17β-雌二醇及类似物与功能单体的相互作用

Interaction of 17β-estradiol and its structural analogues with functional monomers

考察了17β-雌二醇(17β-E)及结构类似物与甲基丙烯酸甲酯(MMA)、甲基丙烯酸(MAA)和三氟甲基丙烯酸(TFMAA)等六种单体的相互作用。分别用紫外光谱(UV)、红外光谱(IR)和高效液相色谱(HPLC)表征了用各单体的乙腈溶液分别与模板的相互作用和用沉淀聚合的分子印迹聚合物(MIP)的特性。结果表明,在全紫外聚合中,印迹17β-E的TFMAA-co-TRIM聚合物的O—H振动吸收峰红移出现在聚合16 h之后,C O振动吸收峰则在聚合24 h后发生红移。三种测试方法均证实TFMAA对17-βE有强相互作用,TFMAA-co-TRIM对雌二醇异构体(17-βE/17-αE)的印迹因子(IF)达到了3.01,分离因子α为2.28,具有良好的选择性。利用紫外法可初步检测各单体的乙腈溶液与模板相互作用强弱,再合成MIP,进行IR和HPLC表征,有助于筛选到对17β-E及结构类似物具有强相互作用的功能单体。

The interaction of 17β-estradiol （17β--E）and its structural analogues with six different functional monomers, namely methyl methacrylate （MMA）, acrylamide （AM）, methacrylamide （MA）, 4-vinylpyridine （4-VP）, methacrylic acid （MAA） and 2- （trifluoromethyl） acrylic acid （TFMAA） has been studied by ultraviolet （UV） spectroscopy, infrared （IR） spectroscopy and high pressure liquid chromatography （HPLC）, and molecularly imprinted polymers （MIP）subsequently synthesized by precipitation polymerization. The O- H and C=O IR absorption maxima shift towards higher wavenumbers after imprinting 17β-E on a TFMAA-co-TRIM copolymer （TRIM= trimethylolpropane trimethacrylate） with the red shift of the O- H groups being apparent after precipitation polymerization for 16 h, and that for the C=O groups being observed after polymerization for 24 h. The strong interaction between TFMAA and 17β-E was confirmed by the high selectivity for 17r-E, as indicated by the values of the separation factor （a） of isomers of 17β-E/17α-E （2.28） and the imprinted factor （IF） （3.01）. The results show that in order to select a suitable functional monomer for fabrication of polymers selective to 17β-E and its structural analogues, preliminary screening may be carried out by monitoring the interaction between monomer and template by UV analysis; subsequently, the MIP should be synthesized, and IR and HPLC employed in order to characterize the properties of the polymer.