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一种简单的柱切换离子色谱技术在去除复杂样品中基质干扰及灵敏荧光测定酸性化合物(药物)方面的应用。

Application of a simple column-switching ion chromatography technique for removal of matrix interferences and sensitive fluorescence determination of acidic compounds (pharmaceutical drugs) in complex samples.

作者信息

Muhammad Nadeem, Subhani Qamar, Wang Fenglian, Guo Dandan, Zhao Qiming, Wu Shuchao, Zhu Yan

机构信息

Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028, China.

Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028, China; Higher Education Department, Punjab, Lahore, Pakistan.

出版信息

J Chromatogr A. 2017 Sep 15;1515:69-80. doi: 10.1016/j.chroma.2017.07.007. Epub 2017 Jul 5.

Abstract

This work illustrates the introduction of a simple, rugged and flexible column-switching ion chromatography (IC) technique for an automated on-line QuEChERS extracted samples extracts washing followed by sensitive fluorescence (FLD) determination of five acidic pharmaceutical drugs namely; clofibric acid (CLO), ibuprofen (IBU), aspirin (ASP), naproxen (NAP) and flurobrofen (FLU) in three complex samples (spinach, apple and hospital sewage sludge). An old anion exchange column IonPac AS11-HC was utilized as a pre-treatment column for on-line washing of inorganic and organic interferences followed by isocratic separation of five acidic drugs with another anion exchange IonPac AS12A analytical column by exploiting the column-switching technique. This novel method exhibited good linearity with correlation coefficients (r) for all drugs were in the range 0.976-0.996. The limit of detection and quantification of all five acidic drugs were in the range 0.024μg/kg to 8.70μg/kg and 0.082μg/kg to 0.029mg/kg, respectively, and better recoveries in the range 81.17-112.5% with percentage relative standard deviations (RSDs) less than 17.8% were obtained. This on-line sample pre-treatment method showed minimum matrix effect in the range of 0.87-1.25 except for aspirin. This simple rugged and flexible column-switching system required only 28min for maximum elimination of matrices and interferences in three complex samples extracts, isocratic separation of five acidic drugs and for the continuous regeneration of pre-treatment column prior to every subsequent analysis. Finally, this simple automated IC system was appeared so rugged and flexible, which can eliminate and wash out most of interference, impurities and matrices in complex samples, simply by adjusting the NaOH and acetonitrile concentration in washing mobile phase with maximum recoveries of acidic analytes of interest.

摘要

本研究展示了一种简单、耐用且灵活的柱切换离子色谱(IC)技术,用于自动在线对经QuEChERS提取的样品提取物进行清洗,随后通过灵敏的荧光检测法(FLD)测定三种复杂样品(菠菜、苹果和医院污水污泥)中的五种酸性药物,即氯贝酸(CLO)、布洛芬(IBU)、阿司匹林(ASP)、萘普生(NAP)和氟洛芬(FLU)。使用一根旧的阴离子交换柱IonPac AS11-HC作为预处理柱,用于在线清洗无机和有机干扰物,随后利用柱切换技术,使用另一根阴离子交换柱IonPac AS12A分析柱对五种酸性药物进行等度分离。该新方法具有良好的线性,所有药物的相关系数(r)在0.976至0.996范围内。所有五种酸性药物的检测限和定量限分别在0.024μg/kg至8.70μg/kg和0.082μg/kg至0.029mg/kg范围内,回收率较好,在81.17 - 112.5%之间,相对标准偏差(RSDs)百分比小于17.8%。这种在线样品预处理方法除阿司匹林外,基质效应在0.87 - 1.25范围内最小。这种简单、耐用且灵活的柱切换系统仅需28分钟即可最大程度地消除三种复杂样品提取物中的基质和干扰物,对五种酸性药物进行等度分离,并在每次后续分析之前对预处理柱进行连续再生。最后,这种简单的自动化IC系统显得非常耐用且灵活,通过调整清洗流动相中的氢氧化钠和乙腈浓度,能够消除和洗脱出复杂样品中的大部分干扰物、杂质和基质,同时使目标酸性分析物的回收率达到最高。

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