Electrochemiluminescence enhanced by isolating ACQphores in pyrene-based porous organic polymer: A novel ECL emitter for the construction of biosensing platform

Abstract

In this work, a pyrene-based porous organic polymer (Py-POP) with strong electrochemiluminescence (ECL) emission was synthesized and used to fabricate an ECL sensor for the extra-sensitive detection of microRNA-155. The ECL intensity of the Py-POP prepared by tetra(p-aminophenyl)methane (TAPM) and 1,3,6,8-tetrakis(4-formylphenyl)pyrene (TFPPy) was about 3.1 times that of TFPPy aggregates, which was primarily ascribed to the elimination of the effect of aggregation-caused quenching (ACQ) by increasing the distance between ACQ luminophores (pyrene cores) in Py-POP. Meanwhile, the strong covalent connections between 1,3,6,8-tetraphenylpyrene (TPPy) and tetraphenylmethane (TPM) units in the rigid framework of Py-POP could partly block the intramolecular motion of TPPy and TPM, which reduced the non-radiative decay and thus further improved the ECL emission. Furthermore, the hydrophobic porous structure of Py-POP was beneficial to the enrichment of lipophilic tripropylamine (TPrA) coreactants in pores of Py-POP, which greatly shortened the electron migration distance between TPrA coreactants and pyrene luminophores on the pore walls of Py-POP, thereby also enhancing the ECL intensity. By using the Py-POP as a new ECL tag and with the help of the strand displacement processes and target recycling, the fabricated ECL biosensor had a sensitive response for microRNA-155 from 1 fM to 1 nM and a detection limit of 0.326 fM. Overall, this work provided a new and feasible strategy to surmount the ACQ effect for enhancing ECL emission, which not only paved a new way to exploit high-performance ECL materials for fabricating extra-sensitive sensors but also broadened the application of POPs in bioanalysis and ECL fields.