Nonlinear phenomena at mercury Hg electrode/room-temperature ionic liquid (RTIL) interfaces: polarographic streaming maxima and current oscillation

The polarographic streaming maxima and cyclic voltammetric anodic current oscillation (CVACO) at a hanging mercury drop electrode (HMDE) in room-temperature ionic liquid (RTIL) have been studied for the first time using cyclic voltammetric, potential step chronoamperometric and pulse voltammetric techniques. The reversible redox reaction of the 2,1,3-benzothiadiazole (BTD)/BTD*- (an anion radical of BTD) couple with a formal potential (E0') of -1.36 V versus Ag/AgCl/NaCl(saturated) in 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) RTIL was typically employed for this purpose. A maximum was observed at the rising part of the normal pulse voltammogram for the reduction of BTD to BTD*- as well as of the reversed pulse voltammogram for the reoxidation of BTD*- to BTD at the HMDE. The conditions of the initiation and control of the CVACO at the HMDE in EMIBF4 were extensively investigated. Generally, the CVACO was enhanced by increasing the concentration of BTD at a given potential scan rate (upsilon) and was attenuated by increasing upsilon. An electrocapillary curve was measured using a dropping mercury electrode in EMIBF4, and the potential of zero charge was determined to be -0.23 V. On the basis of the modern theory of the polarographic streaming maxima of the first kind, the observed streaming maxima and CVACO phenomena are successfully explained to originate from the macroscopic instability at the electrode/solution interface wherein the oscillating mode creates the CVACO.     

Electrooxidation of Formamidine Disulfide Simultaneously Investigated by On-Line High Performance Liquid Chromatography and Cyclic Voltammetry

The electro-oxidation of formamidine disulfide, an important sulfur-containing compound, was simultaneously investigated with on-line high-performance liquid chromatography and cyclic voltammetry. Using a home-made microporous sampler located at the electrode interface, the solution on the electrode surface was in situ sampled and analyzed. The electrochemical scanning was synchronously performed, which allowed the electro-oxidation products to be detected at a given potential. The main products on the surface of platinum electrode were found to be thiourea, formamidine sulfinic acid, cyanamide, and elemental sulfur. Forced convection arising from the sampling played an important role in the electrochemical oxidation. The extraction of electrode surface solution promoted the renewal of reactant and its intermediates, which induced the change of cyclic voltammetry curve. The forced convection also contributed to the redox peak current of the species on the cyclic voltammetry curves through the change of concentration of reactant and its intermediates. This technique can help to explore the reaction mechanism of complex electrochemical reactions.     

Phase-selective a.c. adsorptive stripping voltammetry of lumazine on a hanging mercury drop electrode

The electrochemical behavior of lumazine (LMZ), an important antibacterial agent, has been studied at the hanging mercury drop electrode (HMDE). The nature of the process taking place at the HMDE was clarified. Its adsorption behavior at HMDE has been studied by using a.c and cyclic voltammetry (CV). Both the molecule and its reduced product appeared to be adsorbed at the surface of the electrode. Controlled adsorptive accumulation of LMZ on the HMDE provides the basis for the direct stripping measurement of that compound in the subnanomolar concentration level. Experimental and instrumental parameters for the quantitative determination were optimized. Phase-selective a.c voltammetry provided the best signal and gave a detection limit of 0.15 microg L(-1) (9.0 x 10(-10) mol/L) LMZ in aqueous solution. Molecules or ions which may interfere were studied.     

Phase-selective a.c. adsorptive stripping voltammetry of lumazine on a hanging mercury drop electrode

The electrochemical behavior of lumazine (LMZ), an important antibacterial agent, has been studied at the hanging mercury drop electrode (HMDE). The nature of the process taking place at the HMDE was clarified. Its adsorption behavior at HMDE has been studied by using a.c and cyclic voltammetry (CV). Both the molecule and its reduced product appeared to be adsorbed at the surface of the electrode. Controlled adsorptive accumulation of LMZ on the HMDE provides the basis for the direct stripping measurement of that compound in the subnanomolar concentration level. Experimental and instrumental parameters for the quantitative determination were optimized. Phase-selective a.c voltammetry provided the best signal and gave a detection limit of 0.15 μg L^–1 (9.0 × 10^–10 mol/L) LMZ in aqueous solution. Molecules or ions which may interfere were studied.     

