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Allostery in Guest Binding of Rim‐to‐Rim‐Connected Homoditopic Biscavitands
Author(s) -
Shimoyama Daisuke,
Yamada Hitomi,
Ikeda Toshiaki,
Sekiya Ryo,
Haino Takeharu
Publication year - 2016
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201600410
Subject(s) - allosteric regulation , chemistry , stereochemistry , phosphonate , hydrogen bond , crystallography , cooperative binding , cationic polymerization , nuclear magnetic resonance spectroscopy , binding site , molecule , enzyme , biochemistry , organic chemistry
Rim‐to‐rim‐connected phosphonate biscavitands 1a and 1b were synthesized. Crystal structure analysis and variable‐temperature NMR spectroscopy studies reveal that 1a is more rigid in conformation than 1b . Biscavitands 1a and 1b bind cationic guests G1 – G3 through hydrogen bonding and CH–π interactions, demonstrating positive and negative allosteric effects, respectively. The allosteric effects in guest binding are associated with the conformational flexibilities of 1a and 1b . The positive allosteric effect of 1a is directed by the tightly connected cavities, in which information of the first guest binding is transferred to the remaining cavity, which becomes preorganized. In contrast, a slightly negative allosteric effect is found in more‐flexible 1b .