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三(五氟乙基)三氟磷酸酯基离子液体作为用于萃取环境水体中有机磷酸酯的优良固相微萃取涂层。

Tris(pentafluoroethyl)trifluorophosphate-basd ionic liquids as advantageous solid-phase micro-extraction coatings for the extraction of organophosphate esters in environmental waters.

作者信息

Shi Fengqiong, Liu Jingfu, Liang Kang, Liu Rui

机构信息

State Key Laboratory of Environmental and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China; University of Chinese Academy of Sciences, Beijing 100049, China.

State Key Laboratory of Environmental and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China; University of Chinese Academy of Sciences, Beijing 100049, China.

出版信息

J Chromatogr A. 2016 May 20;1447:9-16. doi: 10.1016/j.chroma.2016.04.021. Epub 2016 Apr 11.

Abstract

Ionic liquids (ILs) containing the tris(pentafluoroethyl)trifluorophosphate [FAP] anion and various cations have great potential in sample preparation because of their excellent hydrophobicity, thermostability and low hydrolysity. In the present study, a [FAP]-based IL, 1-hexyl-3-methylimidazolium tris (pentafluoroethyl) trifluoro phosphate ([HMIM][FAP]), was used as coatings of solid-phase microextraction (SPME) for extracting organophosphate esters (OPEs) from environmental water samples. This SPME fiber was fabricated by coating a stainless steel wire substrate with [HMIM][FAP] via a simple direct dip-coating approach, and the extraction was conducted by the direct immersion solid phase microextraction. Coupling to gas chromatography mass spectrometry (GC-MS), the developed SPME method exhibited excellent selectivity and sensitivity towards the extraction of 11 OPEs from aqueous samples. Satisfactory linearity (R(2)≥0.99) of the calibration curves was obtained over the range of 0.05-50.0ngmL(-1) with the limits of detection (LODs, S/N=3) and limits of quantification (LOQs, S/N=10) ranged from 0.13-7.40ngL(-1) and 0.50-24.0ngL(-1), respectively. The proposed SPME method showed excellent extraction efficiency to OPEs with enrichment factors in the range of 168-2603, and acceptable reproducibility with relative standard deviations (RSDs) ≤15% for single fiber (n=7) and ≤16% for fiber-to-fiber (n=3×3) at a concentration level of 0.5ngmL(-1), respectively. The prepared IL-based fiber was successfully applied to determine eleven common used OPEs in tap water, influent and effluent of sewage treatment plant, with results are comparable to those determined by the reference (UPLC-MS/MS), and spiked recoveries in the range of 84.0-108%, 82.1-123% and 82.8-100%, respectively.

摘要

含有三(五氟乙基)三氟磷酸酯[FAP]阴离子和各种阳离子的离子液体(ILs),因其优异的疏水性、热稳定性和低水解性,在样品制备方面具有巨大潜力。在本研究中,一种基于[FAP]的离子液体,1-己基-3-甲基咪唑三(五氟乙基)三氟磷酸酯([HMIM][FAP]),被用作固相微萃取(SPME)涂层,用于从环境水样中萃取有机磷酸酯(OPEs)。这种SPME纤维是通过简单的直接浸涂方法,将[HMIM][FAP]涂覆在不锈钢丝基质上制成的,萃取通过直接浸入固相微萃取进行。与气相色谱-质谱联用(GC-MS),所开发的SPME方法对从水样中萃取11种OPEs表现出优异的选择性和灵敏度。在校准曲线0.05 - 50.0 ng mL⁻¹范围内获得了令人满意的线性(R²≥0.99),检测限(LODs,S/N = 3)和定量限(LOQs,S/N = 10)分别为0.13 - 7.40 ng L⁻¹和0.50 - 24.0 ng L⁻¹。所提出的SPME方法对OPEs显示出优异的萃取效率,富集因子在168 - 2603范围内,并具有可接受的重现性,在浓度水平为0.5 ng mL⁻¹时,单纤维(n = 7)的相对标准偏差(RSDs)≤15%,纤维间(n = 3×3)的相对标准偏差≤16%。制备的基于离子液体的纤维成功应用于测定自来水中、污水处理厂进水和出水中11种常用的OPEs,结果与参考方法(超高效液相色谱-串联质谱法,UPLC-MS/MS)测定的结果相当,加标回收率分别在84.0 - 108%、82.1 - 123%和82.8 - 100%范围内。

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