Deformable Molecularly Imprinted Nanogels Permit Sensitivity-gain in Plasmonic Sensing

Soft molecularly imprinted nanogels (nanoMIPs), selective for human transferrin (HTR), were prepared via a template assisted synthesis. Owing to their soft matter, the nanoMIPs were observed to deform at binding to HTR: while no relevant changes were observed in the hydrodynamic sizes of HTR-free compared to HTR-loaded nanoMIPs, the HTR binding resulted in a significant increment of the nanoMIP stiffness, with the mean Young's modulus measured by AFM passing from 17 ± 6 kPa to 56 ± 18 kPa. When coupled to a plastic optical fibre (POF) plasmonic platform, the analyte-induced nanoMIP-deformations amplified the resonance shift, enabling to attain ultra-low sensitivities (LOD = 1.2 fM; linear dynamic range of concentrations from 1.2 fM to 1.8 pM). Therefore, soft molecularly imprinted nanogels that obey to analyte-induced deformation stand as a novel class of sensitivity-gain structures for plasmonic sensing.