Nucleotide Recognition in Water by a Guanidinium-Based Artificial Tweezer Receptor
Nucleotide Recognition in Water by a Guanidinium-Based Artificial Tweezer Receptor
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DOI：
10.1002/chem.201003393
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发表时间：
2011-05-01
影响因子：
4.3
通讯作者：
Schmuck, Carsten
中科院分区：
文献类型：
--
作者：
Kuchelmeister, Hannes Y.;Schmuck, Carsten
合成了具有两个对称肽臂的水溶性镊子受体1，这两个对称肽臂通过芳香族支架连接，并且含有赖氨酸、苯丙氨酸和基于胍的阴离子结合位点作为头基。UV/VIS衍生的Job图显示，在中性pH的缓冲水中，受体与核苷酸和磷酸盐形成1：1的复合物。结合常数已通过荧光和UV/维斯光谱测定。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）和10（5）M-1之间。有趣的是，所有单核苷酸的结合都比磷酸盐强至少5至10倍。此外，1有利于腺苷一磷酸（AMP）的结合超过腺苷二磷酸（ADP）和腺苷三磷酸（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，有效结合是由与腔形受体内的核碱基的π-π相互作用支持的强静电接触的结果。
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 pi-pi interactions with the nucleobase within the cavity-shaped receptor.