阴极电泳涂料用树脂－改性聚丁二烯合成工艺研究

液体聚丁二烯（ＬＰＢ）与过氧乙酸反应生成的环氧化聚丁二烯（ＯＰＢ）再与胺化剂反应生成胶化环氧化聚丁二烯（ＤＯＰＢ）是性能优良的电泳涂料用树脂．实验结果表明ＬＰＢ环氧化反应温度只能在１５～６０℃进行，且高温反应时间不能超过５小时；ＬＰＢ的分子量低．则环氧值增大。ＯＰＢ的胶化反应最佳温度为１１０℃，２ｈ内可完成反应．     

电化学阴极沉积制备氧化镍/碳纳米管复合电极的准电容特性

A novel type of composite electrode based on multiwalled carbon nanotubes coated with nano nickel oxide particles has been used in supercapacitors. Nickel oxide cathodically deposited from Ni(NO3)2 solution with carbon nanotubes as the matrix exhibited large pseudocapacitance of 25F/g in 6 mol/L KOH. The morphology of composites was examined by scanning electron microscope (SEM). To characterize the CNTs/nickel oxide composite electrode, a charge discharge cycling test for measuring specific capacitance, cyclic voltammetry, and ac impedance test is executed. The nickel oxide composite exhibiting excellent pseudocapacitive behavior(i.e.high reversibility, high specific capacitance, and low self discharge rate) has been demonstrated to be a potential candidate for the application of electrochemical supercapacitors.     

Tailoring the electrode surface structure by cathodic corrosion in alkali metal hydroxide solution: Nanostructuring and faceting of Au

Nanostructured metals are vital materials in several (electro)chemical applications. Despite the substantial progress in this field, still many limitations are associated with traditional synthetic procedures, including the availability of stable nanoparticles on appropriate supports by avoiding migration and aggregation. On that front, cathodic corrosion has emerged as a powerful technique to tailor the surface structure of metal surfaces on the nanoscale. Cathodic corrosion crucially depends on the electrode potential, the nature and the concentration of cations, as well as the electrode material. Controlling these parameters is essential for applying cathodic corrosion in materials design. In this short review, we discuss the most critical parameters controlling cathodic corrosion and highlight the importance of the nature and the concentration of alkali metal hydroxides in aqueous solution.     

A preparation method and effects of Al–Cr coating on NdFeB sintered magnets

A 50 μm Al–Cr coating on NdFeB sintered magnets was prepared through dipping in solution, shaking dry and heating at 300 °C. The morphology and composition of the Al–Cr coating were investigated with scanning electron microscope, energy dispersive spectrometer and X-ray diffraction. The corrosion resistance of NdFeB sintered magnets with and without the Al–Cr coating was analyzed by normal salt spray, polarization curves and electrochemical impedance spectroscopy. The magnetic properties were measured with a hysteresis loop tracer. The results show that the Al–Cr coating forms an overlapping structure and Al flakes lie nearly parallel to the substrate, which improves the anticorrosion and increases normal salt spray test from 10 to 100 h. The corrosion potential of NdFeB sintered magnets with and without the Al–Cr coating moves positively from −0.67 to −0.48 V, which is in accordance with Nyquist and Bode plots. The Al–Cr coating has little influence on the magnetic properties of the NdFeB sintered magnets.     

Manganese Detection with a Metal Catalyst Free Carbon Nanotube Electrode: Anodic versus Cathodic Stripping Voltammetry

Anodic stripping voltammetry (ASV) and cathodic stripping voltammetry (CSV) were used to determine Mn concentration using metal catalyst free carbon nanotube (MCFCNT) electrodes and square wave stripping voltammetry (SWSV). The MCFCNTs are synthesized using a Carbo Thermal Carbide Conversion method which results in a material that does not contain residual transition metals. Detection limits of 120 nM and 93 nM were achieved for ASV and CSV, respectively, with a deposition time of 60 s. CSV was found to be better than ASV in Mn detection in many aspects, such as limit of detection and sensitivity. The CSV method was used in pond water matrix addition measurements.     

Development of a highly sensitive and selective hyphenated technique (molecularly imprinted micro-solid phase extraction fiber-molecularly imprinted polymer fiber sensor) for ultratrace analysis of folic acid

A simple polymerization strategy is reported in this work which allows molecularly imprinted polymeric fiber (monolith) fabrication for direct use in sensing devices. This is advantageous for achieving higher degree of enrichment of target analyte (folic acid) from the complex matrices of real samples, without any surface fouling, cross-reactivity, and non-specific (false-positive) contributions. In order to measure serum folic acid at ultratrace level to detect spina bifida, a neural tube defect in mother, and other acute cases of proteomic diseases, the hyphenation between molecularly imprinted micro-solid phase extraction fiber and a complementary molecularly imprinted polymer-carbon composite fiber sensor has been found quite efficient. The primitive diagnosis of many chronic diseases is feasible by estimating folic acid as biomarker, with the detection limit as low as 0.0036 ng mL⁻¹ (relative standard deviation = 0.13%, signal/noise = 3) in human blood serum.     

