Molecularly imprinted polymer microspheres containing photoswitchable spiropyran-based binding sites.

Molecularly imprinted polymer microspheres containing photoswitchable spiropyran-based binding sites.
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DOI:
10.1021/am401958e
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发表时间:
2013-09-11
影响因子:
9.5
通讯作者:
Bakker, Eric
Bakker, Eric
中科院分区:
材料科学2区
文献类型:
--
作者:
Renkecz, Tibor;Mistlberger, Guenter;Pawlak, Marcin;Horvath, Viola;Bakker, Eric

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提出了一种制备具有选择性识别和光响应功能的光开关分子印迹聚合物(MIPs)的方法。作为概念验证,通过沉淀聚合法合成了MIP微球,用于识别三嗪类除草剂特丁津。选择性结合位点的形成是基于模板和官能单体甲基丙烯酸之间的氢键相互作用,而可聚合的螺吡喃单元被掺入到聚合物基质中以提供光可控特性。使用三官能单体三甲基丙烯酸异丙酯作为交联剂。通过扫描电子显微镜观察到的印迹颗粒表现出相当大的形态差异相比,他们的nonimprinted同行。平衡重结合研究证实了印迹效应。通过荧光显微镜观察聚合物颗粒的光响应性,并通过光谱进一步表征。当分别观察到分析物释放和吸收时,可以通过交替的UV和可见光照射来调节模板结合行为。由Freundlich模型拟合的结合等温线揭示了结合位点的数量和它们的平均亲和力的光调节。这种简便的合成方法可能会提供一个有吸引力的起点,赋予目前现有的高选择性的MIP与光开关性能,从而扩大螺吡喃为基础的光响应智能材料的范围。
A versatile approach for the preparation of photoswitchable molecularly imprinted polymers (MIPs) is proposed where the selective recognition and the photoresponsive function are assumed by two different monomers. As a proof of concept, MIP microspheres were synthesized by precipitation polymerization for recognizing terbutylazine, a triazine-type herbicide. Formation of the selective binding sites was based upon H-bonding interactions between the template and the functional monomer methacrylic acid, whereas a polymerizable spiropyran unit was incorporated into the polymer matrix to provide light-controllable characteristics. A trifunctional monomer, trimethylolpropane trimethacrylate, was used as a cross-linker. The imprinted particles exhibited considerable morphological differences compared to their nonimprinted counterparts as observed by scanning electron microscopy. The imprinting effect was confirmed by equilibrium rebinding studies. The photoresponsiveness of the polymer particles was visualized by fluorescence microscopy and further characterized by spectroscopy. The template binding behavior could be regulated by alternating UV and visible light illumination when analyte release and uptake was observed, respectively. Binding isotherms fitted by the Freundlich model revealed the photomodulation of the number of binding sites and their average affinity. This facile synthetic approach may give an attractive starting point to endow currently existing highly selective MIPs with photoswitchable properties, thereby extending the scope of spiropyran-based photoresponsive smart materials.
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