Laboratorium für Organische Chemie, ETH Zürich , Hönggerberg, HCI, 8093 Zürich, Switzerland.
J Am Chem Soc. 2014 Feb 12;136(6):2441-9. doi: 10.1021/ja4104292. Epub 2014 Feb 3.
Understanding the distance distribution and dynamics between moieties attached to the walls of a resorcin[4]arene cavitand, which is switchable between an expanded kite and a contracted vase form, might enable the use of this molecular system for the study of fundamental distance-dependent interactions. Toward this goal, a combined experimental and molecular dynamics (MD) simulation study on donor/acceptor borondipyrromethene (BODIPY) dye-labeled cavitands present in the vase and kite forms was performed. Direct comparison between anisotropy decays calculated from MD simulations with experimental fluorescence anisotropy data showed excellent agreement, indicating that the simulations provide an accurate representation of the dynamics of the system. Distance distributions between the BODIPY dyes were established by comparing time-resolved Förster resonance energy transfer experiments and MD simulations. Fluorescence intensity decay curves emulated on the basis of the MD trajectories showed good agreement with the experimental data, suggesting that the simulations present an accurate picture of the distance distributions and dynamics in this molecular system and provide an important tool for understanding the behavior of extended molecular systems and designing future applications.
理解连接到间苯二酚[4]芳烃空腔分子的壁上的部分的距离分布和动态，该空腔分子在扩展的风筝和收缩的花瓶形式之间是可切换的，这可能使这个分子系统能够用于研究基本的距离依赖相互作用。为此，对处于花瓶和风筝形式的供体/受体硼二吡咯甲川（BODIPY）染料标记的空腔分子进行了实验和分子动力学（MD）模拟的组合研究。从 MD 模拟计算的各向异性衰减与实验荧光各向异性数据的直接比较表明了极好的一致性，表明模拟提供了对系统动力学的准确表示。通过比较时间分辨的Förster 共振能量转移实验和 MD 模拟来建立 BODIPY 染料之间的距离分布。基于 MD 轨迹模拟的荧光强度衰减曲线与实验数据吻合良好，这表明模拟呈现了该分子系统中距离分布和动力学的准确情况，并为理解扩展分子系统的行为和设计未来应用提供了重要工具。
