A Combined Parallel Synthesis and Screening of Macrocyclic Lanthanide Complexes for the Cleavage of Phospho Di- and Triesters and Double-Stranded DNA

Abstract
A parallel synthesis of macrocyclic lanthanide−ligand complexes 4Ln has been developed in conjunction with a parallel screening of these ligands for catalysis of phosphate ester hydrolysis. Complexes 4Ln were screened on a 96-well plate reader for their ability to catalyze the hydrolysis of a variety of phosphate esters efficiently. The hydrolysis of bis(4-nitrophenyl) phosphate (BNPP) 5 and p-nitrophenylethyl phosphate 6 was accelerated by up to 150-fold in the presence of the complex 4cGd. The cleavage of a double-stranded DNA plasmid with this same complex obeyed saturation kinetics following a Michaelian model (Km = 7.4 μM, kcat = 4.5 × 10-3 min-1). Our findings demonstrate how a combination of parallel synthesis and screening can expedite compound access, accelerate catalyst identification, and thereby dramatically increase the speed of finding good ligand−metal combinations.

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