Cyclic voltammetry of echinomycin and its interaction with double-stranded and single-stranded DNA adsorbed at the electrode.

Interactions of echinomycin (Echi) with DNA was studied by cyclic voltammetry (CV) with hanging mercury drop electrode (HMDE). Echinomycin was electrochemically active, yielding several signals. Interaction of Echi with dsDNA attached to a hanging mercury drop electrode resulted in high Echi signals, suggesting a strong binding of Echi to dsDNA by bis-intercalation at the electrode surface. Under the same conditions, interaction of Echi with ssDNA produced almost no Echi signal. This behavior is in agreement with a strong binding of Echi to dsDNA and a very weak binding of Echi to ssDNA observed earlier in solution. Echi, thus, appears to be a good candidate for redox indicator in electrochemical DNA hybridization sensors.     

室温离子液体电解液中尖晶石LiMn_2O_4的电化学性质

应用循环伏安、恒电流充放电和电化学阻抗技术研究了尖晶石L iMn2O4于室温离子液体电解液中的电化学性质.实验表明,以室温离子液体作电解液,L iMn2O4的首次放电容量可达108.2 mAh/g、循环效率高于90%,温度和电流密度显著影响电极的电化学性能.交流阻抗测定了L i+在电极/电解液相界面迁移的活化能,为55 kJ/mol.根据界面反应的高活化能解释了L iMn2O4在该离子液体电解液中低温性能和倍率充放电性能不佳的原因.     

Preparation,Electrochemistry, and Electrocatalytic Activity of Lead Pentacyanonitrosylferrate Film Immobilized on Carbon Ceramic Electrode

Lead pentacyanonitrosylferrate (PbPCNF), a new Prussian blue analog, was immobilized on the surface of a carbon ceramic electrode (CCE) prepared by sol‐gel method. The immobilization process consists of adding a certain amount of metallic lead to the electrode matrix before gelation, and chemical derivatization of Pb on the electrode surface to a PbPCNF solid film by immersing the electrode in a solution of sodium pentacyanonitrosylferrate (PCNF). The composition of the synthesized PbPCNF was characterized by FTIR, scanning electron microscopy (SEM), and energy‐dispersive X‐ray (EDX) techniques. The resulting modified electrode showed electroactivity at two redox centers. The electrochemical behavior of the PbPCNF modified carbon ceramic electrode (PbPCNF|CCE) was studied by cyclic voltammetry. Under optimized conditions the peak‐to‐peak separation is only 39 mV, indicative of a surface reaction. Ion effects of the supporting electrolyte suggest that cations have a considerable effect on the electrochemical behavior of the modified electrode. The transfer coefficient (α) and the charge transfer rate constant at the modifying film|electrode interface (k_s) were calculated. The electrocatalytic activity of the modified electrode toward the electro‐reduction of peroxodisulfate was studied in details.     

甲苯-乙醇介质中二茂铁催化分解过氧化氢机理的探讨

甲苯-乙醇介质中二茂铁催化分解过氧化氢机理的探讨;电子转移机理     

Self-assembled monolayers of a hydroquinone-terminated alkanethiol onto gold surface. Interfacial electrochemistry and Michael-addition reaction with glutathione

An electroactive self-assembled monolayer (SAM) was fabricated by covalent attachment of a novel hydroquinone-terminated dodecanethiol onto the gold surface and its electrochemical behavior was investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The capability of the designed SAM in immobilization of organic molecules onto the gold surface was studied utilizing the Michael-addition as a model reaction. The results obtained from cyclic voltammetry, electrochemical impedance and grazing incidence Fourier transform infrared (GI-FTIR) spectroscopy revealed that, upon applying an anodic potential to the Au-SAM electrode system in the presence of glutathione, the electrochemically generated p-quinone participated in a Michael-addition reaction with glutathione and the corresponding Michael adduct was formed at the solid–liquid interface. The kinetic parameters were then derived for this interfacial Michael-addition reaction.     

