Influence of the Solvent on the “Casting” Methodology for MWCNT‐Modified Glassy Carbon and Platinum Electrodes

The choice of electrode material and surface preparation method are usually dictated by the suitability of the electrode to observe an electrochemical parameter, such as heterogeneous electron transfer rate, surface coverage, or redox potential. Thus, the glassy carbon (GC) and platinum (Pt) electrodes were modified with multiwalled carbon nanotubes (MWCNT) by direct “casting” modification using nine different aliquots of solvents. After drying at room temperature, the modified electrode showed distinct redox peaks corresponding to ferrocyanide oxidation/reduction. Using chemometrics, the cyclic voltammograms with higher current intensity were obtained for those in which ethanol, water and acetone as dispersing agents were used for GCE and dimethylformamide, water and acetone for Pt electrode modification.     

Dual microband electrodes: current distributions and diffusion layer ‘titrations’. Implications for electroanalytical measurements

The simulation of transport to double microband electrodes in generator–collector mode is reported focusing especially on the ‘titration curve’ approach to electroanalysis in which a titrant is electrogenerated from a redox active precursor on the generator electrode and reacts homogeneously with the target analyte. The current on the detector electrode reflects the amount of titrant ‘surviving’ passage between the two electrodes. The form of the titration curve – plots of detector current as a function of generator current – is shown to be highly sensitive to the electrode kinetics of the redox couple driven at the generator electrode. Accordingly the naïve use of such methodology for analysis without accompanying simulation and kinetic analysis is fraught with danger. Use of the conformal mapping approach in combination with the ADI method for investigation of the ‘titration’ current distributions at the double band system gives fast and precise simulation of this and similar problems. Convergence analysis is described which allows for the automatic selection of the simulation grid size so as to obtain a chosen accuracy (for example 1%) of the current for all experimentally meaningful values of the geometrical and physico-chemical parameters of the system to be investigated.     

Electrochemistry of ABTS at Glassy Carbon Electrodes

The electrochemical and the mass transport behavior of ABTS^2-/ABTS^·- (2,20-azinobis(3-ethylbenzothiazoline-6-sulfonate)) redox couple at glassy carbon electrode (GCE) in phos-phate buffer solution (PBS, pH=4.4) is studied in detail by cyclic voltammetry combined with rotating disk electrode system. From the i-E curves recorded at different electrode ro-tating rate, rate constant, and transfer coefficient for ABTS^2-?ABTS^·-+e reaction at GCE electrode and the diffusion coefficient of ABTS^2- in PBS are estimated to be 4.6×10^-3 cm/s, 0.28, and 4.4×10^-6 cm²/s, respectively. The transfer coefficient with a value of ca. 0.28 dif-fers largely from the value of 0.5 that is always assumed in the literature. The origins for the difference of the rate constant determined and the challenges for estimating the stan-dard rate constant are discussed. The performance for such ABTS^2- mediated bio-cathode toward oxygen reduction reaction is discussed according to the over-potential drop as well as current output limit associated with the charge transfer kinetics of ABTS^2-?ABTS^·-+eredox reaction and/or the mass transport effect.     

Theoretical Contribution towards Understanding Specific Behaviour of “Simple” Protein‐film Reactions in Square‐wave Voltammetry

