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Abstract: In the paper, a new kind of vitamin B12 (acquo-cobalamine) chemically modified electrode was fabricated and applied in capillary zone electrophoresis coupled with amperometric detection (CZE-AD) for simultaneous determination of six antioxidants in fruits and vegetables. The catalytic electrochemical properties of the chemically modified electrode could obviously enhance oxidation peak heights responses by about five times to glutathione, ascorbic acid, vanillic acid, chlorogenic acid, salicylic acid, and caffeic acid compared with common carbon disk electrode. Furthermore, the effects of working electrode potential, pH and concentration of running buffer, separation voltage and injection time on CZE-AD were investigated. Under the optimum conditions, the six analytes could be completely separated and detected in a borate–phosphate buffer (pH 8.4) within 15min. Their linear ranges were from 2.5×10−7 to 1.0×10−4 molL−1 and the detection limits were as low as 10−8 molL−1 magnitude (S/N =3). The proposed method has been successfully employed to monitor the six analytes in practical samples with recoveries in the range 96.0–106.0% and RSDs less than 5.0%. Above results demonstrate that capillary zone electrophoresis coupled with electrochemical detection using vitamin B12 modified electrode as detector is of convenient preparation, high sensitivity, good repeatability, and could be used in the rapid determination of practical samples. [Copyright &y& Elsevier]

Abstract: Despite the separation efficiency of capillary electrophoresis (CE) is much higher than other chromatographic methods, it is sometimes difficult to perfectly separate the complex ingredients in biological samples. One possible and simple way to develop the separation effect in CE is to add some modifiers in the running buffer. In this paper, the suitable running buffer modifiers were explored to simultaneously separate and detect six typical flavonoids (apigenin, luteolin, kaempferol, quercetin, (+)-catechin and (−)-epicatechin) which are the main active ingredients in chrysanthemum by capillary zone electrophoresis with amperometric detection (CZE-AD). It was found that when β-cyclodextrin (β-CD) and the mixture of methanol and ethanol were used as running buffer modifiers, a baseline separation of the six analytes could be accomplished in less than 20min and the detection limits were as low as 10−7 or 10−8 gml−1. Other factors affecting the CZE separation, such as working potential, pH value and ionic strength of running buffer, separation voltage and sample injection time were extensively investigated. Under the optimum conditions, a successful practical application on the determination of chrysanthemum samples confirmed the validity and practicability of this method. [Copyright &y& Elsevier]