to produce other functional materials with controlled structure.     

Determination of the activity of hydrogen ions in dilute sulfuric acids by use of an ionic liquid salt bridge sandwiched by two hydrogen electrodes

The activities of hydrogen ions in 20-200 μmol dm(-3) H(2)SO(4) solution were estimated by use of an ionic liquid salt bridge (ILSB), made of tributyl(2-methoxyethyl)phosphonium bis(pentafluoroethanesulfonyl)amide (TBMOEPC(2)C(2)N), sandwiched by two hydrogen electrodes. The experimental pH values (pH = -log a(H), where a(H) is the activity of hydrogen ions) were in good agreement, within 0.01 pH unit, with those calculated using the Pitzer model. The difference between the experimental and theoretical pH values at 50 μmol dm(-3) H(2)SO(4) solution was much smaller than that obtained by use of a glass electrode in combination with a reference electrode with a concentrated KCl salt bridge. The source of the small deviation can be explained by the residual diffusion potential due to the dissolution of TBMOEPC(2)C(2)N in the H(2)SO(4) solution (W) and the resultant increase in the ionic strength of W. The use of a reference electrode equipped with an ILSB opens the way to accurately estimate the pH in dilute aqueous solutions, for which we have not had effective means.     

A hydrogen peroxide biosensor based on peroxidase activity of hemoglobin in polymeric film

A Hydrogen peroxide (H2O2) biosensor, based on hemoglobin (Hb) and ortho-phenylenediamine (o-PD) gold electrode, was fabricated. Hb was immobilized onto the electrode surface by electrochemical polymerize method with o-PD. The designed biosensor showed a well defined redox peak which was attributed to the direct electrochemical response of Hb. The immobilized Hb exhibited an excellent electrocatalytical response to the reduction of hydrogen peroxide, enabling the sensitivity determination of H2O2. Factors and performances such as pH, potential, influencing the designed biosensor, were studied carefully. The amperometric detection of H2O2 was carried out at -300 mV in phosphate buffer solution (PBS) (0.1 M) with pH 6.0. This biosensor showed a fast amperometric response (less then 5 s) to H2O2. The levels of the (Relative standard deviation) RSDs (< 3.5%) for the entire analyses reflected a highly reproducible sensor performance. Using the optimized conditions, the detection limit of the biosensor was 1 x 10(-7) M and linear range was from 5 x 10(-6) to 1.25 x 10(-4) M. In addition, this sensor showed long-term stability and good sensitivity.     

Building energy storage device on a single nanowire

Hybrid electrochemical energy storage devices combine the advantages of battery and supercapacitors, resulting in systems of high energy and power density. Using LiPF(6) electrolyte, the Ni-Sn/PANI electrochemical system, free of Li-based electrodes, works on a hybrid mechanism based on Li intercalation at the anode and PF(6)(-) doping at the cathode. Here, we also demonstrate a composite nanostructure electrochemical device with the anode (Ni-Sn) and cathode (polyaniline, PANI) nanowires packaged within conformal polymer core-shell separator. Parallel array of these nanowire devices shows reversible areal capacity of ～3 μAh/cm(2) at a current rate of 0.03 mA/cm(2). The work shows the ultimate miniaturization possible for energy storage devices where all essential components can be engineered on a single nanowire.     

Electrochemical detection of anti-benzo[a]pyrene diol epoxide DNA damage on TP53 codon 273 oligomers

DNA damage from (+/-)-anti-benzo[a]pyrene-7,8-dihydrodiol-9,10-epoxide (BPDE) at a hotspot TP53 gene sequence was electrochemically detected. BPDE was exposed to gold electrode immobilized double-stranded DNA oligomers followed by voltammetric measurements in the presence of redox-active C(12)H(25)V(2+)C(6)H(12)V(2+)C(12)H(25) (V(2+) = 4,4'-bipyridyl or viologen, C12-viologen). Square wave voltammograms from BPDE-exposed DNA-modified electrodes showed the emergence of a C12-viologen-DNA complex at -0.37 V versus Ag/AgCl. The peak current intensity of this redox wave was dependent on both BPDE concentration and exposure time. Controls with alternate xenobiotics and DNA sequences showed this redox wave to be primarily due to BPDE damage at the wild-type DNA sequence. The detection limit was determined to be approximately 170 nM BPDE. Mass spectrometry and UV thermal melting experiments provided insight into the BPDE reaction and mirrored the sensor results. This report demonstrates that an electrochemical hybridization sensor can be used to detect sequence-related xenobiotic DNA damage.     

