A pyrene-based
sp2 carbon-conjugated covalent organic
framework (COF) nanosheet (Py-sp2c-CON) with strong and
stable electrochemiluminescence (ECL) emission was constructed by
CC polycondensation of tetrakis(4-formylphenyl)pyrene (TFPPy)
and 2,2′-(1,4-phenylene)diacetonitrile, which was employed
as a highly efficient ECL emitter to fabricate an ECL biosensor for
the first time. The Py-sp2c-CON exhibited higher ECL intensity
and efficiency than those of TFPPy, bulk Py-sp2c-COF, and
imine-linked pyrene COF, not only because the pyrene luminophores
and aggregation-induced emissive luminogens (cyano-substituted phenylenevinylene)
were topologically linked into Py-sp2c-CON, which greatly
increased the immobilization amount of luminophores and decreased
the aggregation-caused quenching effect and nonradiative transition
but also because the porous ultrathin structure of Py-sp2c-CON effectively shortened transport distances of an electron, ion,
and co-reactant (S2O8
2–),
which made more ECL luminophores be activated and thus efficiently
increased the utilization ratio of luminophores. More interestingly,
when Bu4NPF6 was introduced into the Py-sp2c-CON/S2O8
2– system
as a co-reaction accelerator, the ECL signal of Py-sp2c-CON
was further amplified. As expected, the average ECL intensity of the
Py-sp2c-CON/S2O8
2–/Bu4NPF6 system was about 2.03, 5.76, 24.31,
and 190.33-fold higher than those of Py-sp2c-CON/S2O8
2–, Py-sp2c-COF/S2O8
2–, TFPPy/S2O8
2,– and imine-linked pyrene COF/S2O8
2– systems. Considering these
advantages, the Py-sp2c-CON/S2O8
2–/Bu4NPF6 system was employed
to prepare an ECL biosensor for microRNA-21 detection, which exhibited
a broad linear response (100 aM to 1 nM) and a low detection limit
(46 aM). Overall, this work demonstrated that sp2 carbon
CONs can be directly used as a high-performance ECL emitter, thus
expanding the application scope of COFs and opening a new horizon
to develop new types of ECL emitters.