Ion transfer processes at ionic liquid based redox active drop deposited on an electrode surface

Ion transfer across the boundary formed at an ionic liquid drop deposited on an electrode immersed in aqueous solution, generated by electrochemical redox reaction at the electrode-ionic liquid interface, is studied to obtain information about the ability of anions to be transferred into a room temperature ionic liquid.     

Label‐free Voltammetric Detection of Products of Terminal Deoxynucleotidyl Transferase Tailing Reaction

A label‐free approach that takes advantage of intrinsic electrochemical activity of nucleobases has been applied to study the products of terminal deoxynucleotidyl transferase (TdT) tailing reaction. DNA homooligonucleotides A₃₀, C₃₀ and T₃₀ were used as primers for the tailing reaction to which a dNTP – or a mixture of dNTPs – and TdT were added to form the tails. Electrochemical detection enabled study of the tailing reaction products created by various combinations of primers and dNTPs, with pyrolytic graphite electrode (PGE) being suitable for remarkably precise analysis of the length of tailing reaction products. Furthermore, the hanging mercury drop electrode (HMDE) was able to reveal formation of various DNA structures, such as DNA hairpins and G‐quadruplexes, which influence the behavior of DNA molecules at the negatively charged surface of HMDE. Thus, the described approach proves to be an excellent tool for studying the TdT tailing reactions and for exploring how various DNA structures affect both the tailing reactions and electrochemical behavior of DNA oligonucleotides at electrode surfaces.     

DNA and PNA sensing on mercury and carbon electrodes by using methylene blue as an electrochemical label

Described here are the electrochemical parameters for MB on binding to DNA at hanging mercury drop electrode (HMDE), glassy carbon electrode (GCE), and carbon paste electrode (CPE) in the solution and at the electrode surface. MB, which interacts with the immobilized calf thymus DNA, was detected by using single-stranded DNA-modified HMDE or CPE (ssDNA-modified HMDE or CPE), bare HMDE or CPE, and double-stranded DNA-modified HMDE or CPE (dsDNA-modified HMDE or CPE) in combination with adsorptive transfer stripping voltammetry (AdTSV), differential pulse voltammetry (DPV), and alternating current voltammetry (ACV) techniques. The structural conformation of DNA and hybridization between synthetic peptide nucleic acid (PNA) and DNA oligonucleotides were determined by the changes in the voltammetric peak of MB. The PNA and DNA probes were also challenged with excessive and equal amount of noncomplementary DNA and a mixture that contained one-base mismatched and target DNA. The partition coefficient was also obtained from the signal of MB with probe, hybrid, and ssDNA-modified GCEs. The effect of probe, target, and ssDNA concentration upon the MB signal was investigated. These results demonstrated that MB could be used as an effective electroactive hybridization indicator for DNA biosensors. Performance characteristics of the sensor are described, along with future prospects.     

Voltammetry at a liquid–liquid interface supported on a metallic electrode

A liquid–liquid interface supported on a metallic electrode has been used to study ion transfer (IT) and electron transfer (ET) reactions by cyclic voltammetry. The system is composed of an aqueous droplet supported on a platinum disc electrode and immersed into an organic electrolyte solution. Depending on the nature of the dissolved species present in the aqueous solution, and in the organic electrolyte solution, different electrochemical coupled reactions can be observed. This method enables a fast and convenient method to measure standard transfer potentials for example of ionised drug molecules.     

