Sun Ya Kun, Jia Man, Yang Jian, Huang Yan-Ping, Liu Zhao-Sheng, Aisa Haji Akber
Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, Xinjiang, 830011, China.
State Key Laboratory Basis of Xinjiang Indigenous Medicinal Plants Resource Utilization, Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, Xinjiang, 830011, China.
Anal Bioanal Chem. 2018 Jan;410(2):349-359. doi: 10.1007/s00216-017-0765-0. Epub 2017 Dec 26.
A method of preparing molecularly imprinted polymers (MIPs) with Zn(II) as a metallic pivot was adopted to solve the problem of imprinting compound with intramolecular hydrogen bonds by forming stronger coordination binding interaction among the template-functional monomer-Zn complex. A ternary porogenic system including dimethyl sulfoxide, dimethylformamide, and room temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate was employed to fabricate imprinted monolith with high porosity and good flow-through properties, in which chicoric acid (CA), zinc acetate, 4-vinylpyridine (4-VP), and ethylene glycol dimethacrylate (EDMA) was the template, metallic ion, functional monomer, as well as crosslinker, respectively. The influence of polymerization factors including the 4-VP-CA ratio, monomer-crosslinker ratio, template-Zn ratio on imprinting factors was systematically investigated. When the ratio of 4-VP to CA was 24:1, the greatest IF value (24.81) was achieved on the CA-MIP prepared with zinc acetate. In addition, off-line SPE with the optimal MIPs monolith led to high purity of CA (98.0% ± 0.5%) from extraction of Cichorium intybus L. roots with the recovery of 77.5% ± 2.5% (n = 6). As a conclusion, the strategy of introducing metal ions as metal pivot to prepare MIPs was a powerful method for the MIPs synthesis to the template molecules with intramolecular hydrogen bonds.
采用以Zn(II)为金属枢纽制备分子印迹聚合物（MIPs）的方法，通过在模板-功能单体-Zn络合物之间形成更强的配位结合相互作用，解决具有分子内氢键的印迹化合物的问题。采用包括二甲基亚砜、二甲基甲酰胺和室温离子液体1-丁基-3-甲基咪唑四氟硼酸盐的三元致孔体系制备具有高孔隙率和良好流通性能的印迹整体柱，其中菊苣酸（CA）、醋酸锌、4-乙烯基吡啶（4-VP）和乙二醇二甲基丙烯酸酯（EDMA）分别为模板、金属离子、功能单体和交联剂。系统研究了4-VP-CA比例、单体-交联剂比例、模板-Zn比例等聚合因素对印迹因子的影响。当4-VP与CA的比例为24:1时，用醋酸锌制备的CA-MIP的IF值最大（24.81）。此外，采用最佳MIPs整体柱的离线固相萃取从菊苣根提取物中得到了高纯度的CA（98.0%±0.5%），回收率为77.5%±2.5%（n = 6）。总之，引入金属离子作为金属枢纽制备MIPs的策略是合成针对具有分子内氢键的模板分子的MIPs的有效方法。
