ABSTRACT

We present the synthesis and structure-activity relationships of sulfonatocalix[4]arene hosts bearing novel substitutions. The calix[4]arenes are modified on the upper rim at either one or two of the phenolic units, where the dual modifications are introduced regioselectively on neighbouring or opposing phenols. The calix[4]arenes are mono- or di-functionalised with nitro or formyl groups, with the remaining upper-rim sites in all cases occupied by sulphonates. Equilibrium association constants were determined between each host and the guests nicotine, nornicotine, and cotinine. Indicator displacement-based binding studies show that nicotine binds most strongly to the different members of the library followed by nornicotine, whereas cotinine displays weak to no binding. NMR titrations were carried out with nicotine and show different host-guest interaction geometries for the formyl-calix[4]arenes versus the nitro-calix[4]arenes.

摘要

我们介绍了具有新取代基的磺基杯[4]芳烃主体的合成和构效关系。杯[4]芳烃在上边缘的一个或两个酚类单元上被修饰，其中双重修饰区域选择性地引入相邻或相反的酚类。杯[4]芳烃用硝基或甲酰基进行单或双官能化，在所有情况下，其余的上边缘位点都被磺酸盐占据。确定每个宿主和客人尼古丁、去甲尼古丁和可替宁之间的平衡关联常数。基于指示剂置换的结合研究表明，尼古丁与文库的不同成员结合最强，其次是去甲尼古丁，而可替宁则显示出弱结合甚至没有结合。