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Photoelectrochemical sensor based on AuNPs@WO3@TpPa-1-COF for quantification of DNA methylation levels

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Abstract

A “signal-off” photoelectrochemical (PEC) sensing platform has been designed for the ultrasensitive detection of DNA methylation levels and multiple methylated sites. The platform employs tungsten trioxide and TpPa-1-COF loaded by gold nanoparticle (AuNPs@WO3@TpPa-1-COF) composite material as the photoactive component and p-type reduced graphene (rGO) as an efficient quencher. The PEC signal of AuNPs@WO3@TpPa-1-COF composite is effectively quenched in the presence of p-type rGO, because p-type rGO can compete with AuNPs@WO3@TpPa-1-COF to deplete light energy and electron donors. In addition, a hybrid strand reaction (HCR) amplification strategy fixes more target DNA and then combines with rGO-modified anti-5-methylcytosine antibody to facilitate ultrasensitive DNA methylation detection. Under optimal conditions, DNA methylation can be measured within a linear concentration range of 10–14 to 10–8 M, with an exceptionally low detection limit of 0.19 fM (S/N = 3). At the same time, the platform can conduct quantitative determination of multi-site methylation, with the linear equation △I = 44.19LogA + 61.43, and the maximum number of methylation sites is 5. The sensor demonstrates high sensitivity, excellent selectivity, and satisfactory stability. Furthermore, the proposed signal-off PEC strategy was successfully employed to detect DNA methylation in spiked human serum samples, with recoveries ranging from 93.17 to 107.28% and relative standard deviation (RSD) ranging from 1.15 to 5.49%.

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Funding

Financial support for this work was provided by the National Natural Science Foundation of China (No. 82272430, No. 81873982, and No. 82003109), Special Project of Scientific and Technological Innovation Capability Improvement of the Army Military Medical University (No. 2022XQN04 and No. 2021XQN03), and Special Support from the Chongqing Postdoctoral Research Project (No. 2021XM1018).

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  1. Huamin Liu and Chenghong Li share equal contribution.

Authors and Affiliations

  1. Department of Clinical and Military Laboratory Medicine, College of Medical Laboratory Science, Army Medical University, Chongqing, 400038, China

    Huamin Liu, Chenghong Li, Lina Wang, Lichao Fang, Hui Huang, Jun Deng, Xiaoping Ran, Lulu Li & Junsong Zheng

  2. Emergency Department, 2, Affiliated Hospital of Chongqing Medical University, Chongqing, 400010, China

    Yue Hu & Mimi Li

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  1. Huamin Liu
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Liu, H., Li, C., Wang, L. et al. Photoelectrochemical sensor based on AuNPs@WO3@TpPa-1-COF for quantification of DNA methylation levels. Microchim Acta 191, 167 (2024). https://doi.org/10.1007/s00604-024-06235-1

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