A simple model system for the study of carbohydrate-aromatic interactions
A simple model system for the study of carbohydrate-aromatic interactions
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DOI：
10.1021/ja066633g
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发表时间：
2007-03-14
影响因子：
15
通讯作者：
Bernardi, Anna
中科院分区：
文献类型：
--
作者：
Terraneo, Giancarlo;Potenza, Donatella;Bernardi, Anna
确定了一种分子支架，其能够在单糖和附近的苯环之间建立分子内相互作用。合成了一组含有四种不同单糖（葡萄糖、半乳糖、N-乙酰基-葡糖胺和N-乙酰基-半乳糖胺）的分子，并用于研究这种碳水化合物-芳烃相互作用的程度和性质，以及对所涉及分子的整体3D结构的影响。通过分子建模支持的严格NMR研究评估糖-芳香族距离，发现在整个系列中是恒定的，与糖的性质和连接两个元素的片段的构象行为无关。在B3 LYP/DZV（2d，p）水平上的从头计算理论使相互作用的电子性质的分析。该研究表明，只要有机会，就可以建立持久的分子内芳香糖相互作用，并且可以显着影响整体分子形状和能量。这些结果对寡糖结构模拟物的设计具有重要意义。
A molecular scaffold was identified which enables the establishment of intramolecular interactions between a monosaccharide and a nearby phenyl ring. A group of molecules containing four different monosaccharides ( glucose, galactose, N-acetyl-glucosamine, and N-acetyl-galactosamine) was synthesized and used to investigate the extent and nature of this carbohydrate-arene interaction, as well as the effect on the overall 3D structure of the molecules involved. The sugar-aromatic distance was evaluated by rigorous NMR studies supported by molecular modeling and found to be constant throughout the series, independent of the nature of the sugar and of the conformational behavior of the fragment connecting the two elements. Ab initio calculations at the B3LYP/DZV(2d,p) level of theory enable the analysis of the electronic nature of the interaction. The study shows that, given the opportunity, persistent intramolecular aromatic-sugar interactions can be established and can significantly influence overall molecular shape and energetics. These results have important implications in the design of structural mimics of oligosaccharides.