Anodic Stripping Voltammetry of Heavy Metals at Nanocrystalline Boron‐Doped Diamond Electrode

Boron‐doped Diamond (BDD) electrode has become one of the important tools for heavy metal detection. By studying some analytical parameters of DPASV method, like deposition time and potential in different electrolyte concentrations (acetate buffer), the conditions for detecting very low metal ion levels (Zn, Cd, Pb, and Cu) could be chosen. Diluted electrolyte (0.01 M buffer) was one of the factors favoring low detection and quantification limits, but its quantification range is short in comparison to more concentrated media. For ?1.7 V deposition potential, the detection of single metal at ppb levels was reached in 60 s deposition time. Understanding different metal‐metal interactions shows the limits to the simultaneous determination of heavy metals at BDD. Quantification was possible for the simultaneous determination of Zn, Cd and Pb despite the overlapping of Zn and Cd peaks. The performance of the BDD was compared with that of another C‐based solid electrode: the glassy carbon electrode (without mercury plating). A lower base line current, wider potential range, higher sensitivity (3 to 5 times higher than GC) and longevity of the material were noticed for the BDD.     

5-羟色胺在碳纤维微电极上的电化学测定及伏安行为研究

本文研究了5 羟色胺在Na2HPO4 KH2PO4(pH6.0)缓冲溶液中,于自制的碳纤维微电极上的伏安行为。在此缓冲溶液中5 羟色胺有一对氧化还原峰,峰电位分别为0.2V和0.4V。峰电流与5 羟色胺的浓度分别在4.0×10-6～4.0×10-5mol/L和5.0×10-6～5.0×10-5mol/L范围内呈良好的线性关系,检出限分别为4.70×10-6mol/L和1.76×10-6mol/L。同时利用多种电化学方法求出了动力学参数。     

植物生物分子的电分析化学研究——Ⅸ.多酚氧化酶活性的脉冲极谱法测定

本文用微分脉冲极谱法研究了多酚氧化酶的活性测定和酶的反应动力学。应用于马铃薯等10余种植物样品的酶活力测定,结果良好。方法简便快速,重现性好。     

Broadband and band-selective IMPRESS-gHMBC: compensation of refocusing inefficiency with synchronized inversion sweep

Compensation of refocusing inefficiency in a gHMBC experiment by replacing the rectangular pi pulse with a pair of adiabatic pulses with synchronized inversion sweep (CRISIS) significantly improves the performance of the gHMBC experiment. The CRISIS-gHMBC experiment retains the pure absorptive shapes in F1 and hence results in better lineshape and higher resolution than the current versions of magnitude mode gHMBC spectra. When used as a broadband experiment, CRISIS-gHMBC, owing to better refocusing efficiency of the adiabatic pulse pairs, gives improved performance across the 13C spectral width. Moreover, it is shown that CRISIS-gHMBC is a robust and improved alternative and when used along with the IMPRESS (Improved Resolution using Symmetrically Shifted pulses) technique further increases the sensitivity and resolution without additional experimental time. The IMPRESS-CRISIS combination is demonstrated for broadband gHMBC and band-selective gHMBC experiments. The ICbs-gHMBC [IMPRESS-CRISIS-band-selective gHMBC] experiment is an attractive and better alternative to individual band-selective gHMBC.     

Pulse radiolysis study of I− oxidation with radical anions Cl2 ⋅− in an aqueous solution

Radiation-chemical transformations of chloride solutions in the presence of iodide additives were studied by pulse radiolysis. Radical anion Cl₂ ^⋅− oxidize I⁻ ion, while in the secondary reactions Cl₂ reacts with I⁻ to form a mixed trihalide ion ICl₂ ⁻. A reaction model that satisfactorily describes the experimental data was proposed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1336–1340, June, 2005.     

盐酸吡哆辛及其制剂的二阶导数差示脉冲极谱法定量研究

建立盐酸吡哆辛及其制剂的二阶导数差示脉冲极谱定量分析方法。盐酸吡哆辛在0.1mol/L氢氧化钠溶液-0.1moL/L磷酸二氢钾溶液-水(体积比为1.2:8.8:990)的混合溶液中,于-0.140V(vs·Ag/AgCl)处出现一良好的二阶导数差示脉冲极谱峰,盐酸吡哆辛浓度在3.6×10~(-4)～9.6×10~(-4)mol/L范围内与其峰幅值呈显著的线性关系(P<0.01),线性相关系数r=0.9997,检出限为9.0nmol/L。     

Electrochemical Study of the Lipid‐Transfer Protein

Electrochemical study of barley grain lipid‐transfer protein (LTP) revealed that it may belong to the metal‐binding protein class. Using differential pulse polarography the presence of Cu(II) and Zn(II) ions in the native LTP structure was proved, as well as its affinity for binding Ni(II) ion. Application of a more sensitive electroanalytical technique, such as anodic stripping voltammetry with analyte preconcentration, revealed the presence of Pb(II) and Cd(II) ions and also enabled the following Hg(II) ion binding. Possible biological role of LTP in plant stress response and its contribution to barley phytoextraction potential are discussed.     

Highly conjugated p-quinonoid pi-extended tetrathiafulvalene derivatives: a class of highly distorted electron donors

A new class of pi-extended TTF-type electron donors (11 a-c) has been synthesized by Wittig-Horner olefination of bianthrone (9) with 1,3-dithiole phosphonate esters (10 a-c). In cyclic voltammetry experiments, donors 11 a-c reveal a single, electrochemically irreversible oxidation-yielding the corresponding dicationic products-at relatively low oxidation potentials (approximately 0.7-0.8 V). Theoretical calculations, performed at the DFT level (B3 P86/6-31 G*), predict a highly-folded C(2h) structure for 11 a. In the ground state, the molecule adopts a double saddle-like conformation to compensate the steric hindrance. The calculations suggest that the intramolecular charge transfer associated with the HOMO-->LUMO transition is responsible for an absorption band observed above 400 nm. While the radical cation 11 a*+ retains the folded C(2h) structure predicted for the neutral molecule as the most stable conformation, the dication 11 a(2+) has a fully aromatic D(2) structure, formed by an orthogonal 9,9'-bianthryl central unit to which two singly-charged dithiole rings are attached. The drastic conformational changes that compounds 11 undergo upon oxidation account for their electrochemical properties. By means of pulse radiolysis measurements, radical-induced one-electron oxidation of 11 a-c was shown to lead to the radical cation species (11 a-c*+), which were found to disproportionate with generation of the respective dication species (11 a-c(2+)) and the neutral molecules (11 a-c).     

铜膜差分脉冲阳极溶出伏安法测定药物中铋的含量

研究了铜膜电极代替汞膜电极测定重金属铋的差分脉冲溶出伏安法。实验了同位镀膜法测定铋的条件。在最佳实验条件下,Bi3+浓度在5×10-8~2×10-5mol/L范围内,其溶出峰峰高与浓度呈线性关系,检出限达到1×10-8mol/L。测定了一些药物中铋的含量,结果准确。