基于SI-ATRP技术制备磁性甲基对硫磷分子印迹聚合物及其吸附性能
Synthesis of methyl-parathion molecularly imprinted magnetic nanoparticles via surface-initiated atom transfer radical polymerization (SI-ATRP) and its adsorption properties
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摘要: 基于DFT计算,优选出甲基对硫磷(MP)和功能单体甲基丙烯酸(MAA),4-乙烯基吡啶(4-VP)的配比为1∶2∶1,采用表面引发原子转移自由基聚合(SI-ATRP)技术,制备了核壳式磁性甲基对硫磷分子印迹聚合物(Fe3O4@MPIPs).通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅立叶变换红外光谱仪(FTIR)、X-射线衍射仪(XRD)和振动样品磁强计(VSM)对该磁性印迹聚合物进行了表征,并结合磁固相萃取(M-SPE)技术和气相色谱(GC)研究了其对MP的吸附行为,结果表明,Fe3O4@MPIPs对模板分子MP具有良好的特异性识别作用,在30 min内快速达到吸附平衡,最大吸附量为11.5 mg·g-1;与乐果和马拉硫磷相比,Fe3O4@MPIPs对MP的选择性系数分别为4.57和5.10,相对选择性系数分别为4.11和4.18.气相色谱检测结果表明,该磁性印迹聚合物可用于土豆样品中MP的快速分离富集,其加标回收率为87.4%—99.4%,RSD为3.6%—4.5%;重复使用5次后,Fe3O4@MPIPs回收率仍在90.3%以上,吸附量仍保持在第1次吸附量的82%以上.
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关键词:
- 核壳式磁性分子印迹聚合物 /
- 表面引发原子转移自由基聚合 /
- 甲基对硫磷 /
- 功能单体 /
- DFT计算
Abstract: A super-magnetic methyl parathion surface-molecularly imprinted nanoparticles Fe3O4@MPIPs were prepared via surface initiated atom transfer radical polymerization (SI-ATRP) with a theoretical proposed polymerization ratio of 1:2:1 for methyl parathion (MP):methacrylic acid (MAA):4-vinylpridine (4-VP). The morphology of Fe3O4@MPIPs was characterized by SEM,TEM,FTIR,VSM,and XRD. The adsorption properties were explored via a methodology of combining M-SPE coupled with gas chromatography. Results suggested that the well selective recognition of Fe3O4@MPIPs towards MP,which could reach the sorption equibrium in 30 mins with a max adsorption capacity of 11.5 mg·g-1. The selectivity coefficients of Fe3O4@MIPs for MP/dimethoate and MP/malathion were 4.57 and 5.10,respectively. While the relative selectivity coefficients of Fe3O4@MIPs for MP/dimethoate and MP/malathion were 4.11 and 4.18,respectively. Data tested by gas chromatography further suggested the Fe3O4@MPIPs could be used to fast determine methyl parathion in potato samples,of which the spiked methyl parathion of potato was successfully determined and the recoveries ranging from 87.4% to 99.4% with RSD of 3.6%-4.5% (n=7). The memory and recognition ability to MP for the regenerated adsorbent remain higher than 90.3% (>82% of the first adsorption) after five cycles. -
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