Synthesis of surface protein-imprinted nanoparticles based on metal coordination and anchored carbon dots for enhanced fluorescence detection

Abstract

Molecularly imprinted polymers endowed with photo-luminescent properties have attracted wide research interest in many fields such as biological analysis and diseases diagnosis. Herein, we illustrate a versatile method for the construction of surface protein-imprinted nanoparticles based on metal coordination and anchored carbon dots (CDs) for enhanced fluorescence detection of the target protein. As the fluorescent nanosupports for surface imprinting, CDs-attached SiO₂ nanoparticles were synthesized via thiol-ene click chemistry. With histidine (His)-exposed protein as templates, imprinted nanoshells were formed over the nanosupports via copolymerization of a Cu²⁺-chelating monomer and an oligo (ethylene glycol) monomer, hence producing high-quality imprinted cavities because of both the relatively strong coordination and inhibited non-specific binding. Using lysozyme as a model His-exposed template, the imprinted nanoparticles showed fluorescence enhancement while binding the target protein, and exhibited significantly increased specific fluorescence response than the controls without the metal coordination. They achieved a high imprinting factor of 5.8 and a low limit of detection of 10.1 nM. Furthermore, such sensors were applied to determine lysozyme in diluted chicken egg-white samples with satisfactory recoveries at three spiking levels ranging from 97.9 to 101.4%. Human serum albumin was also used as another template protein for preliminary confirming the generality of the presented strategy.

Keywords: Carbon dots; Fluorescence detection; Metal coordination; Protein imprinting; Surface imprinting; Thiol–ene click chemistry.