马梅花, 牛玉玲, 龚艳茹, 王玥, 王惠军, 龚波林. 基于表面引发原子转移自由基聚合技术制备2,4-二氯苯氧乙酸分子印迹聚合物及其识别特性分析[J]. 农药学学报, 2014, 16(2): 165-173. DOI: 10.3969/j.issn.1008-7303.2014.02.09
    引用本文: 马梅花, 牛玉玲, 龚艳茹, 王玥, 王惠军, 龚波林. 基于表面引发原子转移自由基聚合技术制备2,4-二氯苯氧乙酸分子印迹聚合物及其识别特性分析[J]. 农药学学报, 2014, 16(2): 165-173. DOI: 10.3969/j.issn.1008-7303.2014.02.09
    MA Meihua, NIU Yuling, GONG Yanru, WANG Yue, WANG Huijun, GONG Bolin. Preparation of 2,4-dichlorophenoxyacetic acid molecular-imprinted materials via surface-initiated atom transfer radical polymerization and its recognition character analysis[J]. Chinese Journal of Pesticide Science, 2014, 16(2): 165-173. DOI: 10.3969/j.issn.1008-7303.2014.02.09
    Citation: MA Meihua, NIU Yuling, GONG Yanru, WANG Yue, WANG Huijun, GONG Bolin. Preparation of 2,4-dichlorophenoxyacetic acid molecular-imprinted materials via surface-initiated atom transfer radical polymerization and its recognition character analysis[J]. Chinese Journal of Pesticide Science, 2014, 16(2): 165-173. DOI: 10.3969/j.issn.1008-7303.2014.02.09

    基于表面引发原子转移自由基聚合技术制备2,4-二氯苯氧乙酸分子印迹聚合物及其识别特性分析

    Preparation of 2,4-dichlorophenoxyacetic acid molecular-imprinted materials via surface-initiated atom transfer radical polymerization and its recognition character analysis

    • 摘要: 首次以氯甲基化交联聚苯乙烯树脂(CMCPS)为载体和大分子引发剂、2,4-二氯苯氧乙酸(2,4-D)为模板、丙烯酰胺(AM)为单体、乙二醇二甲基丙烯酸酯(EDMA)为交联剂、溴化铜/2,2'-联吡啶(CuBr/Bpy)为催化剂,采用表面引发原子转移自由基聚合(SI-ATRP)技术,制备了 2,4-二氯苯氧乙酸分子印迹聚合物(2,4-D MIPs),并研究了模板分子与功能单体比例对该印迹聚合物吸附量的影响。通过动态、静态及竞争试验考察了该印迹聚合物对 2,4-D的吸附性能。结果表明:2,4-D MIPs对模板分子 2,4-D具有良好的特异性识别作用;与 2,4-二氯苯酚和 2,4-二氯苯甲醛相比,2,4-D MIPs对 2,4-D的选择性系数分别为2.84和3.75,相对选择性系数分别为2.31和2.29。采用Scatchard模型分析,可以得到两类结合位点,计算得到最大表观吸附量(Qmax)分别为76.92 和142.91 mg/g,离解常数Kd分别为632.91和2 309.47 mg/L。将 2,4-D MIPs作为固相萃取剂,对豆芽样品进行添加回收试验,回收率为86%~104%,相对标准偏差(RSD)为1.9%~10%,方法的检出限为20 ng/g。该印迹聚合物可以富集分离测定2,4-D,稳定性好,并且能重复使用。

       

      Abstract: 2,4-Dichlorophenoxyacetic acid imprinted materials (2,4-D MIPs) were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) method. With chloromethyl polystyrene resin (CMCPS) as carrier and macro-initiator, the imprinted polymers were synthesized by using 2,4-D as template, acrylic amide as functional monomer and ethylene glycol dimethacrylate (EDMA) as cross-linker, and CuBr/2,2'-bipyridine (CuBr/Bpy) as the catalytic system. The influence of ratio of template and monomer on the adsorption capacity of 2,4-D MIPs was discussed in details. The binding properties of 2,4-D MIPs for 2,4-dichlorophenoxyacetic acid were studied with both static and dynamic experimental methods. The results showed that 2,4-D MIPs had specific recognition selectivity and excellent binding selectivity for the template molecule. In respect to 2,4- dichlorophenol and 2,4-dichlorobenzaldehyde, its selectivity coefficient to 2,4-D were 2.84 and 3.75, with relative selectivity coefficient 2.31 and 2.29. From the Scatchard analysis, Qmax (the apparent maximum binding amount) values were calculated to be 76.92 and 142.91 mg/g, respectively, and Kd(the dissociation constant) values were 632.91 and 2 309.47 mg/L. Using 2,4-D MIPs as solid phase materials, the fotified recoveries were among 86%-104%, with relative standard deviations (RSDs) of 1.9%-10%, and the limit of detection (LOD) in the bean sprout samples reached 20 ng/g. In conclusion, these imprinted materials can be used for enrichment or separation of trace amounts of 2,4-D, with merits of good stability, simple handling.

       

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