Pyrenecarboxaldehyde@Graphene Oxide Acted as a Highly Efficient ECL Emitter and Target-Triggered the Recyclable Cascade System as an Amplifier for Ultrasensitive APE1 Activity Detection.

Herein, pyrenecarboxaldehyde@graphene oxide (Pyc@GO) sheets with highly efficient electrochemiluminescence (ECL) as emitters were prepared by a noncovalent combination to develop a neoteric ECL biosensing platform for the ultrasensitive assessment of human apurinic/apyrimidinic endonuclease1 (APE1) activity. Impressively, the pyrenecarboxaldehyde (Pyc) molecules were able to form stable polar functional groups on the surface of GO sheets through the noncovalent π-π stacking mechanism to prevent intermolecular restacking and simultaneously generate Pyc@GO sheets. Compared with the tightly packed PAH nanocrystals, the Pyc@GO sheets significantly reduced internal filtering effects and diminished nonactivated emitters to enhance ECL intensity and achieve strong ECL emission. Furthermore, the APE1-activated initiators could trigger the recyclable cascade amplified system based on the synergistic cross-activation between catalytic hairpin assembly (CHA) and DNAzyme, which improved the signal amplification and transduction ability. Consequently, the developed ECL platform for the detection of APE1 activity displayed exceptional sensitivity with a low detection limit of 4.6 × 10-9 U·mL-1 ranging from 10-8 to 10-2 U·mL-1. Therefore, the proposed strategy holds great promise for the future development of sensitive and reliable biosensing platforms for the detection of various biomarkers.

Ag@Pyc Nanocapsules as Electrochemiluminescence Emitters for an Ultrasensitive Assay of the APE1 Activity.

Herein, Ag@pyrenecarboxaldehyde nanocapsules (Ag@Pyc nanocapsules) as emitters were prepared to construct an ultrasensitive electrochemiluminescence (ECL) biosensor for the detection of the human apurinic/apyrimidinic endonuclease1 (APE1) activity. Ag nanoparticles on the surface of Pyc nanocapsules as coreaction accelerators could significantly promote coreactant peroxydisulfate (S2O82-) to generate massive reactive intermediates of sulfate radical anion (SO4•-), which interacted with the Pyc nanocapsules to achieve a strong ECL response. In addition, with the aid of APE1-triggered 3D DNA machine, trace target could be converted into a large number of mimic targets (MTs), which were positively correlated with the activity of APE1. Consequently, the proposed ECL biosensor realized an ultrasensitive detection of APE1 activity with an exceptional linear working range from 5 × 10-10 to 5 × 10-4 U·µL-1 and a lower limit of detection of 1.36 × 10-11 U·µL-1. This strategy provided a new approach to construct an efficient ternary system for the detection of biomolecules and early diagnosis of diseases.