Gated Molecular Baskets

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The benefit of molecular recognition and encapsulation in directing the course of chemical transformations can be enormous. Designing functionalized hosts capable to perform synchronized operations is our objective. We seek to build information-rich molecules and conduct structure-function studies to learn about sophisticated ways for regulating chemical reactivity in artificial settings. In particular, we propose to develop and study the working mechanisms of basket-like molecules capable to fold and incarcerate a guest compound. The investigation of chemical reactions in their interior as a function of the assembly dynamics, conformation and stereochemistry will also be conducted. The folding process is mediated by intramolecular interactions of the heterocyclic 'flaps' appended to the basket rim. The incarceration of a guest is dictated by its interaction with the flaps or the basket interior. In this way the guest exchange is restricted by the baskets' conformational characteristics, which in turn will allow exploring the relationship between the molecular trafficking and chemical transformations occurring in the confined space. Rapid opening and closing of a flap-like gate or conformational adjustments in response to an external stimulus are also mechanisms by which many enzymes regulate trafficking of substrates, products or solutes in and out of their active sites; the allosteric regulation of activity is thus achieved in the biological world. The proposed research is fundamental. It is directed toward understanding the basic aspects and relationships between molecular assembly, reactivity and recognition in unnatural environments. The potential impact is rather broad then specific: the proposal is aimed to develop science that can potentially influence future technologies and improve the processing of useful chemicals. Its mission is contained in educating graduate and undergraduate students about modern problems in physical organic chemistry. The program can also be portrayed as multidisciplinary whereby students resolve scientific challenges by consulting different chemistry disciplines.