Cationic acyclic cucurbit[n]uril-type containers: synthesis and molecular recognition toward nucleotides.
Cationic acyclic cucurbit[n]uril-type containers: synthesis and molecular recognition toward nucleotides.
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阳离子无环葫芦[n]脲型容器：核苷酸的合成和分子识别。
DOI：
10.1080/10610278.2016.1167893
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发表时间：
2016
影响因子：
3.3
通讯作者：
Isaacs,Lyle
中科院分区：
文献类型：
--
作者：
Sigwalt,David;Zavalij,PeterY;Isaacs,Lyle
我们报道了我们的原型无环CB[n]型分子容器M2的四价阳离子类似物M2 NH3的合成。M1 NH3和M2 NH3在D2 O中具有良好的溶解性，不发生分子间自缔合作用，从而影响其分子识别性能。化合物M1 NH3 andM 2NH 3do，然而，经历了一个分子内的自络合过程，由脲基C=O门户和OCH 2CH 2NH 3臂之间的离子-偶极相互作用驱动沿着在其自身的疏水空腔中包含一个芳香壁。通过1H NMR滴定法测定了M1 NH3和M2 NH3对7个核苷酸的Ka值，发现虽然M2 NH3的效力略高，但Ka值相当适中（Ka在102- 103 M − 1范围内）。电荷较高的客体（如ATP）与M1 NH3和M2 NH3形成的络合物比电荷较低的客体（如ADP、AMP）更强。这项工作突出了脲基C=O门户对无环CB[n]型受体的分子识别行为的主导影响，并提出了增强其对阴离子识别行为的途径（例如，更高电荷的臂）。
We report the synthesis ofM2NH3which is a tetracationic analogue of our prototypical acyclic CB[n]-type molecular containerM2. BothM1NH3andM2NH3possess excellent solubility in D2O and do not undergo intermolecular self-association processes that would impinge on their molecular recognition properties. CompoundsM1NH3andM2NH3do, however, undergo an intramolecular self-complexation process driven by ion–dipole interactions between the ureidyl C=O portals and the OCH2CH2NH3arms along with inclusion of one aromatic wall in its own hydrophobic cavity. TheKavalues forM1NH3andM2NH3towards seven nucleotides were determined by1H NMR titration and found to be quite modest (Kain the 102–103M−1range) althoughM2NH3is slightly more potent. The more highly charged guests (e.g. ATP) form stronger complexes withM1NH3andM2NH3than the less highly charged guest (e.g. ADP, AMP). The work highlights the dominant influence of the ureidyl C=O portals on the molecular recognition behaviour of acyclic CB[n]-type receptors and suggests routes (e.g. more highly charged arms) to enhance their recognition behaviour towards anions.