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用离子印迹聚合物从自来水和河水中选择性固相萃取镧系元素。

Selective solid phase extraction of lanthanides from tap and river waters with ion imprinted polymers.

作者信息

Moussa Manel, Ndiaye Massamba Mbacké, Pinta Thomas, Pichon Valérie, Vercouter Thomas, Delaunay Nathalie

机构信息

Laboratory of Analytical, Bioanalytical Sciences and Miniaturization (LSABM), UMR CBI 8231, ESPCI Paris, PSL Research University, Paris, France; UPMC, Sorbonne Universités, Paris, France.

Laboratory of Analytical, Bioanalytical Sciences and Miniaturization (LSABM), UMR CBI 8231, ESPCI Paris, PSL Research University, Paris, France.

出版信息

Anal Chim Acta. 2017 Apr 22;963:44-52. doi: 10.1016/j.aca.2017.02.012. Epub 2017 Feb 24.

Abstract

For the first time, an ion imprinted polymer (IIP) able to selectively extract simultaneously all the lanthanide ions was successfully synthesized in acetonitrile using Nd as a template ion, methacrylic acid as a complexing monomer, and ethylene glycol dimethacrylate as a cross-linker. A non-imprinted polymer (NIP) was synthesized under the same conditions as those of the IIP, but in the absence of the template ion. After the removal of the template ions, grounding and sieving, the IIP particles were packed in solid phase extraction (SPE) cartridges. The selectivity of the IIP was evaluated by comparing its behavior with the one of the NIP. Each SPE step (percolation, washing, and elution) was optimized in order to find the best compromise between the selectivity and the extraction recoveries. Using the optimized SPE conditions, the extraction recoveries of eight lanthanide ions representative of the lanthanide family were higher than 77% with an average value of 83% with the IIP, whereas, in the case of the NIP, they ranged between 14 and 36% and they were below 3% for the interfering ions from alkali, transition, and post-transition metal families with the IIP. A first evaluation of the reproducibility of the SPE profiles was carried out by performing statistical tests on the data obtained with several cartridges filled with particles obtained from two different IIP and NIP syntheses. Promising results were obtained. The specific capacity, i. e. the adsorption capacity of Nd ions by the specific cavities of the imprinted polymer, was about 9 mg of Nd per gram of IIP (60 μmol g), which is more than enough for the extraction of the lanthanide ions at trace levels. The breakthrough volume was about 1 mL per mg of IIP, leading to an enrichment factor of 15, which allows not only to selectively extract the lanthanides but also to concentrate them. Finally, the imprinted polymer was successfully used to selectively extract lanthanides from tap and river waters spiked at 1 μg L.

摘要

首次以钕为模板离子、甲基丙烯酸为络合单体、乙二醇二甲基丙烯酸酯为交联剂,在乙腈中成功合成了一种能够同时选择性萃取所有镧系离子的离子印迹聚合物(IIP)。在与IIP相同的条件下合成了非印迹聚合物(NIP),但未加入模板离子。去除模板离子、研磨并筛分后,将IIP颗粒填充到固相萃取(SPE)小柱中。通过将IIP的行为与NIP的行为进行比较,评估了IIP的选择性。对每个SPE步骤(渗滤、洗涤和洗脱)进行了优化,以便在选择性和萃取回收率之间找到最佳平衡。使用优化后的SPE条件,IIP对镧系家族中代表性的八种镧系离子的萃取回收率高于77%,平均值为83%;而对于NIP,其回收率在14%至36%之间,对于来自碱金属、过渡金属和后过渡金属家族的干扰离子,IIP的回收率低于3%。通过对从两次不同的IIP和NIP合成中获得的颗粒填充的多个小柱所得到的数据进行统计测试,对SPE谱图的重现性进行了首次评估,获得了有前景的结果。比容量,即印迹聚合物特定空穴对钕离子的吸附容量,约为每克IIP 9毫克钕(60微摩尔/克),这对于痕量水平镧系离子的萃取来说绰绰有余。穿透体积约为每毫克IIP 1毫升,富集因子为15,这不仅能够选择性萃取镧系元素,还能对其进行浓缩。最后,该印迹聚合物成功用于从添加了1微克/升镧系元素的自来水和河水中选择性萃取镧系元素。

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