Copper nanoclusters (Cu NCs) as emerging luminescent metal NCs are gaining increasing attention owing to the comparatively low cost and high abundance of the Cu element in nature. However, it remains challenging to manipulate the optical properties of Cu NCs. Unlike most dispersed Cu NCs, whose luminescence efficiency was restricted by nonexcited relaxation, the Cu NCs confined in a porous poly-L-cysteine (poly-L-Cys) film were generated controllably with enhanced electrochemiluminescence (ECL) by in situ electrochemical reduction. Specifically, poly-L-Cys provided a porous structure to regulate the generation of Cu NCs within its holes, which not only increased the restriction on the intramolecular vibration and rotation of the ligands but also expedited the electron transfer near the electrode surface, reflecting in an enhancement of the ECL signal and efficiency. As an application of the confined Cu NCs, an ECL biosensor with high performance was constructed skillfully for highly sensitive detection of alkaline phosphatase (ALP), which adopted Cu NCs as the ECL luminophore and poly-L-Cys as a coreaction accelerator in a novel ECL ternary system (Cu NCs/S 2 O 8 2− /poly-L-Cys). Furthermore, an ingenious target amplification based on the combination of a DNA walker and click chemistry was developed to convert ALP to DNA strands efficiently, achieving great improvement in the recognition efficiency. As a result, the biosensor had a low detection limit (9.5 × 10 −7 U•L −1 ) and a wide linear range (10 −8 −10 −2 U•L −1 ) for ALP detection, which showed great promise for the detection of non-nucleic acid targets and the diagnosis of diseases.

Here, we described a novel swing arm location-controllable DNA walker based on the DNA tetrahedral nanostructures (DTNs) for nucleic acid detection using the polycyclic aromatic hydrocarbon (PAH) microcrystals (TAPE-Pe MCs) consisting of the nonplanar molecular tetrakis­(4-aminophenyl)­ethene (TAPE) and planar molecular perylene (Pe) as electrochemiluminescence (ECL) luminophores. Specifically, the swing arm strands and track strands were fixed simultaneously on the DTNs to obtain the location-controllable DNA walker, which possessed an improved reaction efficiency compared to that of a fixed swing arm-based DNA walker due to the quantitative and orderly swing arm on the DTNs. On the other hand, the Pe microcrystals doped by TAPE molecules could decrease the π–π stacking of Pe molecules for the ECL efficiency enhancement, achieving a blue-shifted and intense ECL emission. Therefore, we defined this enhanced and blue-shifted ECL phenomenon as “inhibition of conjugation-driven ECL (IC-ECL)”. To prove these principles, a location-controllable DNA walker-based ECL biosensor was developed with microRNA let-7a as target molecules. The ECL biosensor achieved a low detection limit of 4.92 fM within a wide linear range from 10 fM to 100 nM. This approach offers a new insight for ECL efficiency increase and location-controllable strategies with improved reaction efficiency, demonstrating potential in diagnostic analysis.

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In spite of the DNA walkers executing the signal accumulation task in the process of moving along the predetermined paths, the enhancement of walking dynamics and walking path controllability are still challenging due to the unprogrammed arrangements of DNA orbits. Taking these dilemmas into account, a bipedal DNA walker was designed skillfully by the virtue of wireframe orbits assembled by DNA cubes in order, which improved the efficiency and the continuity of walking. It could be attributed to the fact that both the contact chance and the dynamic interaction between walking strands and designated orbits were beneficial to minimize the possibility of derailment and improve the accumulation of signal. In addition, the hollow titanium dioxide nanospheres coated with rubrene (Rub@TiO2 NSs) were prepared by the etching of inner silicon dioxide nanoparticles (SiO2 NPs) to regulate the distribution pattern of rubrene (Rub) molecules and expose more electrochemically active sites for high-efficient electrochemiluminescence (ECL). Benefiting by the pore confinement-enhanced ECL, the electron and mass transfer was significantly accelerated because of the hollow structure of Rub@TiO2 NSs. Subsequently, endogenous dissolved oxygen as the coreactant and palladium nanoparticles (Pd NPs) as the coreaction accelerator were employed to constitute a ternary ECL system with explosive signal response. Combining with this ECL platform, the bipedal walker activated by the target can autonomously and directionally move on the DNA wireframe orbits to release the quenching probes continuously. In this way, the biosensor displayed a low detection limit (2.30 × 10–8 U·mL–1) and a wide linear range (1.0 × 10–7 to 1.0 × 10–1 U·mL–1) for the sensitive detection of Dam methyltransferase (Dam MTase) activity. Therefore, a novel strategy for the accurate quantification of epigenetic targets was developed by virtue of improving the walking dynamics of DNA walker and amplifying the ECL of Rub molecules.