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以乙基紫纳米颗粒与四氯化钼碘配合物作为砷酸钼的探针,采用分光光度法测定水样中的痕量砷。

Spectrophotometric determination of trace arsenic in water samples using a nanoparticle of ethyl violet with a molybdate-iodine tetrachloride complex as a probe for molybdoarsenate.

作者信息

Morita Keisuke, Kaneko Emiko

机构信息

Department of Materials Processing, Graduate School of Engineering, Tohoku University, Aoba 6-6-11-1018, Sendai 980-8579, Japan.

出版信息

Anal Chem. 2006 Nov 15;78(22):7682-8. doi: 10.1021/ac061074h.

Abstract

A new spectrophotometric method was developed for the determination of low ppb levels of arsenic in water. We found that Ethyl Violet with molybdate-iodine tetrachloride complex forms nanoparticles under acidic conditions, which provide a sensitive probe for molybdoarsenate. The nanoparticles form stable particles with a diameter micrometers in size in the presence of heteropolyacid, and the resulting particles give a purple color to the apparently homogeneous solution, the intensity of which depends on the arsenic concentration. The nanoparticle itself is unstable due to conversion of the dye to a colorless carbinol species under acidic conditions without heteropolyacid. Although triphenylmethane dyes have been the subject of a number of investigations, there do not appear to be any reports on the dye particles for trace determination. The calibration curve is linear up to 20 microg L-1 arsenic, and the detection limit is 0.5 microg L-1 (6.6 x 10(-9) mol L-1). The coefficient of variation for spectrophotometry at 10 microg L-1 is 5.8% (n = 8). Furthermore, it is possible to detect concentrations as low as 1 microg L-1 arsenic visually using this method. The interferences from phosphorus and silica were eliminated using an anion exchange column and sodium fluoride as a masking agent, respectively. The proposed method has been successfully applied to water samples in abandoned mine water, groundwater, and river water. There was good agreement between the results obtained by the proposed method and those by hydride generation atomic absorption spectrometry. Since this method is specific for As(V), it is applicable to the speciation of arsenic oxidation states. Our method has enormous practical potential for simple and field detection of arsenic, requiring no complex apparatus or skilled laboratory support.

摘要

开发了一种新的分光光度法用于测定水中低至纳克/升水平的砷。我们发现,乙基紫与钼酸碘四氯化物络合物在酸性条件下形成纳米颗粒,该纳米颗粒为砷酸钼提供了一种灵敏的探针。在杂多酸存在下,纳米颗粒形成直径为微米级的稳定颗粒,所得颗粒使原本均匀的溶液呈现紫色,其颜色强度取决于砷的浓度。由于在没有杂多酸的酸性条件下染料会转化为无色的甲醇类物质,所以纳米颗粒本身不稳定。尽管三苯甲烷染料已成为多项研究的主题,但似乎没有关于用于痕量测定的染料颗粒的报道。校准曲线在砷浓度高达20微克/升时呈线性,检测限为0.5微克/升(6.6×10⁻⁹摩尔/升)。在10微克/升时分光光度法的变异系数为5.8%(n = 8)。此外,使用该方法可以目视检测低至1微克/升的砷浓度。分别使用阴离子交换柱和氟化钠作为掩蔽剂消除了磷和硅的干扰。所提出的方法已成功应用于废弃矿井水、地下水和河水中的水样。所提出的方法与氢化物发生原子吸收光谱法所得结果之间具有良好的一致性。由于该方法对As(V)具有特异性,因此适用于砷氧化态的形态分析。我们的方法在简单现场检测砷方面具有巨大的实际潜力,无需复杂设备或熟练的实验室支持。

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