A tailor-made porous molecularly imprinted polymer (MIP) thin-film was prepared by in situ photo-radical polymerization on a glass slide and used as a microextraction adsorbent. Detection was carried out using gas chromatography-mass spectrometry (GC-MS) to afford a method suitable for the selective determination of trace concentrations of polycyclic aromatic sulfur heterocycles (PASHs) in seawater. PASHs are one of the most problematic aromatic organic pollutants, as they are considered more persistent and toxic compared to other analogous aromatic compounds in the environment. The optimized thin-film consisted of a 2-thiophenecarboxaldehyde pseudo-template with 1-vinylimidazole (1-Vim) as the functional monomer, bisphenol A dimethacrylate (BPADMA) as the cross-linker, acetonitrile as the porogen, and polyethylene glycol to boost porosity through formation of interpenetrating polymer networks. The adsorption behaviours of the thin-film, including adsorption kinetics, binding isotherms, and selectivity of MIP thin-film were investigated in detail. The highest imprinting factors (2.3-3.0) and adsorption capacity for targeted PASHs were achieved at a template:monomer:cross-linker ratio of 1:4:8. The method with no sample or film pretreatment showed very good reproducibility for the extraction of PASHs from spiked seawater samples (RSDs ≤ 6.0%, n = 3), was linear (R2 > 0.9960) over a range of 0.5-40 µg L-1, and gave limits of detection n the range of 0.029-0.166 µg L-1.

中文翻译：

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分子印迹聚合物薄膜作为微萃取吸附剂，用于选择性测定海水中痕量浓度的多环芳族硫杂环。

通过在载玻片上进行原位光自由基聚合制备了量身定制的多孔分子印迹聚合物（MIP）薄膜，并将其用作微萃取吸附剂。使用气相色谱-质谱仪（GC-MS）进行检测，从而提供一种适用于选择性测定海水中痕量浓度的多环芳族硫杂环化合物（PASHs）的方法。PASH是最成问题的芳族有机污染物之一，因为与环境中其他类似的芳族化合物相比，PASH被认为更具持久性和毒性。优化的薄膜由2-噻吩甲醛甲醛假模板组成，其中1-乙烯基咪唑（1-Vim）作为功能单体，双酚A二甲基丙烯酸酯（BPADMA）作为交联剂，乙腈作为致孔剂，和聚乙二醇通过形成互穿聚合物网络来提高孔隙率。详细研究了薄膜的吸附行为，包括吸附动力学，结合等温线和MIP薄膜的选择性。在模板：单体：交联剂比例为1：4：8的情况下，获得了针对目标PASH的最高印迹因子（2.3-3.0）和吸附能力。没有样品或膜预处理的方法显示出从加标海水样品中提取PASH的重现性非常好（RSDs≤6.0％，n = 3），在0.5-40 µg L-1范围内呈线性（R2> 0.9960） ，给出的检出限为0.029-0.166 µg L-1。对MIP薄膜的选择性和选择性进行了详细研究。在模板：单体：交联剂比例为1：4：8的情况下，获得了针对目标PASH的最高印迹因子（2.3-3.0）和吸附能力。没有样品或膜预处理的方法显示出从加标海水样品中提取PASH的重现性非常好（RSDs≤6.0％，n = 3），在0.5-40 µg L-1范围内呈线性（R2> 0.9960） ，给出的检出限为0.029-0.166 µg L-1。对MIP薄膜的选择性和选择性进行了详细研究。在模板：单体：交联剂比例为1：4：8的情况下，获得了针对目标PASH的最高印迹因子（2.3-3.0）和吸附能力。没有样品或膜预处理的方法显示出从加标海水样品中提取PASH的重现性非常好（RSDs≤6.0％，n = 3），在0.5-40 µg L-1范围内呈线性（R2> 0.9960） ，给出的检出限为0.029-0.166 µg L-1。