Surface reactions of uniformly adsorbed redox molecules at working electrode surface are seen as adequate models to studying chemical reactivity of many lipophilic enzymes. When considered under pulse voltammetric techniques, these systems show several uncommon features, whose origin is still not completely clear. The phenomena of “quasireverible maximum”, “splitting” of the net peak in square‐wave voltammetry, and the very steep descent of Faradaic currents of simple surface redox reactions exhibiting fast electron transfer are just some of the features that make these systems quite interesting for further elaborations. In this work, we present a set of theoretical calculations under conditions of square‐wave voltammetry in order try to explain some of aforementioned phenomena. The major goal of our work is to get insight to some voltammetric and chrono‐amperometric features of two considered surface reactions, i. e. (1) the “simple” surface redox reaction, and (2) surface redox reaction coupled to follow‐up irreversible chemical reaction of electrochemically generated redox species (or surface ECirr). We focus on the role of created Red(ads) (here in the reduction pulses only) to the current components of calculated square‐wave voltammograms exhibiting fast electrode reaction. We show that the irreversible chemical removal of electrochemically generated Red(ads) species, created in the potential pulses where half‐reaction of reduction Ox(ads)+ne‐?→Red(ads) is “defined” to take place, causes significant increase of all square‐wave current components. The results presented in this work show how complex the chrono‐amperometric features of surface redox reactions under pulse voltammetric conditions might be. In addition, we point out that both half reactions of a given simple surface redox process can occur, at both, “only reduction” and “only oxidation” potential pulses in square‐wave voltammetry. This, in turn, contributes to the occurrence of many phenomena observed in simple protein‐film voltammetry reactions. The effects of chemical reaction rate to the features of calculated square‐wave voltammograms of surface ECirr systems with fast electrode reaction are reported for the first time in this work.     

Reconstituted Enzymes on Electropolymerizable FAD‐Modified Metallic Nanoparticles: Functional Units for the Assembly of Effectively “Wired” Enzyme Electrodes

Au nanoparticles are functionalized with thioaniline electropolymerizable units and mercaptophenyl boronic acid ligands. Flavin adenine dinucleotide (FAD) is linked to the boronic acid ligands and apo‐glucose oxidase, apo‐GOx, is reconstituted on the FAD cofactor units to yield enzymes in a structurally‐aligned configuration in respect to the Au NPs. Electropolymerization of the enzyme‐functionalized Au NPs on a thioaniline‐modified Au electrode yields a three‐dimensional bis‐aniline‐crosslinked Au NPs/reconstituted glucose oxidase matrix on the electrode that reveals effective electrical contacting with the electrode.     

A “vertex electron pair” scheme (VEPS) for describing the skeletal electron distribution in borane-type clusters

A predominantly localized electron pair scheme is outlined for describing the electron distribution and bonding in closo borane anions B_nH_n²⁻ and related electron deficient deltahedral clusters, in which a skeletal electron pair is assigned to each vertex, one pair being regarded as delocalized just inside the roughly spherical surface on which the skeletal atoms lie. The scheme gives a clearer picture of the electron distribution than is conveyed by resonating 2- and 3-centre bonds in the polyhedron edges and faces, and allows the bond orders of the polyhedron edge links to be calculated readily. The consequence of formal removal of BH²⁺ units from closo species B_nH_n²⁻ to generate nido species B_n−1H_n−1⁴⁻ and arachno species B_n−2H_n−2⁶⁻ is explored, and seen to allow rationalization of two features of such deltahedral-fragment clusters: (i) why a high-connectivity vertex is left vacant and (ii) why the frontier orbitals of such species concentrate electronic charge around their open faces. Moreover, in the case of D_4‘h B₄H₄⁶⁻ (cf. C₄H₄²⁻) and D_5h B₅H₅⁶⁻ (cf. C₅H₅⁻), the approach leads directly to the familiar picture for aromatic ring systems in which the highest filled, doubly degenerate π-bonding molecular orbital concentrates electronic charge in rings above and below the polygon on which the skeletal nuclei lie. It also leads to the expectation that arachno clusters with non-adjacent vacant vertices will be more stable than those with adjacent vacant vertices.     

磺化石墨烯/活性炭复合电极的制备及其不对称电容器脱盐

在还原剂NaBH₄存在下, 采用对氨基苯磺酸重氮盐与氧化石墨(GO)表面共价键合制备磺化石墨烯(GP-SO₃H). 傅里叶变换红外光谱(FTIR)证明磺酸基团在石墨烯表面接枝. 采用扫描电子显微镜(SEM)研究了磺化石墨烯的表面形貌. 以磺化石墨烯为添加剂, 制备了磺化石墨烯/活性炭(GP-SO₃H/AC)复合电极. 循环伏安及阻抗分析结果表明, 该复合电极的电容特性及导电性有明显改善. 以活性炭电极为对电极组装了不对称电容器(GP-SO₃H/AC|AC), 研究了该不对称电容器的电化学脱盐性能. 与对称电容器(AC|AC)相比, 不对称电容器中由于电极内磺酸基团对反离子的屏蔽作用, 电容器的电流效率达到89.4%以上, 脱盐量提高2.4倍, 单个循环脱盐量达到10.87 mg/g.     

