Analytical & Testing Center of Beijing Normal University, Beijing Key Laboratory, Beijing 100875, China.
J Chromatogr A. 2012 Jan 13;1220:7-13. doi: 10.1016/j.chroma.2011.11.065. Epub 2011 Dec 8.
Surface molecular imprinted polymers (MIPs) on silica gel particles for highly selective recognition of tetrabromobisphenol A (TBBPA) were prepared by a sol-gel process. Diphenolic Acid (DPA) and bisphenol A (BPA), whose structures were similar to that of TBBPA were selected as dummy template molecules, and 3-aminopropyltriethoxysilane (APTES) and tetramethoxysilane (TEOS) were chosen as functional monomer and cross-linker, respectively. The obtained materials were characterized by FT-IR with diffuse reflectance accessory and the results indicated polymers were successfully grafted on the surface of silica gel supporters. The maximum static adsorption capacities for TBBPA of the DPA-MIPs, BPA-MIPs and non-imprinted polymers (NIPs) were 45, 38 and 22 mg g(-1) respectively, and the results of dynamic adsorption showed that the adsorption equilibrium can be achieved within 15 min for DPA- and BPA-MIPs. Both the DPA- and BPA-MIPs have higher selectivity for TBBPA than that of NIP when they are used as the sorbents for the solid phase extraction (SPE), while the adsorption property of DPA-MIPs was superior to that of BPA-MIPs at low concentration levels of TBBPA. The results indicated DPA-MIPs had more high affinity binding sites for TBBPA, which demonstrated that the strong interactions between the template and the functional monomer were favorable to form high affinity binding sites and improve the selectivity of the polymers. A corresponding analytical method for determination of the TBBPA residues in environmental samples was developed. The recoveries of TBBPA in tap water, river water and lake water were in the range from 85% to 97% with relative standard deviations below 7%, and its limit of detection can reach 2 ng mL(-1).
采用溶胶-凝胶法在硅胶颗粒上制备了用于高选择性识别四溴双酚 A（TBBPA）的表面分子印迹聚合物（MIPs）。选择二酚酸（DPA）和双酚 A（BPA）作为虚拟模板分子，其结构与 TBBPA 相似，3-氨丙基三乙氧基硅烷（APTES）和四甲氧基硅烷（TEOS）分别作为功能单体和交联剂。用带有漫反射附件的傅里叶变换红外光谱（FT-IR）对得到的材料进行了表征，结果表明聚合物已成功接枝到硅胶载体的表面。DPA-MIPs、BPA-MIPs 和非印迹聚合物（NIPs）对 TBBPA 的最大静态吸附容量分别为 45、38 和 22mg g(-1)，动态吸附结果表明，DPA-和 BPA-MIPs 的吸附平衡可在 15min 内达到。当 DPA-和 BPA-MIPs 用作固相萃取（SPE）的吸附剂时，它们对 TBBPA 的选择性均高于 NIP，而在 TBBPA 浓度较低时，DPA-MIPs 的吸附性能优于 BPA-MIPs。结果表明，DPA-MIPs 对 TBBPA 具有更多的高亲和力结合位点，这表明模板与功能单体之间的强相互作用有利于形成高亲和力结合位点，提高聚合物的选择性。建立了一种用于测定环境样品中 TBBPA 残留量的分析方法。TBBPA 在自来水中、河水中和湖水中的回收率在 85%至 97%之间，相对标准偏差低于 7%，检测限可达 2ng mL(-1)。