Homocysteine Voltammetry at a Mercury Electrode in the Presence of Nickel Ions

At a mercury electrode, Hcy and Cys yield similar cathodic stripping peaks connected to the reduction of the pertinent mercury thiolate. However, due the different behavior as a ligand for nickel ion, the above compounds perform very differently in the presence of this ion. Whereas the nickel ion at a high enough concentration suppresses the Cys peak, in the case of Hcy it causes the cathodic peak to shift to more negative potentials. The peculiar behavior of Hcy is due to the stabilization of the mercury thiolate surface layer by intermolecular Ni²⁺ bridges within the surface layer. Conversely, in the case of Cys, the nickel ion strongly competes with the mercury ion and leads to the formation of a surface adsorbed bis‐cysteinatonickelate complex, which prevents the formation of mercury cysteinate. Such a difference allows determining Hcy by cathodic stripping voltammetry in the presence of nickel ion with no Cys interference.     

碳糊电极阴极溶出伏安法测定当归中阿魏酸

采用碳糊电极作工作电极,阴极溶出伏安法对阿魏酸进行测定。在0.05mol.L-1盐酸溶液中,当有0.04mmol.L-1氯化钠溶液,0.004g.L-1十二烷基硫酸钠溶液存在时,1.1V(vs.SCE)富集180s,以100mV.s-1扫描速率从1.0V扫描至0V。阿魏酸在碳糊电极上于0.46V处产生一灵敏的阴极溶出伏安峰,峰电流与阿魏酸浓度在2.2×10-7～1.1×10-5 mol.L-1范围内呈线性关系,检出限(3S/N)为4.0×10-8 mol.L-1。初步探讨了阿魏酸的电化学性质,此方法用于测定当归中阿魏酸的含量,并以此样品为基体做回收试验,测得回收率在104.0%～109.1%之间,测定值的相对标准偏差(n=6)在2.6%～5.3%之间。     

Voltammetric determination of Se(IV) and Se(VI) in saline samples—Studies with seawater, hydrothermal and hemodialysis fluids

Determination of Se(IV) and Se(VI) in high saline media was investigated by cathodic stripping voltammetry (CSV). The voltammetric method was applied to assay selenium in seawater, hydrothermal and hemodialysis fluids. The influence of ionic strength on selenium determination is discussed. The CSV method was based on the co-electrodeposition of Se(IV) with Cu(II) ions and Se(VI) determined by difference after sample UV-irradiation for photolytic selenium reduction. UV-irradiation was also used as sample pre-treatment for organic matter decomposition. Detection limit of 0.030 μg L⁻¹ (240 s deposition time) and relative standard deviation (RSD) of 6.19% (n = 5) for 5.0 μg L⁻¹ of Se(IV) were calculated. Linear calibration range for selenium was observed from 1.0 to 100.0 μg L⁻¹. Concerning the pre-treatment step, best results were obtained by using 60 min UV-irradiation interval in H₂O₂/HCl medium. Se(VI) was reduced to the Se(IV) electroactive species with recoveries between 91.7% and 112.9%. Interferents were also investigated.     

A reagentless DNA biosensor based on cathodic electrochemiluminescence at a C/CxO1−x electrode

A reagentless signal-on electrochemiluminescence (ECL) biosensor for DNA hybridization detection was developed based on the quenching effect of ferrocene (Fc) on intrinsic cathodic ECL at thin oxide covered glassy carbon (C/C_xO_1−x) electrodes. To construct the DNA biosensor, molecular beacon (MB) modified with ferrocene (3′-Fc) was attached to a C/C_xO_1−x electrode via the covalent bound between labeled amino (5′-NH₂) and surface functional groups. It was found that the immobilization of the probe on the electrode surface mainly depended on the fraction of surface carbonyl moiety. When a complementary target DNA (cDNA) was present, the stem-loop of MB on the electrode was converted into a linear double-helix configuration due to hybridization, resulting in the moving away of Fc from the electrode surface, and the restoring of the cathodic ECL signal. The restoration of the ECL intensity was linearly changed with the logarithm of cDNA concentration in the range of 1.0 × 10⁻¹¹ to 7.0 × 10⁻⁸ M, and the detection limit was ca. 5.0 pM (S/N = 3). Additionally, single-base mismatched DNA can be effectively discriminated from the cDNA. The great advantage of the biosensor lies in its simplicity and cost-effective with ECL generated from the electrode itself, and no adscititious luminophore is required.