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101.
《Electroanalysis》2006,18(22):2225-2231
The mechanism of electrochemical behavior of catechol in the presence of thiaproline is investigated by cyclic voltammetry, controlled‐potential coulometry and spectrophotometric tracing of the reaction coordinate. The results indicate that thiaproline participate in with an ECEC mechanism in a nucleophilic (Michael) addition to o‐quinone. Effect of pH of buffer solution on reaction pathway is studied and showed that addition of thiaproline to the o‐quinone is performed only in solutions with pHs higher than 5. These results indicate that the addition of thiaproline is occurred first from amine functional group. In the second step, the addition of carboxylate group of thiaproline to C‐5 of catechol results the final product with a lactone ring in its structure. Observation of two isosbestic point in absorption spectrum during the progress of the electrolysis together with the FT‐IR results for final product can be presented as evidence for two step addition of thiaproline to catechol. Final product, due to the electron donor property of thiaproline, more easily oxidized respect to the former catechol and as a result, a new redox couple is obtained for this compound in lower potentials. The easier anodic oxidation of addition product (relative to catechol) caused to an increase in anodic current for catechol, which is proportional to the thiaproline concentration. The differential pulse voltammetry (DPV) is applied as a sensitive voltammetric method for the detection of thiaproline. A linear range from 5×10?8 to 5×10?6 M with a detection limit of 1×10?8 M is resulted for thiaproline. With respect to the reversibility of the electrochemical reactions in the mechanism, and also more facile oxidation of the addition products, the square‐wave voltammetry is presented as a method with considerably more sensitivity for the detection of sub‐micromolar amounts of thiaproline. The advantageous properties of the voltammetric method for thiaproline detection lie in its excellent catalytic activity, sensitivity and simplicity. 相似文献
102.
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104.
本文比较了在标准石墨管,热解涂层和全热解石墨管中钒的吸收信号形状。用全热解石墨管和EDTA铵盐作基体改进剂,直接测定水系沉积物中痕量钒。方法的特征量为61pg/0.0044A。 相似文献
105.
~~Pulse radiolysis of one-electron oxidation of rare tricyclic nucleoside derivative@赵红卫$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China
@江致勤$Department of Chemistry, Tongji Unviersity!Shanghai 200092,China
@窦大营$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China
@吴铁一$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China
@王文锋$Shanghai… 相似文献
106.
原子吸收光谱法测定拉伸断口铬镍钼钛钢样品中主成分 总被引:4,自引:0,他引:4
研究了毫克级铬镍钼风样品中主成分镍的火焰原子吸收光谱法(FAAS法)和铬、钼、钒、钛、铝的塞曼恒温平台石墨炉原子吸收光谱法(ZSTPF-AAS法)。采用了微波溶样技术作为防污染样品预处理技术,采用石墨管硅涂层改进技术提高了仪器的测试精度。其中铬、镍、钼、钒、钛、铝的相对标准偏差分别为2.7%,0.97%,8.6%,7.3%,1.7%,7.3%。其加标回收率分别为96.5%,97%,96.7%,93%,98%,91%。通过分析,发现在较低温度下铬镍钼钛钢断面上有轻微的钼偏析现象,可能是拉伸断裂的主要化学影响因素。 相似文献
107.
The boundary effect on the drag on two identical, nonuniformly structured flocs moving along the axis of a cylindrical tube
filled with a Newtonian fluid is investigated at a small to medium larger Reynolds number. A two-layer model is adopted to
simulate various possible structures of a floc, and the flow field inside is described by Darcy–Brinkman model. The results
of numerical simulation reveal that a convective flow is present in the rear region of a floc when Reynolds number is on the
order of 40. The presence of the tube wall and/or the porous structure of a floc has the effect of reducing that convective
flow. For a fixed level of the volume-average permeability of a floc, the influence of the tube wall on the drag depends upon
floc structure; the influence on a nonuniformly structured floc is more significant than that on a uniformly structured floc.
The more nonuniform the floc structure, the more appreciable the deviation of the drag coefficient–Reynolds number curve from
a Stokes’-law-like relation becomes. The smaller the volume-average permeability of a floc and/or the smaller the separation
distance between the two flocs, the greater is the deviation, but the presence of the tube wall has the effect of reducing
that deviation. 相似文献
108.
The present paper deals with the speciation of selenium in potatoes (enriched or not in selenium). The study was carried out by using differential pulse cathodic stripping voltammetry (DPCSV) for quantifying selenium. Results obtained provide evidence that the selenium content in the protein fraction is rather independent from the selenium added to the plants during their growth. On the contrary, the amount of Se in the non-protein fraction (water and starch) in Se-enriched sample is significantly higher than in non-enriched one, suggesting that it is the main selenium-storing site. In this fraction the Se(VI)/Se(IV) ratio seems independent from selenium application but it may be related to the redox conditions. The accumulation of selenium in the non-protein fraction is tentatively ascribed to the “Se–starch interaction” that should be able to modulate both the Se absorption into proteins and, possibly, its toxic effect for the plant itself. 相似文献
109.
Voltammetric behaviour and determination of moxifloxacin in pharmaceutical products and human plasma
Erk N 《Analytical and bioanalytical chemistry》2004,378(5):1351-1356
The oxidative behaviour of moxifloxacin was studied at a glassy carbon electrode in different buffer systems using cyclic, differential pulse, and Osteryoung square-wave voltammetry. The oxidation process was shown to be irreversible over the entire pH range studied (2.0–10.0) and was diffusion-controlled. The methods were performed in Britton–Robinson buffer and the corresponding calibration graphs were constructed and statistical data were evaluated. When the proposed methods were applied at pH 6.0 linearity was achieved from 4.4×10–7 to 1.0×10–5 mol L–1. Applicability to tablets and human plasma analysis was illustrated. Furthermore, a high-performance liquid chromatographic method with diode-array detection was developed. A calibration graph was established from 4.0×10–6 to 5.0×10–5 mol L–1 moxifloxacin. The described methods were successfully employed with high precision and accuracy for estimation of the total drug content of human plasma and for pharmaceutical dosage forms of moxifloxacin. 相似文献
110.