Organic Dots Embedded in Mesostructured Silica Xerogel as High-Performance ECL Emitters: Preparation and Application for MicroRNA-126 Detection

Unlike the organic micro/nanocrystals prepared using an emerging reprecipitation method, a novel method of embedding 1-pyrenecarboxaldehyde dots (PycDs) into a mesostructured silica xerogel (PycDs@MSX) for use as electrochemiluminescence (ECL) emitters was first proposed to achieve an extremely strong ECL response, with peroxydisulfate (S2O8 2–) used as a coreactant. In this method, (i) PycDs@MSX could ensure the reversal of the PycDs environment from hydrophobic to hydrophilic and (ii) PycDs@MSX could provide massive porous channels, allowing for access of hydrophilic reactive intermediates (i.e., sulfate anion radicals, SO4 •–), which could accelerate the rate of mass transfer and electron transfer between S2O8 2– and PycDs. Using Ag nanoparticles as a coreaction accelerator and a 3D DNA nanomachine as a signal amplification strategy, the proposed ECL biosensing platform was constructed and achieved ultrasensitive detection of microRNA-126 with an excellent linear range (from 100 aM to 100 pM) and a low detection limit (13.0 aM). More importantly, this work not only developed an innovative avenue to improve the ECL efficiency of organic emitters in aqueous phases but also provided a powerful strategy for biochemical analysis and disease diagnosis applications.