Magnetic cationic covalent organic framework for selective enrichment of phenoxy carboxylic acid herbicides prior to quantification by LC–MS/MS

IF 5.3 2区化学 Q1 CHEMISTRY, ANALYTICAL

Microchimica Acta Pub Date : 2025-09-22 DOI:10.1007/s00604-025-07528-9

Guiju Xu, Xingyun Zhao, Chenghao Hou, Hongwei Zhang, Baoyu Li, Chunlei Yang

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引用次数: 0

Abstract

A magnetic ionic covalent organic framework (iCOF) was prepared with dimidium bromide (DB) as the ionic building blocks and named as Fe₃O₄@DB-iCOF. The Fe₃O₄@DB-iCOF was applied as magnetic solid-phase extraction (MSPE) adsorbent for the enrichment of phenoxy carboxylic acid herbicides (PCAs). Various MSPE parameters including pH, ionic strength, adsorbent dosage, extraction time, eluent type, and eluent volume were optimized. The coexistence interference and recycle experiments confirmed the Fe₃O₄@DB-iCOF possesses the selectivity characteristics of mixed-mode ion-exchange adsorbent and good reusability towards PCAs. The density function theory (DFT) computational adsorption energy verified the adsorption process is exothermic and spontaneous. The molecular dynamics (MD) simulation confirmed the crucial role of electrostatic interaction in driving adsorption process. A novel method for analyzing trace PCAs residues in water samples has been established by combining the Fe₃O₄@DB-iCOF based MSPE with liquid chromatography tandem mass spectrometry (LC–MS/MS). The proposed method exhibits wide linear range (10–2000 ng L⁻¹) and high sensitivity with limits of detection in the range 0.8–1.9 ng L⁻¹. The proposed method was utilized to determine PCAs in river and lake water, with spiked recoveries ranging from 90.8 to 103.1%, confirming its good accuracy.

Graphical Abstract

Abstract Image

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磁性阳离子共价有机框架在LC-MS /MS定量前选择性富集苯氧羧酸类除草剂

以溴化二镉（DB）为离子单元制备了磁性离子共价有机骨架（iCOF），命名为Fe3O4@DB-iCOF。采用Fe3O4@DB-iCOF作为磁性固相萃取（MSPE）吸附剂富集苯氧羧酸类除草剂（PCAs）。对pH、离子强度、吸附剂用量、萃取时间、洗脱液种类、洗脱液体积等MSPE参数进行了优化。共存干扰和循环实验证实了Fe3O4@DB-iCOF具有混合模式离子交换吸附剂的选择性和对PCAs良好的可重复使用性。密度泛函理论（DFT）计算吸附能验证了吸附过程是放热自发的。分子动力学（MD）模拟证实了静电相互作用在驱动吸附过程中的关键作用。建立了一种基于Fe3O4@DB-iCOF的MSPE与LC-MS /MS相结合分析水样中痕量PCAs残留的新方法。该方法线性范围宽（10 ~ 2000 ng L−1），灵敏度高，检出限在0.8 ~ 1.9 ng L−1。将该方法用于河流和湖泊水体中PCAs的测定，加标回收率在90.8% ~ 103.1%之间，具有较好的准确度。图形抽象

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来源期刊

Microchimica Acta 化学-分析化学

CiteScore

9.80

自引率

5.30%

发文量

410

审稿时长

2.7 months

期刊介绍： As a peer-reviewed journal for analytical sciences and technologies on the micro- and nanoscale, Microchimica Acta has established itself as a premier forum for truly novel approaches in chemical and biochemical analysis. Coverage includes methods and devices that provide expedient solutions to the most contemporary demands in this area. Examples are point-of-care technologies, wearable (bio)sensors, in-vivo-monitoring, micro/nanomotors and materials based on synthetic biology as well as biomedical imaging and targeting.