Electrochemical Aberrant Methylation Detection Based on Ferrocenyl Naphthalene Diimide Carrying β‐Cyclodextrin,FNC

Electrochemical detection of the specific gene carrying aberrant methylated cytosine was achieved by ferrocenyl naphthalene diimide carrying β‐cyclodextrin (β‐CD), FNC, coupled with the probe‐DNA‐immobilized electrode. The five CpG sites in a 24‐base sequence were selected as the target DNA on the CDH4 gene, which is associated with colorectal cancer. When methylated and unmethylated samples hybridized with the DNA probe (HS‐M24) immobilized on the electrode, an increased current signal was observed in the electrolyte containing FNC and correlated with the amount of target DNA. Furthermore, an increase in current (115 %) was observed when the PCR product of 105 bp was hybridized on the HS‐M24‐immobilized electrode, whereas a background level of current increase was observed in the case of unmethylated product. Such large discrimination ability might be due to the inter‐ and/or intra‐complex formation of ferrocene with β‐CD of FNC on the surface of the electrode.     

Evaluation,Pitfalls and Recommendations for the “Water Layer Test” for Solid Contact Ion‐selective Electrodes

The “water layer test” is a crucial validation step of solid‐contact ion‐selective electrodes. It can confirm or contest the claim that the tested electrode is indeed a genuine solid contact electrode without an aqueous film between the ion‐selective membrane and its solid contact. Information about the presence of a water layer is essential for the interpretation of drifts in the electrode potentials commonly experienced with solid contact electrodes. Since its publication, the water layer test has been ubiquitously used, but without a standardized protocol the interpretation (or misinterpretation) of the test results led to uncertainties in the conclusions. Through both experiments and simulations based on theoretical models we have investigated the experimental parameters that can influence the results of the water layer test. We propose guidelines to minimize the possibility of misinterpretation of the results of the water layer test by considering the key factors that affect the shape of transients recorded during the water layer test. Most importantly, we emphasize the importance of allowing sufficient time for conditioning the tested electrode before the water layer test and providing adequate time for equilibration during the experiment. Using a thin ion‐selective membrane and thin solid‐contact layer for the tests is also recommended.     

Theoretical Investigation of Electrochemical Signal from Nanoscale Systems

In this paper, we report a theoretical study exploring the stochastic signal from electrochemical detection toward the nanometer scale systems. By using a discrete simulation as well as a statistical theory, this work investigates the distribution of the capturing times for redox molecules that released at a given distance from an electrode. We find that the capturing times tend to distribute over a wider range with a larger distance between the molecule’s source and the electrode, and thus the corresponding electrochemical signal would be somewhat less repeatable.     

Pt-WO3/C电极表面活化对乙二醇和CO氧化的作用

用丙酮和四氢呋喃混合溶液对Pt—WO3/C电极进行表面活化处理后，乙二醇在Pt—WO3/C电极上的电催化氧化活性大幅度提高．发现无论在中性溶液中还是在酸性溶液中，表面活化处理后的Pt—WO3/C电极，乙二醇的起始氧化电位负移，氧化峰电流在酸性介质中增加到表面活化处理前的3．2倍：中性介质中增加到表面处理前的4．7倍，其主要原因是表面活化处理后，一方面增加了催化剂Pt的活性表面，另一方面也促进了电极表面吸附的CO的电氧化，减少了CO对电极表面的毒化作用．     

Enhanced Electrochemical Capacitive Properties of Nickel‐Cobalt Oxide Nano‐flakes Materials

Nickel‐cobalt oxide nano‐flakes materials are successfully synthesized by a facile chemical co‐precipitation method followed by a simple calcination process. The studies show that the as‐prepared nickel‐cobalt oxides with different Ni/Co ratio are composed of NiO and Co₃O₄ compounds. The Co_0.56Ni_0.44 oxide material, which exhibits a mesoporous structure with a narrow distribution of pore size from 2 to 7 nm, possesses markedly enhanced charge‐discharge properties at high current density compared with the pure NiO and pure Co₃O₄. The Co_0.56Ni_0.44 oxide electrode shows a specific capacitance value of 1227 F/g at 5 mA/cm², which is nearly three times greater than that of the pure NiO electrode at the same current density.     

