Allosterically Regulated Supramolecular Catalysis of Acyl Transfer Reactions for Signal Amplification and Detection of Small Molecules

The advent of methods for the construction of supramolecular assemblies provides a route to
exploring the benefits of artificial allosteric catalysts. To expand our ability to control reactions using
supramolecular catalysts capable of changing shape in response to chemical input signals, we report the
development and high yield syntheses of multidomain modular supramolecular catalysts. These structures
can be chemically interconverted between relatively inactive and catalytically active states depending on
their shape. Furthermore, this class of supramolecular catalysts can be made to respond to a range of
analytes via the introduction of specific structure control elements responsible for binding analyte molecules.
Herein, we describe several of these catalysts and their ability to regulate acyl transfer reactions allosterically.
In addition, the generality of this approach to signal amplification and detection is examined by incorporating
the acyl transfer reaction into a small molecule detection scheme consisting of (i) analyte binding to structure
control sites of the catalytic supramolecular assemblies, (ii) enhanced catalytic activity turned on by the
resulting shape change, thereby allowing for signal amplification of the binding event, and (iii) signal detection
by analysis of the products of the catalytic reaction.