Nanopore discrimination of rare earth elements

Rare earth elements (REEs), including scandium, yttrium and lanthanides, are strategic resources with unique electric, luminescent and magnetic properties. However, owing to their highly similar physiochemical properties, the identification and separation of all REEs are challenging. Here a Mycobacterium smegmatis porin A nanopore is engineered to contain a nitrilotriacetic acid ligand at its pore constriction. By the further introduction of a secondary ligand N_α,N_α-bis(carboxymethyl)-L-lysine hydrate (ANTA), a dual-ligand sensing strategy was established. A unique property of this strategy is that a variety of REE(III) ions report characteristic blockage features containing three-level transitions, which are critical in discriminating different REE(III)s. The nanopore events of REE(III)s also demonstrate a clear periodicity, suggesting the observation of the lanthanide contraction effect at a single-molecule regime. Assisted by machine learning, all 16 naturally occurring REE(III)s have been identified by the nanopore with high accuracy. This sensing strategy is further applied in analysing bastnaesite samples, suggesting its potential use in geological exploration.