Chemical Adsorption onto an ITO Substrate of Single‐Wall Carbon Nanotube Functionalized by Carboxylic Groups as an Efficient Support for Electrocatalyst

A single‐wall carbon nanotube functionalized by carboxylic groups (SWNT‐CA) was found to be adsorbed on an indium tin oxide (ITO) electrode by chemical interaction between carboxylic groups and the ITO surface. The adsorption experiments indicated that the narrow pH conditions (around pH 3.0) exist for its adsorption which is restricted by preparation of stable fluid dispersion (favorable at higher pH) and by the chemical interaction (favorable at lower pH). Atomic force microscopic (AFM) measurements suggest that fragmented SWNT‐CA are adsorbed, primarily lying on the surface. Electrochemical impedance analysis indicated that an electrochemical double layer capacitance of the SWNT‐CA/ITO electrode is considerably higher than that for the ITO electrode, suggesting that the interfacial area between the electrode surface and the electrolyte solution is enlarged by the SWNT‐CA layer. Pt particles were deposited as a catalyst on the bare ITO and SWNT‐CA‐coated ITO (SWNT‐CA/ITO) electrodes to give respective Pt‐modified electrodes (denoted as a Pt/ITO electrode and a Pt/SWNT‐CA/ITO electrode, respectively). The cathodic current for the Pt/SWNT‐CA/ITO electrode was 1.7 times higher than that for the Pt/ITO electrode at 0.0 V, showing that the Pt/SWNT‐CA/ITO electrode works more efficiently for O₂ reduction at 0.0 V due to the SWNT‐CA layer. The enhancement by the SWNT‐CA layer is also effective for electrocatalytic proton reduction. It could be ascribable to the enlarged interfacial area between the electrode surface and the electrolyte solution.     

8-羟基脱氧鸟苷在壳聚糖/石墨烯修饰电极上的电化学及DNA氧化损伤检测

采用循环伏安(CV)、线性扫描伏安(LSV)和示差脉冲伏安(DPV)等方法研究了8-羟基脱氧鸟苷(8-OHdG)在壳聚糖(Chi)/石墨烯(GR)修饰的玻碳电极(GCE)上的电化学行为,8-OHdG在该修饰电极上氧化峰电流与其浓度在3.5×10-7~1.4×10-4 mol/L范围内呈良好的线性关系,检测限为6.4×10-8 mol/L(S/N=3)。 将Chi/GR/GCE用于检测DNA氧化损伤,8-OHdG在修饰电极上的氧化峰电流与损伤的DNA质量浓度在10~300 mg/L范围内呈良好的线性关系,损伤DNA检出限为0.026 mg/L(S/N=3)。     

Fabrication of a novel Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MoO<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> film modified electrode and its application as an electrochemical sensor of iodate

A novel organic gel film modified electrode was simply and conveniently fabricated by casting Li_xMoO_y and polypropylene carbonate (PPC) onto the surface of a gold electrode. The cyclic voltammetry and amperometry studies demonstrated that the Li_xMoO_y film modified electrode has a high stability and a good electrocatalytic activity for the reduction of iodate. In amperometry, a good linear relationship between the steady current and the concentration of iodate was obtained in the range from 3×10^–7 to 1×10^–4 mol L^–1 with a correlation coefficient of 0.9997 and a detection limit of 1×10^–7 mol L^–1.     

