Tuning surface‐cross‐linking of molecularly imprinted cross‐linked micelles for molecular recognition in water
Tuning surface‐cross‐linking of molecularly imprinted cross‐linked micelles for molecular recognition in water
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DOI：
10.1002/jmr.2769
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发表时间：
2018-11
影响因子：
2.7
通讯作者：
Shi-Ze Zhang;Yan Zhao
中科院分区：
文献类型：
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作者：
Shi-Ze Zhang;Yan Zhao
水中的分子识别是超分子化学的一个重要挑战。通过点击反应和自由基聚合对含模板的表面活性剂胶束进行表面核双交联，产生具有客体互补结合位点的分子印迹纳米粒子（MINP）。 MINP 受体的一个重要特性是表面活性剂的炔丙基与二叠氮交联剂之间的表面交联。减少两个叠氮化物之间的碳原子数可以增强 MINP 的结合亲和力，这可能是通过在客体结合之前保持印迹结合位点更加开放来实现的。结合袋的深度可以通过模板的亲水/疏水基团的分布来控制，并且发现除了带相反电荷的 MINP 和客体之间的静电相互作用之外，它还会影响结合。具有烷氧基胺基团的交联剂可实现两阶段双表面交联，从而将结合常数增强一个数量级，这可能是通过将 MINP 的结合袋扩展到极性区域来实现的。非常相似的异构体结构之间的结合选择性也得到改善。
Molecular recognition in water is an important challenge in supramolecular chemistry. Surface‐core double cross‐linking of template‐containing surfactant micelles by the click reaction and free radical polymerization yields molecularly imprinted nanoparticles (MINPs) with guest‐complementary binding sites. An important property of MINP‐based receptors is the surface‐cross‐linking between the propargyl groups of the surfactants and a diazide cross‐linker. Decreasing the number of carbons in between the two azides enhanced the binding affinity of the MINPs, possibly by keeping the imprinted binding site more open prior to the guest binding. The depth of the binding pocket can be controlled by the distribution of the hydrophilic/hydrophobic groups of the template and was found to influence the binding in addition to electrostatic interactions between oppositely charged MINPs and guests. Cross‐linkers with an alkoxyamine group enabled two‐stage double surface‐cross‐linking that strengthened the binding constants by an order of magnitude, possibly by expanding the binding pocket of the MINP into the polar region. The binding selectivity among very similar isomeric structures also improved.