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伏安法研究强致癌剂 7,12-二甲基苯并[a]蒽:在批量水相和人尿样品中的吸附溶出伏安法定量测定以及在石墨电极上检测 DNA 相互作用。

Voltammetric studies on the potent carcinogen, 7,12-dimethylbenz[a]anthracene: Adsorptive stripping voltammetric determination in bulk aqueous forms and human urine samples and detection of DNA interaction on pencil graphite electrode.

机构信息

Yüzüncü Yil University, Faculty of Science and Letter, Department of Analytical Chemistry, Campus Zeve, 65080 Van, Turkey.

出版信息

Talanta. 2010 Jan 15;80(3):1347-55. doi: 10.1016/j.talanta.2009.09.035.

Abstract

7,12-Dimethylbenz[a]anthracene (DMBA), is a widely studied polycyclic aromatic hydrocarbon that has long been recognized as a very potent carcinogen. Initially, the electrochemical oxidation of DMBA at the glassy carbon and pencil graphite electrodes in non-aqueous media (dimethylsulphoxide with lithium perchlorate) was studied by cyclic voltammetry. DMBA was irreversibly oxidized in two steps at high positive potentials, resulting in the ill-resolved formation of a couple with a reduction and re-oxidation wave at much lower potentials. Special attention was given to the use of adsorptive stripping voltammetry together with a medium exchange procedure on disposable pencil graphite electrode in aqueous solutions over the pH range of 3.0-9.0. The response was characterized with respect to pH of the supporting electrolyte, pre-concentration time and accumulation potential. Using square-wave stripping mode, the compound yielded a well-defined voltammetric response in acetate buffer, pH 4.8 at +1.15V (vs. Ag/AgCl) (a pre-concentration step being carried out at a fixed potential of +0.60V for 360s). The process could be used to determine DMBA concentrations in the range 2-10nM, with an extremely low detection limit of 0.194nM (49.7ngL(-1)). The applicability to assay of spiked human urine samples was also illustrated. Finally, the interaction of DMBA with fish sperm double-stranded DNA based on decreasing of the oxidation signal of adenine base was studied electrochemically by using differential pulse voltammetry with a pencil graphite electrode at the surface and also in solution. The favorable signal-to-noise characteristics of biosensor resulted in low detection limit (ca. 46nM) following a 300-s interaction. These results displayed that the electrochemical DNA-based biosensor could be used for the sensitive, rapid, simple and cost effective detection of DMBA-DNA interaction.

摘要

7,12-二甲基苯并[a]蒽(DMBA)是一种广泛研究的多环芳烃,长期以来被认为是一种非常有效的致癌物质。最初,通过循环伏安法研究了 DMBA 在非水介质(二甲基亚砜与高氯酸锂)中的玻璃碳和铅笔石墨电极上的电化学氧化。DMBA 在高正电势下不可逆地氧化为两步,导致在低得多的电势下形成一对还原和再氧化波。特别注意使用吸附溶出伏安法以及在 pH 值为 3.0-9.0 的水溶液中使用一次性铅笔石墨电极进行介质交换程序。响应特征与支持电解质的 pH 值、预浓缩时间和积累电位有关。使用方波溶出模式,在 pH 值为 4.8 的醋酸盐缓冲液中,该化合物在 +1.15V(相对于 Ag/AgCl)处产生了明确的伏安响应(在固定电位 +0.60V 下进行预浓缩 360s)。该过程可用于测定 2-10nM 范围内的 DMBA 浓度,检测限极低,为 0.194nM(49.7ngL(-1))。还说明了该方法在测定加标人尿样中的适用性。最后,通过使用表面铅笔石墨电极的差分脉冲伏安法研究了 DMBA 与鱼精子双链 DNA 的相互作用,基于腺嘌呤碱基氧化信号的降低。生物传感器具有良好的信噪比特征,在 300s 的相互作用后,检测限低至约 46nM。这些结果表明,基于电化学的 DNA 生物传感器可用于敏感、快速、简单且经济有效的检测 DMBA-DNA 相互作用。

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