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Enzyme-free nucleic acid dual-amplification strategy combined with mimic enzyme catalytic precipitation reaction for the photoelectrochemical detection of microRNA-21

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Abstract

A novel photoelectrochemical (PEC) biosensor based on an enzyme-free nucleic acid dual-amplification strategy combined with a mimic enzyme to catalyze the deposition of a quencher is reported for the ultrasensitive detection of miRNA-21. A limited amount of target miRNA-21 can trigger the formation of long DNA duplexes on the electrode, owing to the synergistic effect of the enzyme-free nucleic acid dual-amplification strategy of entropy-driven strand displacement reaction (ESDR) amplification and hybridization chain reaction (HCR) amplification. The embedded manganese porphyrin (MnPP) in the long DNA duplexes acts as a horseradish peroxidase (HRP)–mimicking enzyme to catalyze the transformation of benzo-4-chlorohexadienone on the electrode surface, resulting in a significant reduction in photocurrent intensity. As a photosensitive material, BiOCl-BiOI is used as a tag to provide strong initial PEC signals. Based on the cascade integration of the enzyme-free nucleic acid dual-amplification strategy and the mimic enzyme-catalyzed precipitation reaction, the current PEC biosensor exhibits outstanding performance for miRNA-21 detection with an ultralow detection limit (33 aM) and a wide quantification range (from 100 aM to 1 nM). This work provides a new avenue toward the ultrasensitive detection of miRNAs, and is expected to be used for clinical and biochemical samples.

Graphical abstract

A unique PEC biosensor with the BiOCl-BiOI composite, as the photosensitive material, has been developed for ultrasensitive miRNA-21 determination based on the combination of an enzyme-free nucleic acid dual-amplification strategy and mimic enzyme catalytic precipitation reaction.

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Scheme 1
Fig. 1

taken from BiOCl-BiOI composites

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Funding

This work was financially supported by the National Natural Science Foundation of China (22064010, 51862014, 21775089, 22074080), Changjiang Scholar Program of the Ministry of Education of China (Q2019258), and the Taishan Scholar Program of Shandong Province (tsqn201909106).

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Authors and Affiliations

  1. Key Laboratory of Chemical Utilization of Plant Resources of Nanchang, College of Science, Jiangxi Agricultural University, Nanchang, 330045, People’s Republic of China

    Yan Zhao, Feng Gao, Fengli Qu, Mingfang Li & Limin Lu

  2. College of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, 273165, Shandong, China

    Yan Zhao, Xiaomeng Li, Mei-Hao Xiang & Fengli Qu

Authors
  1. Yan Zhao
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  2. Xiaomeng Li
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  3. Mei-Hao Xiang
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  4. Feng Gao
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  5. Fengli Qu
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  6. Mingfang Li
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  7. Limin Lu
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Correspondence to Fengli Qu or Limin Lu.

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Supplementary Information

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604_2022_5345_MOESM1_ESM.docx

Supplementary file1 Materials and reagents, DNA and RNA sequence, optimization of experimental conditions, mechanism of the electron transformation, and additional data. (DOCX 286 KB)

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Zhao, Y., Li, X., Xiang, MH. et al. Enzyme-free nucleic acid dual-amplification strategy combined with mimic enzyme catalytic precipitation reaction for the photoelectrochemical detection of microRNA-21. Microchim Acta 189, 249 (2022). https://doi.org/10.1007/s00604-022-05345-y

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