期刊
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
卷 104, 期 52, 页码 20737-20742出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.0706407105
关键词
cucurbituril entropy control; ferrocene derivatives; host-guest complexation; thermodynamics
资金
- NIGMS NIH HHS [GM061300, R01 GM061300, GM075350, R44 GM075350] Funding Source: Medline
The molecular host cucurbit[7]uril forms an extremely stable inclusion complex with the dicationic ferrocene derivative bis(trimethylammoniomethyl)ferrocene in aqueous solution. The equilibrium association constant for this host-guest pair is 3 x 1015 M-1 (K-d = 3 x 10(-16) M), equivalent to that exhibited by the avidin-biotin pair. Although purely synthetic systems with larger association constants have been reported, the present one is unique because it does not rely on polyvalency. Instead, it achieves its extreme affinity by overcoming the compensatory enthalpy-entropy relationship usually observed in supramolecular complexes. Its disproportionately low entropic cost is traced to extensive host desolvation and to the rigidity of both the host and the guest.
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