丁磺酸内酯对锂离子电池性能及负极界面的影响

用循环伏安(CV)、电化学阻抗谱(EIS)、扫描电镜(SEM)、能谱分析(EDS)及理论计算等方法研究了添加剂丁磺酸内酯(BS)对锂离子电池负极界面性质的影响. 研究表明, 在初次循环过程中, BS具有较低的最低空轨道能量, 优先于溶剂在石墨电极上还原分解, 并形成固体电解质相界面膜(SEI膜). 在含BS的电解液中形成的SEI膜的热稳定性高, 在70 ℃下储存24 h后, 膜电阻和电荷迁移电阻大小基本保持不变, 而在不含BS的电解液中形成的SEI膜的热稳定性较差, 在70 ℃下储存24 h后, 膜电阻和电荷迁移电阻大小有明显的增加. 从BS对锂离子电池电化学性能影响的研究表明, 加入少量的BS能够显著提高锂离子电池的室温放电容量、低温及高温储存放电性能.     

Motion of redox molecules in solution monitored by the highly-sensitive EQCM technique

The behavior of redox molecules in solution that was not detected by electrochemical techniques was measured by a highly-sensitive electrochemical quartz crystal microbalance (EQCM) technique that has been improved in this study to obtain a high sensitivity of EQCM measurement in solution. The improved EQCM technique allowed to monitor the motion of a redox molecule, that is an access of the molecule to an electrode surface and repulsion from the surface during redox. An EQCM technique currently in use has measured adsorption of redox molecules on an electrode surface or polymerization on the surface caused by a chemical reaction following redox, which exhibits an enough large mass change response to detect with an EQCM measurement. However, access and repulsion of redox molecule, which is a slight motion of the molecule near on electrode surface, has not been detected and investigated by an EQCM technique, because the mass change response seems to be very small. In this study, the redox behavior of methyl viologen on a bare gold surface, pyridinethiol surface and methylpyridinethiol surface was investigated. Although the three electrodes give the same cyclic voltammogram of methyl viologen, the three are different in QCM response recorded at the same time as the voltammetry. Access/repulsion of methyl viologen within an electrical double layer was monitored by the highly-sensitive EQCM technique.     

Motion of redox molecules in solution monitored by the highly-sensitive EQCM technique

The behavior of redox molecules in solution that was not detected by electrochemical techniques was measured by a highly-sensitive electrochemical quartz crystal microbalance (EQCM) technique that has been improved in this study to obtain a high sensitivity of EQCM measurement in solution. The improved EQCM technique allowed to monitor the motion of a redox molecule, that is an access of the molecule to an electrode surface and repulsion from the surface during redox. An EQCM technique currently in use has measured adsorption of redox molecules on an electrode surface or polymerization on the surface caused by a chemical reaction following redox, which exhibits an enough large mass change response to detect with an EQCM measurement. However, access and repulsion of redox molecule, which is a slight motion of the molecule near on electrode surface, has not been detected and investigated by an EQCM technique, because the mass change response seems to be very small. In this study, the redox behavior of methyl viologen on a bare gold surface, pyridinethiol surface and methylpyridinethiol surface was investigated. Although the three electrodes give the same cyclic voltammogram of methyl viologen, the three are different in QCM response recorded at the same time as the voltammetry. Access/repulsion of methyl viologen within an electrical double layer was monitored by the highly-sensitive EQCM technique.     

Electrically driven motion of an air bubble on hemispherical oil/water interface by three-phase boundary reactions

