Although porphyrins make up a promising class of electrochemiluminescence
(ECL) luminophors, their aggregation-caused quenching (ACQ) characteristics
lead to inferior ECL efficiency (ΦECL). Furthermore,
current application of porphyrins is limited to cathodic emission.
This work creatively exploited a cage-like porous complex (referred
to as SWU-1) as the microreactor to recede the ACQ effect while modulating
dual ECL emission of meso-tetra(4-carboxyphenyl)porphine (TCPP), which
self-assembled with SWU-1 to form TCPP@SWU-1 nanocapsules (TCPP@SWU-1
NCs). As the microreactor, SWU-1 not only effectively constrained
TCPP aggregation to improve electron–hole recombination efficiency
but also improved stability of anion and cation radicals, thus significantly
enhancing the dual emission of TCPP. Compared with TCPP aggregates,
the resulting TCPP@SWU-1 NCs exhibited significantly enhanced anodic
and cathodic emission, and their ΦECL was increased
by 8.7-fold and 3.9-fold, respectively. Furthermore, black hole quencher-2
(BHQ2) can simultaneously quench anodic and cathodic signals. TCPP@SWU-1
NCs coupling BHQ2 conveniently achieved an ECL ratio detection of
miRNA-126, and the limit of detection (S/N = 3) was 4.1 aM. This work
pioneered the development of the cage-like porous complex SWU-1 as
the microreactor to alleviate defects of the ACQ effect and mediate
dual emission of TCPP. The coupling of dual-emitting TCPP@SWU-1 NCs
and dual-function moderator BHQ2 created a novel single-luminophor-based
ratio system for bioanalysis and provided a promising ECL analysis
approach for miRNA-126.