Molecular imprinting technology has been widely studied as a technique to obtain molecular recognition by artificial means. Selecting functional monomers or polymerization conditions plays a key role to optimize molecularly imprinted polymer (MIP) synthesis. To date, there have been few reports well exploiting the effect of crosslinkers. Here, in this study, we synthesized the MIPs using poly(ethyleneglycol) dimethacrylate with different units of ethylene oxide (n = 1 to 23) as crosslinkers to observe the molecular recognition abilities. The MIPs were attached to the surface of mono-dispersed polymer beads. The obtained spherical MIPs and non-imprinted polymers were filled in a column for high performance liquid chromatography. Then the retention selectivity toward TR active substances was evaluated. The result revealed that the recognition ability did not improve regardless of the amount of ethylene oxide. With the crosslinker (n = 9), extremely high retention selectivity was observed, which provides at most around ten times as large imprinting factors in comparison with other MIPs. Interestingly, we obtained the highest recognition ability at around polymerization temperature from the evaluation of the recognition ability toward temperature shift using the MIP (n = 9). In general, hydrogen bonding based on MIPs provides high recognition ability at low temperature, whereas, this study indicates that the use of flexible crosslinkers may enable the synthesis of MIPs that precisely memorize the conditions of polymerization. Lastly, we simultaneously analyzed the TR active substances using the column filled with MIPs (n = 9). The result showed relatively linear correlation between the retention strength of each substance and phycological activity toward TR obtained by yeast assay. Therefore, we can conclude that an induced fit like the receptor emerged by constructing the flexible molecular recognition field.

中文翻译：

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分子印迹聚合物中长链交联剂增强分子识别，有效分离 TR 活性物质

分子印迹技术作为一种通过人工手段获得分子识别的技术已被广泛研究。选择功能单体或聚合条件对于优化分子印迹聚合物（MIP）合成起着关键作用。迄今为止，很少有报道充分利用交联剂的作用。在本研究中，我们使用具有不同环氧乙烷单元（ n = 1至23）的聚（乙二醇）二甲基丙烯酸酯作为交联剂合成了MIP，以观察分子识别能力。 MIP 附着在单分散聚合物珠的表面。将获得的球形MIP和非印迹聚合物填充到高效液相色谱柱中。然后评估对TR活性物质的保留选择性。结果表明，无论环氧乙烷的量如何，识别能力都没有提高。使用交联剂 ( n = 9)，观察到极高的保留选择性，与其他 MIP 相比，其最多提供约十倍的印迹因子。有趣的是，通过使用 MIP（ n = 9）评估温度变化的识别能力，我们在聚合温度附近获得了最高的识别能力。一般来说，基于MIP的氢键在低温下提供了高识别能力，而本研究表明，使用柔性交联剂可以合成能够精确记忆聚合条件的MIP。最后，我们使用填充有 MIP 的色谱柱（n = 9）同时分析了 TR 活性物质。结果表明，每种物质的保留强度与通过酵母测定获得的 TR 的生理活性之间存在相对线性相关。因此，我们可以得出结论，通过构建柔性分子识别场，出现了类似受体的诱导契合。