Our electrochemical cell consisted of a ferrocene-included hemispherical nitrobenzene (NB) droplet on the glassy carbon (GC) electrode which was immersed in the aqueous solution including sodium sulfate and sodium dodecyl sulfate (SDS). When an air bubble was injected near the boundary between the oil and the aqueous phase, it stayed at the top of the hemisphere on the boundary so that the lower half of the bubble was put in oil and the other half was in water. From the force balance of surface tension and buoyancy of the bubble, the bubble took an energetic minimum at the interface. It sank into the oil phase when ferrocene in the oil was electrochemically oxidized through the GC electrode by the three-phase boundary reaction. The electrochemical reduction caused the bubble to move back toward the aqueous phase. The motion of the bubble was synchronized with the redox reaction of ferrocene. The potential step oxidation showed such a rapid response that the motion could not be attributed to diffusion of ferricenium ion from the three-phase boundary to the bubble. Our idea of explaining the rapidity was the translational motion of the SDS layer along the boundary, which was driven by the difference in the surface concentration of SDS caused by the electrochemical generation of the ferricenium ion. The motion of the SDS layer was demonstrated by the shrinkage of the oil layer spread on the water surface when SDS solution was dropped on the oil layer. The spreading velocity was close to the velocity of propagating the oxidation of ferrocene to the bubble.     

Scanning electrochemical microscopy study of ion transfer process across water/2-nitrophenyloctylether interface supported by hydrophobic carbon ceramic electrode

A carbon ceramic electrode (CCE) modified with the redox probe—decamethylferrocene solution in hydrophobic organic solvent—2-nitrophenyloctyl ether and immersed into an aqueous solution was studied by scanning electrochemical microscopy (SECM). After the electrochemical oxidation of decamethylferrocene, its cations were detected near the electrode surface in the aqueous phase. This indicates that some fraction of the redox-active cations electrochemically produced in the organic phase is transferred across the liquid/liquid interface. They are reduced at the SECM tip and form a solid deposit. The amount of deposited decamethylferrocene was estimated by the anodic reaction at the tip. It is affected by the substrate–tip distance, deposition time, and electrolyte concentration. The SECM images of unmodified and modified CCEs are consistent with their heterogeneous structure.     

Comparison of the voltammetric studies at mercury and glassy carbon electrodes for the interaction of lumichrome with DNA and analytical applications

The determination of the interaction between lumichrome (LC), one of the products of decomposition of the biologically important flavins, and calf thymus double-stranded DNA was performed by using cyclic voltammetry (CV) and differential pulse stripping voltammetry (DPSV) in connection with a hanging mercury drop electrode (HMDE) or glassy carbon electrode (GCE). The nature of the process taking place at both electrode surfaces was clarified. It was found that the addition of DNA to a buffered LC solution results in the decrease of redox peak currents with changes in the peak potentials at both electrodes. We assume that LC interacting with DNA produces an electrochemically inactive supramolecular complex via intercalation. There was a difference between the electrochemical parameters determined at the HMDE and those at the GCE. The binding constants ( K) of the LC-DNA complex at HMDE and GCE were determined through the changes of peak currents and their values at the 10(5) level and 10(4) level with each nucleotide residue of DNA binding one LC molecule, respectively. Furthermore, the calibration graph for the determination of DNA was obtained by the decrease in the DPSV peak current of LC in the presence of DNA. Different variables, such as the concentration of LC, the accumulation time and solution conditions, were studied and optimised to maximize the sensitivity; in addition, the detection limit and the reproducibility were determined.     

Fe(Ⅱ)-EDTA剪切DNA在悬汞电极上的电化学行为研究

在足迹图谱技术中,Fe(Ⅱ）-EDTA常被作为DNA断裂工具用于双链DNA的非特异性断裂^[1],因而Fe(Ⅱ）-EDTA作为核酸构象变化的探针及DNA－配体复合物分析的羟基自由基足迹试剂在生物化学、分子生物学和基因工程学等中获得广泛应用^[2]。虽然DNA在汞电极上的电化学行为研究报道较多^[3-7],但有关Fe(Ⅱ）-EDTA非特异性剪切DNA的电化学研究报道较少^[8-10]。本文对Fe(Ⅱ）-EDTA剪切DNA在悬汞电极上的电化学行为进行了初步研究。结果表明,由于Fe(Ⅱ）-EDTA对DNA的裂解作用,导致DNA的结构发生变化,使DNA在悬汞电极上的电化学行为发生变化,还原峰电流显著增大,因而用电化学方法研究DNA的裂解有望成为研究DNA结构变化的辅助手段。