Hao Yi, Gao Ruixia, Shi Lu, Liu Dechun, Tang Yuhai, Guo Zengjun
Institute of Analytical Science, Xi'an Jiaotong University, Xi'an 710049, China.
Institute of Analytical Science, Xi'an Jiaotong University, Xi'an 710049, China.
J Chromatogr A. 2015 May 29;1396:7-16. doi: 10.1016/j.chroma.2015.03.083. Epub 2015 Apr 7.
Endocrine disrupting compounds (EDCs) are a potential risk for wildlife and humans for their existence in water. The efficient extraction and clean-up steps are required before detection of low concentration levels of EDCs. In this work, a novel water-compatible magnetic molecularly imprinted nanoparticles is synthesized for the selective extraction of 17β-estradiol (E2) in environmental water samples. The preparation is carried out by introducing aldehyde groups to the surface of amino-functionalized magnetic nanoparticles through a simple one-step modification, followed by copolymerization of functional monomer gelatin and template E2 via surface imprinting technique. The gelatin with abundant active groups could not only act as functional monomer reacting with template, but also assemble covalently at the surface of magnetic nanoparticles. At the same time, gelatin would improve the water-compatibility of imprinted materials for attaining high extraction efficiency. To obtain high imprinting effect, the preparation conditions are optimized in detail using Central composite design-response surface methodology. The resultant polymers have uniform spherical shape with a shell thickness of about 8nm, stable crystalline form, and super-paramagnetic property. Meanwhile, the obtained polymers have high capacity of 12.87mgg(-1) and satisfactory selectivity to template molecule. To testify the feasibility of the magnetic imprinted polymers in sample pretreatment, a method for determination of trace E2 in environmental water samples was set up by combination of solid-phase extraction (SPE) using the prepared polymers as sorbents and HPLC for rapid isolation and determination of E2. The limit of detection of proposed method is 0.04ngmL(-1), the intra- and inter-day relative standard deviations (RSDs) are less than 4.6% and 5.7%, respectively. The recoveries of E2 from environmental water samples are in the range from 88.3% to 99.1% with the RSDs less than 7.2%.
内分泌干扰化合物（EDCs）因其存在于水中，对野生动物和人类构成潜在风险。在检测低浓度的EDCs之前，需要高效的提取和净化步骤。在这项工作中，合成了一种新型的水相兼容磁性分子印迹纳米粒子，用于选择性提取环境水样中的17β-雌二醇（E2）。通过简单的一步修饰将醛基引入氨基功能化磁性纳米粒子表面，然后通过表面印迹技术使功能单体明胶与模板E2发生共聚反应来进行制备。具有丰富活性基团的明胶不仅可以作为与模板反应的功能单体，还能在磁性纳米粒子表面共价组装。同时，明胶会提高印迹材料与水的兼容性，以获得高提取效率。为了获得高印迹效果，采用中心复合设计-响应面法详细优化了制备条件。所得聚合物具有均匀的球形，壳层厚度约为8nm，晶体形态稳定，具有超顺磁性。同时，所获得的聚合物对模板分子具有12.87mg g⁻¹的高吸附容量和令人满意的选择性。为了验证磁性印迹聚合物在样品预处理中的可行性，建立了一种通过使用制备的聚合物作为吸附剂的固相萃取（SPE）与用于快速分离和测定E2的高效液相色谱（HPLC）相结合的方法来测定环境水样中痕量E2。所提出方法的检测限为0.04ng mL⁻¹，日内和日间相对标准偏差（RSDs）分别小于4.6%和5.7%。环境水样中E2的回收率在88.3%至99.1%之间，RSDs小于7.2%。
