We have recently reported that a computationally designed catalyst nicknamed AlleyCat facilitates C-H proton abstraction in Kemp Elimination at neutral pH in a selective and calcium-dependent fashion by a factor of ~100,000 (PNAS, 2011 , 108, 6823). This was achieved by introducing a single glutamic acid residue in a hydrophobic environment thus increasing the effective pKa of the carboxylate. Kemp Elimination produced colored product that can be easily read out thus making AlleyCat a catalytically amplified metal sensor. Linking catalytic activity to metal ion binding offers a number of advantages such as low background noise, relative ease of function modification.Here we present our efforts to expand the repertoire of metals that can be sensed using this approach to lanthanides, in particular, Tb(III). We have redesigned metal-binding EF-hand motifs in AlleyCat to incorporate larger metal ions to create a lanthanide-dependent switchable Kemp Eliminase.

Design of a lanthanide-dependent switchable Kemp eliminase

244th National Meeting (2012)

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