Tianjin Key Laboratory on Technologies Enabling Development of Clinical Therapeutics and Diagnostics (Theranostics), School of Pharmacy, Tianjin Medical University, Tianjin, 300070, China.
Anal Bioanal Chem. 2018 Aug;410(21):5183-5193. doi: 10.1007/s00216-018-1166-8. Epub 2018 Jun 7.
The dendritic effect of nano mesoporous molecular sieve was first used to enhance molecular recognition of molecularly imprinted polymers (MIPs)-based polyhedral oligomeric silsesquioxanes (POSS). In this study, the MIPs were made using S-naproxen (S-NAP) as template molecule, 4-vinylpyridine (4-VP) as functional monomer, ethylene glycol dimethacrylate as cross-linker, 1-butyl-3-methylimidazoliumtetrafluoroborate ([BMIM]BF)/DMSO as binary porogens, 1-propylmethacrylate-heptaisobutyl substituted as POSS monomer, and mesoporous molecular sieve (Mobil composition of matter No. 41, MCM-41) as dendritic scaffold. The influence of synthesis parameters on the imprinting effect, including the content of POSS monomer and derivatized MCM-41-MPS, the ratio of template to monomer, and the ratio of binary porogens were also investigated, respectively. The morphology of the polymers was characterized by scanning electron microscopy, nitrogen adsorption, and X-ray powder diffraction. The results showed that POSS&MCM-41-MPS MIP had a stronger imprinting effect with an imprinting factor 6.86, which is approximately 2.4, 2.3, and 3 times than that of POSS MIP, MCM-41-MPS MIP, and conventional MIP, respectively. The increase of affinity might be attributed to impediment of the chain motion of polymer due to improved POSS aggregation and the dipole interaction between the POSS units by introduce of MCM-41-MPS as scaffolds. The resulting POSS&MCM-41-MPS MIP was used as adsorbent for the enrichment of S-NAP in solid-phase extraction with a high recovery of 97.65% and the value of RSD was 0.94%.
纳米介孔分子筛的树枝状效应首次被用于增强基于印迹聚合物（MIPs）的多面体低聚倍半硅氧烷（POSS）的分子识别。在这项研究中，以 S-萘普生（S-NAP）为模板分子、4-乙烯基吡啶（4-VP）为功能单体、乙二醇二甲基丙烯酸酯为交联剂、1-丁基-3-甲基咪唑四氟硼酸盐（[BMIM]BF）/DMSO 为二元致孔剂、1-丙基甲基丙烯酸庚基取代 POSS 单体和介孔分子筛（Mobil 组成物质编号 41，MCM-41）作为树枝状支架，制备了 MIPs。考察了合成参数对印迹效果的影响，包括 POSS 单体和衍生化的 MCM-41-MPS 的含量、模板与单体的比例、二元致孔剂的比例等。通过扫描电子显微镜、氮气吸附和 X 射线粉末衍射对聚合物的形态进行了表征。结果表明，POSS&MCM-41-MPS MIP 具有较强的印迹效应，印迹因子为 6.86，分别约为 POSS MIP、MCM-41-MPS MIP 和常规 MIP 的 2.4、2.3 和 3 倍。亲和力的增加可能归因于引入 MCM-41-MPS 作为支架后 POSS 聚集和 POSS 单元之间的偶极相互作用阻碍了聚合物链的运动。所得 POSS&MCM-41-MPS MIP 被用作固相萃取中 S-NAP 的富集剂，其回收率高达 97.65%，RSD 值为 0.94%。
