Vázquez-González Violeta, Mayoral María J, Aparicio Fátima, Martínez-Arjona Paula, González-Rodríguez David
Nanostructured Molecular Systems and Materials Group, Organic Chemistry Department, Science Faculty, Universidad Autónoma de Madrid, 28049, Madrid, Spain.
Inorganic Chemistry Department, Chemistry Faculty, Universidad Complutense de Madrid, 28040, Madrid, Spain.
Chempluschem. 2021 Jun 16;86(8):1087-1096. doi: 10.1002/cplu.202100255.
Nanotubes are a fascinating kind of self-assembled structure which have a wide interest and potential in supramolecular chemistry. We demonstrated that nanotubes of defined dimensions can be produced from dinucleobase monomers through two decoupled hierarchical cooperative processes: cyclotetramerization and supramolecular polymerization. Here we analyze the role of peripheral amide groups, which can form an array of hydrogen bonds along the tube axis, on this self-assembly process. A combination of H NMR and CD spectroscopy techniques allowed us to analyze quantitatively the thermodynamics of each of these two processes separately. We found out that the presence of these amide directors is essential to guide the polymerization event and that their nature and number have a strong influence, not only on the stabilization of the stacks of macrocycles, but also on the supramolecular polymerization mechanism.
纳米管是一种引人入胜的自组装结构，在超分子化学领域具有广泛的研究兴趣和潜力。我们证明了特定尺寸的纳米管可以通过两个解耦的分级协同过程由二核苷酸碱基单体生成：环四聚化和超分子聚合。在此，我们分析了沿管轴可形成一系列氢键的外围酰胺基团在这种自组装过程中的作用。核磁共振氢谱（¹H NMR）和圆二色光谱（CD）技术的结合使我们能够分别定量分析这两个过程中每一个的热力学。我们发现这些酰胺导向基团的存在对于引导聚合事件至关重要，并且它们的性质和数量不仅对大环堆叠的稳定性有强烈影响，而且对超分子聚合机制也有很大影响。
