Supramolecular allosteric catalysts

INOR 67

Nathan C Gianneschi, ngiannes@scripps.edu, Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, CA 92037, SonBinh T. Nguyen, stn@northwestern.edu, Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113, and Chad A. Mirkin, chadnano@northwestern.edu, Department of Chemistry and the International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113.
Supramolecular chemistry has great potential as a tool in the construction of synthetic systems that mimic chemical strategies utilized in the natural world, such as allosteric regulation of enzyme activity. We present synthetic toroidal and tweezer shaped allosteric catalysts assembled using metal coordination chemistry. Allosteric control is afforded via selective and reversible reactions occurring at structure control domains which convert “closed”, rigid structures with small cavities, into “open”, dilated species. This shape change facilitates and modulates reactions occurring at catalytic domains located within the cavity. These supramolecular allosteric catalysts were adapted for signal amplification and detection. The strategy involves analyte binding induced, allosteric catalyst activation and subsequent product formation, coupled to signal transduction. This methodology represents a potentially general approach to sensitive small molecule detection. These studies demonstrate the utility of combining structure control and catalytically active sites within supramolecular architectures to achieve catalytic control and novel functionality.