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一石二鸟:基于离子液体和原子转移自由基聚合的表面分子印迹聚合物用于土霉素的选择性快速去除及灵敏测定

Kill two birds with one stone: Selective and fast removal and sensitive determination of oxytetracycline using surface molecularly imprinted polymer based on ionic liquid and ATRP polymerization.

作者信息

Chen Yanran, Tang Yun, Liu Yiwei, Zhao Faqiong, Zeng Baizhao

机构信息

College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, Hubei Province, PR China.

College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, Hubei Province, PR China.

出版信息

J Hazard Mater. 2022 Jul 15;434:128907. doi: 10.1016/j.jhazmat.2022.128907. Epub 2022 Apr 14.

Abstract

Oxytetracycline (OTC) residue in food and environment has potential threats to ecosystem and human health, thus its sensitive monitoring and effective elimination are very important. In this work, a new molecularly imprinted polymer (MIP) composite was prepared through atom transfer radical polymerization by using OTC as template, gold nanoparticles modified carbon nanospheres (Au-CNS) as supporter, ionic liquids (IL) as functional monomer and cross-linking agent. The obtained MIP-IL@Au-CNS composite was characterized by Fourier transform infrared absorption spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. It displayed high imprinting factor (5.50) and adsorption capacity (56.7 mg g), and could achieved the adsorption equilibrium in short time (about 15 min). Results also illustrated that the adsorption process basically conformed to the quasi-second-order kinetic model and Freundlich model, and MIP-IL@Au-CNS could be recycled at least 5 times. Furthermore, a sensitive OTC electrochemical sensor was developed by combining MIP-IL@Au-CNS with IL-modified carbon nanocomposites (IL@N-rGO-MWCNT). The resulting sensor demonstrated a linear response to OTC in the wide range of 0.02-20 μM, and the detection limit was down to 5 nM. It also had the advantages of high selectivity, fast elution/regeneration and simple construction procedure. The sensor had been applied to the detection of real samples, and acceptable recovery (96.4%-106%) and RSD (3.2%-6.2%) were obtained. This work expands the application of IL-based MIP in pollutant monitoring and enriching.

摘要

食品和环境中的土霉素(OTC)残留对生态系统和人类健康存在潜在威胁,因此对其进行灵敏监测和有效去除非常重要。在本研究中,以OTC为模板,金纳米粒子修饰的碳纳米球(Au-CNS)为载体,离子液体(IL)为功能单体和交联剂,通过原子转移自由基聚合制备了一种新型分子印迹聚合物(MIP)复合材料。采用傅里叶变换红外吸收光谱、X射线光电子能谱、扫描电子显微镜和透射电子显微镜对所得的MIP-IL@Au-CNS复合材料进行了表征。该复合材料显示出高印迹因子(5.50)和吸附容量(56.7 mg g),并能在短时间内(约15分钟)达到吸附平衡。结果还表明,吸附过程基本符合准二级动力学模型和Freundlich模型,且MIP-IL@Au-CNS可循环使用至少5次。此外,将MIP-IL@Au-CNS与IL修饰的碳纳米复合材料(IL@N-rGO-MWCNT)相结合,开发了一种灵敏的OTC电化学传感器。所得传感器在0.02 - 20 μM的宽范围内对OTC呈现线性响应,检测限低至5 nM。它还具有选择性高、洗脱/再生快和构建过程简单的优点。该传感器已应用于实际样品的检测,获得了可接受的回收率(96.4% - 106%)和相对标准偏差(3.2% - 6.2%)。本研究拓展了基于离子液体的分子印迹聚合物在污染物监测和富集方面的应用。

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