Zhao Qi, Li Huiyu, Xu Yang, Zhang Fengshuang, Zhao Jiahui, Wang Long, Hou Juan, Ding Hong, Li Yi, Jin Haiyan, Ding Lan
College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China.
College of Life Sciences, Jilin University, Changchun 130012, China.
J Chromatogr A. 2015 Jan 9;1376:26-34. doi: 10.1016/j.chroma.2014.12.021. Epub 2014 Dec 12.
Single-hole hollow molecularly imprinted microspheres (h-MIMs) were prepared by hard template method and applied to extract six triazine pesticides in cereal samples, followed by HPLC-MS/MS detection. The synthesis mechanism of the h-MIMs has been studied. The h-MIMs exhibited bigger specific surface area and much higher binding capacity than the molecularly imprinted polymers prepared by precipitation polymerization (p-MIPs) and surface polymerization (s-MIPs). Besides, the adsorption rate of h-MIMs to prometryn was significantly higher than that of p-MIPs and s-MIPs. Owing to the hollow structure of the h-MIMs, more binding cavities were located on the inner and outer surfaces of the h-MIMs, which could facilitate the removal of template molecules from the polymers and the rebinding of the target molecules to the polymers. Under the optimal conditions, the detection limits of triazines are in the range of 0.08-0.16ngg(-1). At the spiked level (5ngg(-1)), the recoveries of triazines are in the range of 81±4% to 96±4%. The proposed method was successfully applied to determine six triazines in five cereal samples. Atrazine was found in two rice samples and a wheat sample with the contents of 5.1, 6.7 and 5.6ngg(-1), respectively. Ametryn and prometryn were found in a maize sample with the contents of 7.6 and 7.3ngg(-1), respectively.
采用硬模板法制备了单孔空心分子印迹微球（h-MIMs），并将其应用于谷物样品中六种三嗪类农药的提取，随后进行HPLC-MS/MS检测。研究了h-MIMs的合成机理。h-MIMs比沉淀聚合法（p-MIPs）和表面聚合法（s-MIPs）制备的分子印迹聚合物具有更大的比表面积和更高的结合容量。此外，h-MIMs对扑草净的吸附速率明显高于p-MIPs和s-MIPs。由于h-MIMs的空心结构，更多的结合腔位于h-MIMs的内外表面，这有利于模板分子从聚合物中去除以及目标分子与聚合物的重新结合。在最佳条件下，三嗪类农药的检测限在0.08-0.16ng g(-1)范围内。在加标水平（5ng g(-1)）下，三嗪类农药的回收率在81±4%至96±4%范围内。该方法成功应用于五种谷物样品中六种三嗪类农药的测定。在两个水稻样品和一个小麦样品中检测到莠去津，含量分别为5.1、6.7和5.6ng g(-1)。在一个玉米样品中检测到莠灭净和扑草净，含量分别为7.6和7.3ng g(-1)。
