title: Chemistry inside molecular containers in the gas phase.
abstract: 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.
authors.affiliation: Melville Laboratory for Polymer Synthesis, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK.
authors.forename: Tung-Chun
authors.initials: TC
authors.lastname: Lee
authors.forename: Elina
authors.initials: E
authors.lastname: Kalenius
authors.forename: Alexandra I
authors.initials: AI
authors.lastname: Lazar
authors.forename: Khaleel I
authors.initials: KI
authors.lastname: Assaf
authors.forename: Nikolai
authors.initials: N
authors.lastname: Kuhnert
authors.forename: Christian H
authors.initials: CH
authors.lastname: Grün
authors.forename: Janne
authors.initials: J
authors.lastname: Jänis
authors.forename: Oren A
authors.initials: OA
authors.lastname: Scherman
authors.forename: Werner M
authors.initials: WM
authors.lastname: Nau