Premium
Molecular Stiffening by Macrocycle Clustering
Author(s) -
Yin Hang,
Cheng Qian,
Rosas Roselyne,
Viel Stéphane,
Monnier Valerie,
Charles Laurence,
Siri Didier,
Gigmes Didier,
Yemloul Mehdi,
Wang Ruibing,
Kermagoret Anthony,
Bardelang David
Publication year - 2025
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202420880
Subject(s) - isothermal titration calorimetry , chemistry , allosteric regulation , stiffening , molecular dynamics , molecule , biophysics , computational chemistry , materials science , biochemistry , organic chemistry , biology , composite material , enzyme
Abstract Allosteric stiffening of a portion of a protein surface is a strategy used in nature to regulate protein oligomerization and provide crucial functions for cells. However, a similar strategy to selectively control part of a compound dynamics remains elusive. Here we show that cucurbit[ n ]uril (CB[ n ]) macrocycles can bind almost all portions of a tetratopic guest molecule, stiffening the different parts of the guest to different extents. “Host–guest” interactions were found to be instrumental in selectively “freezing” guest molecular motions. The combination of 1 H‐NMR (1D, 2D), DOSY, VT‐NMR, isothermal titration calorimetry (ITC), mass spectrometry and molecular modelling enabled to highlight the crucial role of cucurbit[8]uril (CB[8]) binding in the selective hardening of relevant portions of the guest molecule. Beyond implications for bioinspired systems mimicking control of a system dynamic to create a new function, this approach has relevance for improving room temperature phosphorescence, and could also be used to allosterically control organocatalysis in water.