Institute of Organic Chemistry, University of Duisburg-Essen, Universitätsstrasse 7, 45141 Essen, Germany.
Chemistry. 2011 May 2;17(19):5311-8. doi: 10.1002/chem.201003393. Epub 2011 Apr 1.
The water-soluble tweezer receptor 1 with two symmetric peptidic arms, which are connected by an aromatic scaffold and contain lysine, phenylalanine, and a guanidinium-based anion-binding site as headgroup, has been synthesized. UV/Vis-derived Job plots show that the receptor forms 1:1 complexes with nucleotides and phosphate in buffered water at neutral pH. Binding constants have been determined by fluorescence and UV/Vis spectroscopy. All nucleotides tested were bound very efficiently, even in pure water, with binding constants between 10(4) and 10(5) M(-1) . Interestingly, all mononucleotides were bound much stronger than phosphate by a factor of at least 5 to 10. Furthermore 1 favors the binding of adenosine monophosphate (AMP) over adenosine diphosphate (ADP) and adenosine triphosphate (ATP), which is unprecedented for artificial nucleotide receptors reported so far. According to NMR spectroscopy and molecular modeling studies, the efficient binding is a result of strong electrostatic contacts supported by π-π interactions with the nucleobase within the cavity-shaped receptor.
已经合成了一种具有两个对称肽臂的水溶性双齿受体，该受体由一个芳香支架连接，头部基团包含赖氨酸、苯丙氨酸和胍基阴离子结合位点。紫外/可见衍生的 Job 图表明，在中性 pH 的缓冲水中，受体与核苷酸和磷酸盐形成 1:1 复合物。通过荧光和紫外/可见光谱法测定了结合常数。所有测试的核苷酸都非常有效地结合，即使在纯水中，结合常数在 10(4)到 10(5) M(-1)之间。有趣的是，所有的单核苷酸与磷酸盐的结合强度至少相差 5 到 10 倍。此外，1 有利于单磷酸腺苷 (AMP)的结合，而不是二磷酸腺苷 (ADP)和三磷酸腺苷 (ATP)，这是迄今为止报道的人工核苷酸受体前所未有的。根据 NMR 光谱和分子建模研究，这种高效结合是由于腔内受体与碱基之间的强静电接触得到支持，同时还存在π-π相互作用。
