Sensitive, selective analysis of selenium oxoanions using microchip electrophoresis with contact conductivity detection.

Sensitive, selective analysis of selenium oxoanions using microchip electrophoresis with contact conductivity detection.
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DOI:
10.1021/ac502013k
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发表时间:
2014-08-19
影响因子:
7.4
通讯作者:
Henry, Charles S.
Henry, Charles S.
中科院分区:
化学1区
文献类型:
--
作者:
Noblitt, Scott D.;Staicu, Lucian C.;Ackerson, Christopher J.;Henry, Charles S.

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常见的硒氧阴离子亚硒酸盐(SeO32-)和亚硒酸盐(SeO42-)在摄入量略低于1毫克/天时是有毒的。这些阴离子目前通过各种传统分析技术进行监测,这些技术耗时、昂贵、需要大量样品,和/或缺乏便携性。为了满足快速和廉价分析硒氧阴离子的需求,我们提出了第一个微芯片毛细管区带电泳法(MCE),在氯酸盐、硫酸盐、硝酸盐、亚硝酸盐、氯酸盐、磺酸盐、甲烷磺酸和氟化物存在下针对这些物种进行分离,可以同时进行监测。化学的设计是为了在非理想的基质中提供高选择性。在pH为4附近操作可避免常见弱酸的干扰。提高了从氯化物中的分离分辨率,以提高对高盐度基质的耐受性。因此,在高达1.5 mM的氯化钠存在下,亚硒酸盐可以被定量,而且亚硒酸盐分析对氯化物的分析更加可靠。使用接触电导检测,对电导率等于背景电解液的样品的检测下限分别为53 NM(4.2 ppb Se)和380 NM(30 Ppb Se)。分析时间,包括进样,为∼2分钟。MCE方法与离子色谱(IC)进行了对比验证,使用了添加的BBL肉汤样品,在分析时间为<10%的情况下,其准确度略高于离子色谱。通过监测培养在LB肉汤中的细菌对亚硒酸盐的消耗,证明了该技术在实际样品中的适用性。
The common selenium oxoanions selenite (SeO32–) and selenate (SeO42–) are toxic at intake levels slightly below 1 mg day–1. These anions are currently monitored by a variety of traditional analytical techniques that are time-consuming, expensive, require large sample volumes, and/or lack portability. To address the need for a fast and inexpensive analysis of selenium oxoanions, we present the first microchip capillary zone electrophoresis (MCE) separation targeting these species in the presence of chloride, sulfate, nitrate, nitrite, chlorate, sulfamate, methanesulfonate, and fluoride, which can be simultaneously monitored. The chemistry was designed to give high selectivity in nonideal matrices. Interference from common weak acids is avoided by operating near pH 4. Separation resolution from chloride was enhanced to improve tolerance of high-salinity matrices. As a result, selenate can be quantified in the presence of up to 1.5 mM NaCl, and selenite analysis is even more robust against chloride. Using contact conductivity detection, detection limits for samples with conductivity equal to the background electrolyte are 53 nM (4.2 ppb Se) and 380 nM (30 ppb) for selenate and selenite, respectively. Analysis time, including injection, is ∼2 min. The MCE method was validated against ion chromatography (IC) using spiked samples of dilute BBL broth and slightly outperformed the IC in accuracy while requiring <10% of the analysis time. The applicability of the technique to real samples was shown by monitoring the consumption of selenite by bacteria incubated in LB broth.
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