Electrochemical Oxidation of Methionine Mediated by a Fullerene‐C60 Modified Gold Electrode

The usefulness of a C₆₀‐fullerene modified gold (Au) electrode in mediating the oxidation of methionine in the presence of potassium ions electrolyte has been demonstrated. During cyclic voltammetry, an oxidation peak of methionine appearing at +1.0 V vs. Ag/AgCl was observed. The oxidation current of methionine is enhanced by about 2 times using a C₆₀ modified gold electrode. The current enhancement is significantly dependent on pH, temperature and C₆₀ dosage. Calibration plot reveals linearity of up to 0.1 mM with a current sensitivity of close to 50 mA L mol^?1 and detection limit of 8.2×10^?6 M. The variation of scan rate study shows that the system undergoes diffusion‐controlled process. Diffusion coefficient and rate constant of methionine were determined using hydrodynamic method (rotating disk electrode) with values of 1.11×10^?5 cm² s^?1 and 0.0026 cm s^?1 respectively for unmodified electrode while the values of diffusion coefficient and rate constant of methionine using C₆₀ modified Au electrode are 5.7×10^?6 cm² s^?1 and 0.0021 cm s^?1 respectively.     

Performance evaluation of a capillary electrophoresis electrochemical chip integrated with gold nanoelectrode ensemble working and decoupler electrodes

This paper presents a capillary electrophoresis poly(methyl methacrylate) (PMMA) based microchip for electrochemical detection applications featuring embedded gold nanoelectrode ensemble (GNEE) working and decoupler electrodes. In fabricating the microchip, the GNEE films are pressed directly onto the metallic electrode structures using a hot embossing technique, and the microfluidic channels are then sealed using a low-temperature azeotropic solvent bonding method. The detection performance of the microchip is evaluated using dopamine and catechol analytes for illustration purposes. The experimental results show that the GNEE working electrode provides a significantly higher signal response than that obtained from a bulk gold electrode when applied to the detection of dopamine analyte. Compared to a conventional bulk palladium decoupler electrode, the GNEE decoupler electrode reduces both the amplitude of the charge current (3.5 nA vs. 18.7 nA) and the baseline drift at higher separation voltages. The measured baseline current drift for the microchip equipped the proposed GNEE decoupler electrode is around three times smaller than the microchip with the palladium decoupler electrode under the applied separation electric field from 40 V/cm to 240 V/cm. Finally, when detecting a mixture of 1mM dopamine and 1mM catechol, the calculated signal response of the microchip with a GNEE decoupler electrode is approximately five times higher than that obtained from a microchip with a bulk Pd decoupler electrode, resulting in the detection limit of 1 microM for the proposed GNEE-based microchip device. Overall, the results indicate that the proposed capillary electrophoresis-electrochemical detection (CE-ED) microchip with embedded GNEE working and decoupler electrodes provides an ideal solution for sample detection in lab-on-a-chip and micro total analysis applications.     

基于金纳米棒-壳聚糖复合膜的葡萄糖生物传感器

本文采用金纳米棒-壳聚糖复合膜固定葡萄糖氧化酶构建电流型葡萄糖生物传感器.通过电化学交流阻抗法和循环伏安法对酶膜状态进行了表征,得到了相应的等效电路和动力学参数.实验结果表明,金纳米棒-壳聚糖复合膜可以辅助电子传递,提高电极的电流响应,并使生物传感器的使用温度范围有很大的扩展.此传感器表现出对葡萄糖溶液浓度的优良响应,线性范围在2.78×10^-5mol/L—2.22×10^-3mol/L,响应灵敏度约为7.819μA·cm^-2(mmol/L)^-1,表观米氏常数为10mmol/L.本工作还研究了温度和溶液pH值对电极电流响应的影响.     

Enhancement of Electrochemiluminescence of Porous Silicon with Tri‐n‐propylamine as Co‐reactant

Visible light emission can be stimulated by applying a cyclic bias to a porous silicon/tri‐n‐propylamine (PS/TPrA) solid/liquid system. With the presence of 2.5 mM TPrA, the electrochemiluminescence intensity of the in situ formed PS electrode is 450 times higher than the blank solution. An applied voltage as low as 1.2 V is capable of generating light emission, indicating that current‐induced chemical reactions are an aid to the generation of charge carriers. A mechanism involving oxidation of TPrA followed by hole injection is proposed. The system also shows good ECL stability. In addition, the ECL emission can be inhibited by diphenols rather than phenol.