On-chip electric field driven electrochemical detection using a poly(dimethylsiloxane) microchannel with gold microband electrodes

An external electric field driven in-channel detection technique for on-chip electrochemical detection in micro fabricated devices is described based on a microfluidic system containing an array of 20 microband electrodes. It is shown that an external electric field induces a potential difference between two gold microband electrodes in a poly(dimethylsiloxane) (PDMS) microchannel, and that this enables the electrochemical detection of electroactive species such as ascorbic acid and Fe(CN) 6 (4-). The results, which are supported by simulations of the behavior of the microband electrodes in the microfluidic system, show that the induced potential difference between the electrodes can be controlled by altering the external electric field or by using different microbands in the microband array. As the obtained currents depend on the concentrations of electroactive species in the flowing solution and the detection can be carried out anywhere within the channel without interference of the external electric field, the present approach significantly facilitates electrochemical detection in capillary electrophoresis. This approach consequently holds great promise for application in inexpensive portable chip-based capillary electrophoresis (CE) devices.     

Real-time pH microscopy down to the molecular level by combined scanning electrochemical microscopy/single-molecule fluorescence spectroscopy

A new technique combining scanning electrochemical microscopy (SECM) and single-molecule fluorescence spectroscopy was developed to accomplish locally and temporally defined pH adjustments in buffer solutions and on surfaces monitored by fluorescence alteration of pH-sensitive fluorophores in real time. Local pH gradients were created by electrochemical generation of H(+) or OH(-) during redox reactions at ultramicro- or nanoelectrodes with radii from 5 microm to 35 nm. Ratiometric fluorescence measurements were performed with a confocal laser microscope using two detectors for different spectral regions. Time-resolved pH measurements were carried out with freely diffusing SNARF-1-dextran. For pH measurements on surfaces, total internal reflection fluorescence microscopy was used in combination with a CCD camera. The fluorophore SNAFL-succinimidyl ester was bound to amino-terminated octadecylsilane-coated coverslips. Local pH determinations could be accomplished with an accuracy of 0.2 unit. The measured pH profiles showed a strong dependence on the tip diameter, the buffer/mediator concentration ratio, and the tip-surface distance. As an application for bionanotechnology using SECM-induced pH changes on the molecular level, the proton-driven ATP synthesis by single membrane-bound F(0)F(1)-ATP synthases was investigated. ATP synthesis resulted in stepwise subunit rotation within the enzyme that was monitored by single-molecule fluorescence resonance energy transfer.     

Electrochemical sensor for detecting ultratrace nitroaromatic compounds using mesoporous SiO2-modified electrode

An electrochemical sensor for ultratrace nitroaromatic compounds (NACs) using mesoporous SiO2 of MCM-41 as sensitive materials is reported. MCM-41 was synthesized and characterized by scanning electron microscope, transmission electron microscopy, and small-angle X-ray diffraction. Glassy carbon electrodes modified with MCM-41 show high sensitivity for cathodic voltammetric detection of NACs (including 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitrobenzene (TNB), 2,4-dinitrotoluene, and 1,3-dinitrobenzene) down to the nanomolar level. The high sensitivity is attributed to the strong adsorption of NACs by MCM-41 and large surface area of the working electrode resulting from MCM-41 modification. The voltammetric response is fast, and the detection of NACs can be finished within 14 s. SiO2 nanospheres were similarly used to modify glassy carbon electrodes for electrochemical detection of TNT and TNB. The detection limit of SiO2 nanosphere-modified electrodes is lower than that of MCM-41-modified electrodes, possibly due to the smaller surface area of SiO2 nanospheres than mesoporous MCM-41. The results show mesoporous SiO2-modified glassy carbon electrodes, particularly MCM-41-modified electrodes, open new opportunities for fast, simple, and sensitive field analysis of NACs.     

Ultramicroelectrode array behavior of one-dimensional organic conductor electrodes

Tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) electrodes were prepared by two methods that produced electrodes with different structures. This was confirmed by scanning electron microscopy, which also revealed the ultramicroelectrode arraylike structure of TTF-TCNQ electrodes. Electrochemical behavior at both types of electrodes followed the predictions of the theory for ultramicroelectrode arrays. At the two types of surfaces that were prepared, apparent electrochemical rate constants of ferricyanide and ascorbate were different. The resulting changes in the apparent rate constants of redox couples such as ferricyanide and ascorbate as a function of surface structure suggest that at TTF-TCNQ control over reactivity can be achieved through structural manipulation.     

Electrochemical treatment of paper mill wastewater using three-dimensional electrodes with Ti/Co/SnO2-Sb2O5 anode

The properties of the interlayer and outer layer of Ti/Co/SnO2-Sb2O5 electrode were studied, and the electrochemical behavior was examined as well. As a result of unsatisfactory treatment using Ti/Co/SnO2-Sb2O5 electrode, electrochemical disposal of paper mill wastewater employing three-dimensional electrodes, combining active carbon granules serving as packed bed particle electrodes, with Ti/Co/SnO2-Sb2O5 anode, was performed. The outcome demonstrates that efficient degradation was achieved. The residual dimensionless chemical oxygen demand (COD) concentration reached 0.137, and color removal 75% applying 167 mA cm(-2) current density at pH 11 and 15 g l(-1) NaCl. The instant current efficiency, energy cost, electrochemical oxidation index (EOI) and kinetic constant of the reaction were calculated. At the same time, the influence of pH and current density on COD abatement and decolorization was also investigated, respectively.