4.8 Article

MicroRNA-Triggered Deconstruction of Field-Free Spherical Nucleic Acid as an Electrochemiluminescence Biosensing Switch

期刊

ANALYTICAL CHEMISTRY
卷 93, 期 41, 页码 13928-13934

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acs.analchem.1c02965

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资金

  1. NNSF of China [22022408]
  2. Natural Science Foundation Project of CQ CSTC [cstc2018jcyjAX0546]
  3. Fundamental Research Funds for the Central Universities [XDJK2019TJ002]

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A new field-free and highly ordered spherical nucleic acid (SNA) nanostructure was self-assembled using ferrocene-labeled DNA tweezers and DNA linkers, serving as an ECL switch for improved recognition efficiency. Combined with mesoporous silica nanospheres (mSiO(2) NSs) filled with Rub-Pt nanoparticles (Rub-Pt@mSiO(2) NSs), a highly sensitive detection platform for let-7b microRNA was achieved through target-triggered SNA deconstruction, highlighting potential applications in biomarker analyses.
Herein, a new field-free and highly ordered spherical nucleic acid (SNA) nanostructure was self-assembled directly by ferrocene (Fc)-labeled DNA tweezers and DNA linkers based on the Watson-Crick base pairing rule, which was employed as an electrochemiluminescence (ECL) quenching switch with improved recognition efficiency due to the high local concentration of the ordered nanostructure. Moreover, with a collaborative strategy combined with the advantages of both self-accelerated approach and pore confinement-enhanced ECL effect, the mesoporous silica nanospheres (mSiO(2) NSs) were prepared to be filled with rubrene (Rub) as ECL emitters and Pt nanoparticles (PtNPs) as coreaction accelerators (Rub-Pt@mSiO(2) NSs), which demonstrated high ECL response in the aqueous media (dissolved O-2 as coreactant). When the SNA nanostructure was immobilized on the Rub-Pt@mSiO(2) NSs-modified electrode, it presented a signal off state owing to the quenching effect of the Fc molecules. As a proof of concept, the SNA-based ECL switch platform was applied in the detection of microRNA let-7b (let-7b). Impressively, in the presence of the target let-7b, a deconstruction of the SNA nanostructure was actuated, causing the Fc to leave the electrode surface and achieved an extremely high ECL recovery (signal on state). Hence, a sensitive determination for let-7b was realized with a low detection limit of 1.8 aM ranging from 10 aM to 1 nM by employing the Rub-Pt@mSiO(2) NSs-based ECL platform combined with the target-triggered SNA deconstruction, which also offered an ingenious method for the further applications of biomarker analyses.

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