Department of Science and Environment , Roskilde University , Universitetsvej 1 , DK-4000 , Roskilde , Denmark.
J Phys Chem B. 2018 May 10;122(18):4821-4827. doi: 10.1021/acs.jpcb.8b02579. Epub 2018 Apr 30.
The strong binding of the adamantyl moiety to the cavity of β-cyclodextrin makes it a common binding motif in supramolecular chemistry and a common model system. Despite the attention, there are still unresolved questions regarding the orientation of the adamantane derivatives in the inclusion complexes-do they protrude from the wide or narrow opening of the cyclodextrin hosts? A combined analysis of ROESY NMR and molecular dynamics simulations allows the conclusion that positively charged adamantane derivatives are oriented with the hydrophilic group protruding from the wider opening of the cyclodextrin, while negatively charged adamantane derivatives form two coexisting types of complexes where the hydrophilic group respectively protrudes from the wide and narrow opening. Interestingly, structural modifications of the cyclodextrin host only have a slight impact on the guest orientation.
金刚烷部分与β-环糊精空腔的强结合使其成为超分子化学中的常见结合基序和常见模型体系。尽管受到关注，但关于金刚烷衍生物在包合物中的取向仍存在未解决的问题——它们是从环糊精主体的宽开口还是窄开口突出？ROESY NMR 和分子动力学模拟的综合分析允许得出这样的结论：带正电荷的金刚烷衍生物的取向是亲水基团从环糊精的较宽开口突出，而带负电荷的金刚烷衍生物形成两种共存类型的配合物，其中亲水基团分别从宽开口和窄开口突出。有趣的是，对环糊精主体的结构修饰仅对客体取向有轻微影响。
