Departamento de Engenharia Química, Instituto Superior de Engenharia de Lisboa, Instituto Politécnico de Lisboa, R. Conselheiro Emídio Navarro, 1, 1959-007 Lisboa, Portugal.
Centro de Química-Vila Real, Universidade de Trás-os-Montes e Alto Douro, 5001-801 Vila Real, Portugal.
Molecules. 2021 Aug 18;26(16):5000. doi: 10.3390/molecules26165000.
Supramolecular chemistry has become a central theme in chemical and biological sciences over the last decades. Supramolecular structures are being increasingly used in biomedical applications, particularly in devices requiring specific stimuli-responsiveness. Fullerenes, and supramolecular assemblies thereof, have gained great visibility in biomedical sciences and engineering. Sensitive and selective methods are required for the study of their inclusion in complexes in various application fields. With this in mind, two new fluorescent bis-calix[4]arene-carbazole conjugates ( and ) have been designed. Herein, their synthesis and ability to behave as specific hosts for fullerenes C and C is described. The optical properties of the novel compounds and their complexes with C and C were thoroughly studied by UV-Vis and steady-state and time-resolved fluorescence spectroscopies. The association constants () for the complexation of C and C by and were determined by fluorescence techniques. A higher stability was found for the C@ supramolecule ( = 5.6 × 10 M; Δ = -6.48 kcal/mol). Evidence for the formation of true inclusion complexes between the host and C/C was obtained from NMR spectroscopy performed at low temperatures. The experimental findings were fully corroborated by density functional theory (DFT) models performed on the host-guest assemblies (C@ and C@).
超分子化学在过去几十年中已成为化学和生物科学的核心主题。超分子结构越来越多地应用于生物医学领域，特别是在需要特定刺激响应的设备中。富勒烯及其超分子组装体在生物医学科学和工程中已经得到了广泛的关注。需要敏感和选择性的方法来研究它们在各种应用领域的复合物中的包合作用。考虑到这一点，设计了两种新型荧光双杯[4]芳烃-咔唑缀合物（和）。本文描述了它们的合成及其作为富勒烯 C 和 C 的特定主体的能力。通过紫外可见光谱和稳态和时间分辨荧光光谱法对新化合物及其与 C 和 C 的复合物的光学性质进行了彻底研究。通过荧光技术确定了 C 和 C 与和复合物的结合常数（）。发现 C@超分子的稳定性更高（= 5.6×10 M；Δ= -6.48 kcal/mol）。从在低温下进行的 NMR 光谱中获得了主体和之间形成真正的包合复合物的证据/C。实验结果得到了基于密度泛函理论（DFT）模型对主体-客体组装体（C@和 C@）的充分证实。
