An Integrated Two Phases Approach to Zn2+ Ions Electroreduction on Hg

The following two numerical models have been applied to zinc cations electroreduction in 1 M NaClO₄ water solution: a classical EE model describing the concentration of involved species in solution (semi infinitive diffusion region), an extended EE model describing both: the concentration of involved species in solution and the concentration of metallic zinc inside mercury drop (in limited area of diffusion). In the latter model the inner part of mercury drop and surrounding solution were treated as dynamic interrelated system. Both models were applied to experimental cyclic voltammetric CV data in 1 M NaClO₄, the results compared and discussed. The concentration profiles of all species including metallic zinc inside mercury drop were performed. The presented integrated model is essential for theoretical and analytical aspects of the electrochemistry of mercury soluble metal cations and amalgams.     

Structure and electrochemical behaviour of 4,7-diazaheptyl-trimethoxy-silane and vinyl-trialkoxy-silane adsorbed at silver surface

Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li⁺ cations were calculated and visualised by the AM1d and PM5 semi-empirical methods.     

甲基对硫磷的快速测定及电化学性质

研究了杀虫剂甲基对硫磷的电化学性质。在pH10．38的Bdtton—Robinson缓冲溶液中，采用微分脉冲溶出伏安法在悬汞电极上得到一个还原峰，峰电位为-0．5V(vs．Ag/AgCl)，本工作对实验条件进行了深入的研究，结合线性扫描伏安法等手段。研究了体系的电化学行为。实验表明，甲基对硫磷在汞电极上具有吸附性，电极反应具有不可逆性。该法用于水果及水样中甲基对硫磷残余量的测定，结果满意。     

On-line cysteine modification for protein analysis: new probes for electrochemical tagging nanospray mass spectrometry

A series of electrogenerated selective electrophiles based on substituted benzoquinones has been characterized as tags for l-cysteine and cysteine residues in proteins. The electrophiles are generated electrochemically from the corresponding hydroquinones. It is shown from mass spectrometry analysis that the electrogenerated benzoquinone can tag the biomolecules. The rate constants pertaining to the addition of l-cysteine onto the electrogenerated benzoquinones have been determined using electrochemical techniques. The substitution patterns have been unraveled leading to the assessment of site-specific rate constants. It is shown that the rate constants are primarily dependent on the electronic nature of the substituents as expressed by the Hammett substitution constant. The apparent tagging yields observed for l-cysteine in nanospray mass spectrometry experiments do not correspond to the yields expected from the electrochemical study, as the ionisation efficiencies are highly dependent on the tag. Finally, the on-line tagging has been tested using β-lactoglobulin A and myoglobin. Based on these results, it is concluded that the tagging reaction is selective towards cysteine when it takes place in the nanospray interface. The results show that the methodology presented can be used for a rapid characterization and identification of reactive sites in biomolecules.     

Maintenance of Soft Calibration Models in the Determination of Zinc,Cadmium, Lead and Copper by Differential Pulse Anodic Stripping Voltammetry

A strategy for constructing a global multivariate calibration model that includes calibration samples measured over time on different days is developed and applied in electroanalysis. Both synthetic and real samples (tap, extracted and river water) are analyzed by differential‐pulse anodic stripping voltammetry, showing the suitability of the global model constructed that provides successful results similar to those of the usual multivariate calibration. In addition the capability of discrimination of this model is evaluated in prediction for the mean of three replicates with estimation of probability of false noncompliance, α, and false compliance, β, being found 3.1, 11.2, 6.7 and 64.7 nM for nominal concentrations of zinc, cadmium, lead and copper of 96.0, 40.4, 37.3 and 328.0 nM respectively when α=β=0.05. It has been proven that the use of the global calibration does not imply a loss of multivariate analytical sensitivity, using this parameter as quality index of the analytical procedure. The viability of using calibration maintenance strategies with electroanalytical techniques is shown, providing a way to save time and experimental effort when these techniques are used in routine analysis.     

Electrochemical studies of glutathione monolayer assembled on a polycrystalline gold electrode

The glutathione (GSH) monolayer and complex monolayer of GSH-metallic ion on polycrystalline gold electrode were studied by using K₃Fe(CN)₆ as the redox probe. As for the GSH monolayer, it was found that the metallic ions could open the ion-gate in the monolayer dramatically in the order La³⁺> Pb²⁺>>Ba²⁺>Ca²⁺ whereas Zn²⁺ ion closed the ion-gate. The complexes of GSH-metallic ions were capable of self-assembling the different kind of monolayer. All the differences were related to the structural configuration of the anchored GSH molecule, which changed with different metallic ions or pH. Biography:Fang Cheng (1971-) male, Ph. D, research direction: electroanlysis.     

镍-酸性铬兰K络合物吸附波

用微分脉冲溶出伏安法研究了镍(11)与酸性铬兰K(ACBK)所生成的络合物在悬汞电极上的电化学特性及电化学反应机理，发现电极反应为镍与酸性铬兰K所生成的络合物吸附在电极表面后发生的不可逆还原。在HCl-硼砂介质中(pH8．67)，络合物在-316mV处有一吸附还原峰，其峰电流与镍浓度在0．001～0．010μ/mL范围内呈现良好的线性关系，其最低检出浓度为0．0005μg／mL。     

吸附溶出伏安法测定毗喳酮的研究

本文报道了用吸附溶出伏安法测定毗喳酮.以悬汞电极为工作电极，在Na}B,O,-NaOH介质(pH=10)中，毗喳酮产生一尖锐的吸附还原峰,E，二一1. 29V (vs. SCE )，峰电流与毗喳酮浓度在2. 0 X 10-'-8. 0 X 10-smol " L-’范围内呈良好的线性关系.检测限为2. 0 X 10-0mol " L-'(富集90s).本文对毗喳酮在悬汞电极上的电化学行为进行了探讨，对测定毗喳酮的最佳条件进行了详细的选择，利用本法测定了片剂中毗喳酮含量，结果满意.     

铅溴络合物极谱吸附波的研究

本文研究了铅溴络合物在高氯酸－磷酸－草酸介质中的极谱行为。确定底液组成为５％ＮａＢｒ－１１％ＨＣｌＯ４－５％Ｈ３ＰＯ４－０．８％Ｈ２Ｃ２Ｏ４。工作曲线线性范围为０－１５０μｇ／５０ｍｌ检测下限达０．０１μｇ／ｍｌ体系选择性好，应用于实际样品的测定，获得满意结果。     

硼酸对镍-镁合金电沉积和电化学性质的影响

该文报道了分别用0．05、0．10、0．15、0．33、0．50g／mL的硼酸进行电沉积镍-镁合金的实验。原子吸收光谱实验的结果表明，沉积相中包含不等量的镍和镁，电流效率也随硼酸量的不同而发生不同趋势的变化。从极化实验的结果，讨论了硼酸在电沉积中所起的作用是阻碍氢气的析出。在溶出伏安图中，能观察到5种不同强度的Mg2Ni峰，与XRD得到的结果相吻合。循环伏安测量结果证明镍-镁合金沉积薄膜电极具有良好的充／放电性能。