Awino Joseph K, Zhao Yan
Department of Chemistry, Iowa State University, Ames, Iowa 50011-3111, USA.
Org Biomol Chem. 2017 Jun 7;15(22):4851-4858. doi: 10.1039/c7ob00764g.
Chiral molecular recognition is important to biology, separation, and asymmetric catalysis. Because there is no direct correlation between the chiralities of the host and the guest, it is difficult to design a molecular receptor for a chiral guest in a rational manner. By cross-linking surfactant micelles containing chiral template molecules, we obtained chiral nanoparticle receptors for a number of 4-hydroxyproline derivatives. Molecular imprinting allowed us to transfer the chiral information directly from the guest to host, making the molecular recognition between the two highly predictable. Hydrophobic interactions between the host and the guest contributed strongly to the enantio- and diastereoselective differentiation of these compounds in water, whereas ion-pair interactions, which happened near the surface of the micelle, were less discriminating. The chiral recognition could be modulated by tuning the size and shape of the binding pockets.
手性分子识别对生物学、分离及不对称催化而言至关重要。由于主体与客体的手性之间不存在直接关联，所以难以合理设计针对手性客体的分子受体。通过交联含有手性模板分子的表面活性剂胶束，我们获得了针对多种4-羟基脯氨酸衍生物的手性纳米颗粒受体。分子印迹使我们能够将手性信息直接从客体传递至主体，从而使两者之间的分子识别具有高度可预测性。主体与客体之间的疏水相互作用对这些化合物在水中的对映体和非对映体选择性区分起到了重要作用，而发生在胶束表面附近的离子对相互作用的区分能力则较弱。手性识别可通过调整结合口袋的大小和形状来调节。
