Molecular Recognition by Zn(II)-Capped Dynamic Foldamers.
Molecular Recognition by Zn(II)-Capped Dynamic Foldamers.
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Zn(II) 封端的动态折叠体的分子识别。
DOI：
10.1002/open.201900362
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发表时间：
2020
期刊：
影响因子：
2.3
通讯作者：
Eccles N
中科院分区：
文献类型：
--
作者：
Eccles N
合成了两个含锌(II)螯合N-末端的α-氨基异丁酸(BQPA)折叠分子，并与文献报道的带有双(喹啉)/单(吡啶)基(BQPA基)的AIB折叠分子(BQPA基)进行了比较。用吡啶取代BQPA封端的喹啉基臂得到BPPA封端的折叠体，再用1，2，3-三氮唑取代连接的吡啶基得到BPTA封端的折叠体。测量了它们将手性信息从N-末端与锌(II)结合的羧酸盐传递到C-末端构象优先的基于甘氨酰胺的核磁共振报告的能力。喹啉基臂的重要性显而易见，因为带有吡啶基臂的分子不能报告乙腈中手性羧酸盐的存在。低溶解度、X-射线结晶学和~1H核磁共振波谱表明，叶间相互作用抑制了羧酸盐的结合。然而，改变溶剂为甲醇，发现在低温下，BPTA封端的Folamer的锌(II)络合物可以观察到手性信息的端到端传递。
Two α‐aminoisobutyric acid (Aib) foldamers bearing Zn(II)‐chelating N‐termini have been synthesized and compared with a reported Aib foldamer that has a bis(quinolinyl)/mono(pyridyl) cap (BQPA group). Replacement of the quinolinyl arms of the BQPA‐capped foldamer with pyridyl gave a BPPA‐capped foldamer, then further replacement of the linking pyridyl with a 1,2,3‐triazole gave a BPTA‐capped foldamer. Their ability to relay chiral information from carboxylate bound to Zn(II) at the N‐terminus to a glycinamide‐based NMR reporter of conformational preference at the C‐terminus was measured. The importance of the quinolinyl arms became readily apparent, as the foldamers with pyridyl arms were unable to report on the presence of chiral carboxylate in acetonitrile. Low solubility, X‐ray crystallography and1H NMR spectroscopy suggested that interfoldamer interactions inhibited carboxylate binding. However changing solvent to methanol revealed that the end‐to‐end relay of chiral information could be observed for the Zn(II) complex of the BPTA‐capped foldamer at low temperature.