Self-enhanced electrochemiluminescence of gold nanoclusters via host-guest assembly for ultrasensitive protein biosensing
摘要
Host-guest assembly-induced Au NCs (DMPDA@ ATT-Au NCs) with highly efficient self-enhanced electrochemiluminescence (ECL) were developed for sensitive detection of soluble urokinase-type plasminogen activator receptor (suPAR), a neotype biomarker in kidney diseases. Impressively, DMPDA@ ATT-Au NCs were assembled via host-guest recognition between the ligand 6-aza-2-thiothymine (ATT) protected Au NCs and the coreactant N, N-Dimethyl-1,3-propanediamine (DMPDA) through hydrogen-bond, which exhibited strong ECL signal due to the synergistic enhancement effect of the inhibition of non-radiative transitions by suppressing the rotation of the ligand ATT molecule and the reduction of energy loss by shortening the distance of electron transfer between the Au NCs and DMPDA. Furthermore, trace suPAR was transformed to enormous DNA network nanostructure with participation of high-efficiency dual-catalyst hairpin assembly (DCHA) system and DNA self-assembly, thereby significantly improving the detection sensitivity. Consequently, based on the DMPDA@ ATT-Au NCs as excellent ECL emitter and DCHA induced DNA network nanostructure as signal amplifier, the developed ECL biosensor realized the sensitive detection of suPAR with a detection limit (DL) of 1.48 fg/mL, which represents a sensitivity gain of about five orders of magnitude compared to a standard ELISA kit (DL: ng/mL). In three clinical samples, the biosensor showed excellent agreement with ELISA at high concentrations, and successfully quantified trace suPAR levels below the DL of ELISA kit. This strategy offers a novel ECL enhancement strategy of AuNCs to construct sensitive biosensing platform, which holds potential for extension to trace-level detection of other biomarkers toward clinical biomarker analysis, diagnostic evaluation, and treatment surveillance.
Graphical abstract