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A ratiometric lanthanide-free fluorescent probe based on two-dimensional metal-organic frameworks and carbon dots for the determination of anthrax biomarker

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Abstract

A lanthanide-free fluorescent probe has been constructed for the first time based on two-dimensional metal-organic frameworks (2D MOFs) and carbon dots (CDs) for ratiometric determination of dipicolinic acid (DPA), the biomarker of Bacillus anthracis. The fluorescence intensity at 659 nm increased due to the release of organic ligands TCPP resulting from the selective interaction between DPA and Zn2+ of 2D MOFs. CDs provided a reference signal at 445 nm which was almost unaffected, realizing self-calibration DPA sensing. F659/F445 versus the concentration of DPA shows good linear relationships in the range 0.01–0.2 μM and 0.2–10 μM under 390-nm excitation, with a detection limit of 7 nM. The ratiometric probe was prepared from 2D lanthanide-free MOFs so that the drawbacks of lanthanide-based probes were overcome. The proposed sensing system was successfully applied to the determination of DPA in spiked biological samples. These results suggest that a novel, simple, and selective strategy of determining DPA with 2D lanthanide-free MOFs is implemented.

Zn-TCPP nanosheets and a blue carbon dots (b-CDs) are synthesized to construct the ratiometric probe, which can exhibit fluorescence at 445and 659 nm with 390-nm excitation. Dipicolinic acid (DPA) can deprive the junction ions of Zn-TCPP nanosheets, triggering the collapse ofZn-TCPP nanosheets. The fluorescence at 659 nm is enhanced due to the release of TCPP, while the peak of b-CDs at 445 nm is almost not affected. Thus, the fluorescence intensity ratio (F659/F445) can serve as the response signal for sensitive DPA sensing.

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Funding

This work was supported by the National Natural Science Foundation of China (No. 61775099, 21705080, and 81973283), Natural Science Foundation of Jiangsu Province (BK20171043 and BK20171487), Science and Technology Development Fund of Nanjing Medical University-Major Project (No. NMUD2018004), and R&D fund for Smart Health Technology Innovation of Nanjing Medical University and Jiangsu Salt Group (No. NMU-SY201801).

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Authors and Affiliations

  1. School of Pharmacy, Nanjing Medical University, Nanjing, 211166, Jiangsu, People’s Republic of China

    Jian Bao, Jie Mei, Xia Cheng, Dandan Ren, Guanhong Xu, Fangdi Wei, Qin Hu & Yao Cen

  2. Key Laboratory of Cardiovascular & Cerebrovascular Medicine, School of Pharmacy, Nanjing Medical University, Nanjing, 211166, Jiangsu, People’s Republic of China

    Guanhong Xu, Fangdi Wei, Qin Hu & Yao Cen

  3. Key Laboratory of Toxicology, Ningde Normal University, Ningde, 352000, Fujian, People’s Republic of China

    Yong Sun

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  1. Jian Bao
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Bao, J., Mei, J., Cheng, X. et al. A ratiometric lanthanide-free fluorescent probe based on two-dimensional metal-organic frameworks and carbon dots for the determination of anthrax biomarker. Microchim Acta 188, 84 (2021). https://doi.org/10.1007/s00604-021-04701-8

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