Matsui Jun, Goji Shou, Murashima Takashi, Miyoshi Daisuke, Komai Satoshi, Shigeyasu Aiko, Kushida Takuho, Miyazawa Toshifumi, Yamada Takashi, Tamaki Katsuyuki, Sugimoto Naoki
Anal Chem. 2007 Feb 15;79(4):1749-57. doi: 10.1021/ac060441m.
Molecular crowding, an important feature of the molecular environments in biological cells, was applied to the synthesis of antibody-mimic polymers selective for a group of biologically active compounds, the triazine herbicides. Synthesis of these polymers was conducted using molecular imprinting under molecular crowding conditions, whereby atrazine (a template molecule) was complexed with methacrylic acid (a functional monomer) in the presence of a macromolecular crowding agent (either poly(methyl methacrylate) (PMMA) or polystyrene (PS)) followed by cross-linking with ethylene glycol dimethacrylate. After removal of atrazine from the polymer matrix, the retention properties and selectivity of the resultant polymers were assessed by chromatographic tests. The addition of a crowding-inducing agent resulted in polymers with superior retention properties and excellent selectivity for triazine herbicides, as compared to polymers prepared without addition of a crowding-inducing agent. An imprinted polymer prepared in the presence of PS as a crowding agent exhibited a retention factor for atrazine an order of magnitude larger than that of an imprinted polymer prepared in the absence of a crowding agent. NMR results suggest that the crowding agent is capable of promoting hydrogen bond formation between atrazine and methacrylic acid, which could account for the effect of crowding on molecular imprinting.
分子拥挤是生物细胞内分子环境的一个重要特征，已被应用于合成对一组生物活性化合物——三嗪类除草剂具有选择性的抗体模拟聚合物。这些聚合物的合成是在分子拥挤条件下通过分子印迹进行的，即阿特拉津（一种模板分子）在大分子拥挤剂（聚甲基丙烯酸甲酯（PMMA）或聚苯乙烯（PS））存在下与甲基丙烯酸（一种功能单体）络合，然后与乙二醇二甲基丙烯酸酯交联。从聚合物基质中去除阿特拉津后，通过色谱测试评估所得聚合物的保留特性和选择性。与未添加拥挤诱导剂制备的聚合物相比，添加拥挤诱导剂得到的聚合物具有优异的保留特性和对三嗪类除草剂的出色选择性。在PS作为拥挤剂存在下制备的印迹聚合物对阿特拉津的保留因子比在没有拥挤剂的情况下制备的印迹聚合物大一个数量级。核磁共振结果表明，拥挤剂能够促进阿特拉津与甲基丙烯酸之间形成氢键，这可以解释拥挤对分子印迹的影响。
