Dual-Ligand Europium-Organic Gels as a Highly Efficient Anodic Annihilation Electrochemiluminescence Emitter for Ultrasensitive Detection of MicroRNA.

In this study, a novel europium dual-ligand metal-organic gel (Eu-D-MOGs) with high-efficient anodic annihilation electrochemiluminescence (ECL) was synthesized as an ECL emitter to construct a biosensor for ultrasensitive detection of microRNA-221 (miR-221). Impressively, compared to the ECL signal of europium single-ligand metal-organic gels (Eu-S-MOGs), the ECL signal of Eu-D-MOGs was significantly improved since the two organic ligands could jointly replace the H2O and coordinate with Eu3+, which could remarkably reduce the nonradiative vibrational energy transfer caused by the coordination between H2O and Eu3+ with a high coordination demand. In addition, Eu-D-MOGs could be electrochemically oxidized to Eu-D-MOGs•+ at 1.45 V and reduced to Eu-D-MOGs•- at 0.65 V to achieve effective annihilation of ECL, which overcame the side reaction brought by the remaining emitters at negative potential. This benefited from the annihilation ECL performance of the central ion Eu3+ caused by its redox in the electrochemical process. Furthermore, the annihilation ECL signal of Eu3+ could be improved by sensitizing Eu3+ via the antenna effect. In addition, combined with the improved rolling circle amplification-assisted strand displacement amplification strategy (RCA-SDA), a sensitive biosensor was constructed for the sensitive detection of miR-221 with a low detection limit of 5.12 aM and could be successfully applied for the detection of miR-221 in the lysate of cancer cells. This strategy offered a unique approach to synthesizing metal-organic gels as ECL emitters without a coreactant for the construction of ECL biosensing platforms in biomarker detection and disease diagnosis.

Aggregation-Induced Electrochemiluminescence of Copper Nanoclusters by Regulating Valence State Ratio of Cu(I)/Cu(0) for Ultrasensitive Detection of MicroRNA.

In this work, Cu nanoclusters (Cu NCs) with strong aggregation-induced electrochemiluminescence (AIECL) as emitters were used to construct an ECL biosensor for ultrasensitive detection of microRNA-141 (miR-141). Impressively, the ECL signals enhanced with the increased content of Cu(I) in the aggregative Cu NCs. When the ratio of Cu(I)/Cu(0) in aggregative Cu NCs was 3.2, Cu NCs aggregates showed the highest ECL intensity, in which Cu(I) could enhance the cuprophilic Cu(I)···Cu(I) interaction to form rod-shaped aggregates for restricting nonradiative transitions to obviously improve the ECL response. As a result, the ECL intensity of the aggregative Cu NCs was 3.5 times higher than that of the monodispersed Cu NCs. With the aid of the cascade strand displacement amplification (SDA) strategy, an outstanding ECL biosensor was developed to achieve the ultrasensitive detection of miR-141, whose linear range varied from 10 aM to 1 nM with a detection limit of 1.2 aM. This approach opened an avenue to prepare non-noble metal nanomaterials as robust ECL emitters and provided a new idea for detection of biomolecules for diagnosis of disease.