6533b835fe1ef96bd129f5a9
RESEARCH PRODUCT
Chemistry inside molecular containers in the gas phase.
Khaleel I. AssafTung-chun LeeJanne JänisWerner M. NauElina KaleniusAlexandra I. LazarChristian H. GrünNikolai KuhnertOren A. Schermansubject
Bicyclic molecule010405 organic chemistryChemistryGeneral Chemical EngineeringGeneral ChemistryActivation energy010402 general chemistry01 natural sciencesCombinatorial chemistry0104 chemical sciences3. Good healthGas phaseChemical physicsCucurbiturilta116description
Inner-phase chemical reactions of guest molecules encapsulated in a macromolecular cavity give fundamental insight into the relative stabilization of transition states by the surrounding walls of the host, thereby modelling the situation of substrates in enzymatic binding pockets. Although in solution several examples of inner-phase reactions are known, the use of cucurbiturils as macrocyclic hosts and bicyclic azoalkanes as guests has now enabled a systematic mass spectrometric investigation of inner-phase reactions in the gas phase, where typically the supply of thermal energy results in dissociation of the supramolecular host-guest assembly. The results reveal a sensitive interplay in which attractive and repulsive van der Waals interactions between the differently sized hosts and guests need to be balanced with a constrictive binding to allow thermally activated chemical reactions to compete with dissociation. The results are important for the understanding of supramolecular reactivity and have implications for catalysis.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2013-04-07 | Nature chemistry |