替代模板分子印迹聚合物的制备及其用于人尿、牛血清和啤酒中7种双酚类物质的选择性固相萃取

摘要

以酚酞（PP）为替代模板，采用本体聚合法制备了选择性识别7种双酚类物质（BPs）的分子印迹聚合物（ MIP）。将制备的 PP-MIP用作固相萃取（ SPE）填料，成功应用于人尿、牛血清和啤酒样品中7种 BPs 的分离净化。建立了同时测定人尿、牛血清和啤酒样品中的7种 BPs的 MIP-SPE-HPLC分析方法。3种样品中7种 BPs的方法检出限范围均为1.2~2.0μg／L。结果表明，7种 BPs在0.02~2 mg／L范围内线性关系良好，相关系数（ r）大于0.9998；空白样品中加标水平为100和500μg／L的回收率范围为90.1％~107.1％，相对标准偏差（ RSD）不高于8.1％。该方法简便、准确、灵敏、可靠，可用于人尿、牛血清和啤酒中7种 BPs的快速检测。%A molecularly imprinted polymer( MIP)for selective recognition of seven bisphenols ( BPs)was prepared using dummy template phenolphthalein( PP)by bulk polymerization. The characterization results of scanning electron microscopy and nitrogen adsorption-desorption measurements showed that the prepared PP-MIP possessed narrow particle diameter distribu-tion(40-60 μm),a specific surface area(SBET)of 359. 77 m2/g and a total pore volume(Vt) of 0. 730 cm3/g. The adsorption capacity for bisphenol A( BPA)of PP-MIP was evaluated by static adsorption experiment. And the Scatchard analysis revealed that the maximum specific adsorption capacity of PP-MIP was 4. 661 μmol/g. Good class selectivity for BPA and its six structural analogues of bisphenol B(BPB),bisphenol E(BPE),bisphenol AF(BPAF),bis-phenol S( BPS),bisphenol AP( BPAP)and bisphenol Z( BPZ)was demonstrated by the chro-matographic evaluation experiment. The prepared PP-MIP was successfully used as solid-phase extraction(SPE)sorbent for the separation and purification of the seven BPs in human urine, bovine serum and beer samples. Meanwhile,an accurate and sensitive MIP-SPE-HPLC method was established for the determination of the seven BPs in human urine,bovine serum and beer samples. The limits of detection( LODs)for the three samples were in the range of 1. 2-2. 0μg/L. The results showed that good linearities were obtained in the range of 0. 02-2 mg/L for the seven BPs and the correlation coefficients( r)were higher than 0. 999 8. The recoveries of the BPs spiked in blank samples at two spiked levels(100 and 500 μg/L for each BP)were in the range of 90. 1%-107. 1% with the RSDs≤8. 1%. The proposed method is simple and reliable for the rapid detection of the seven BPs in human urine,bovine serum and beer samples.