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Aspartic acid assisted one-step synthesis of stable CsPbX3@Asp-Cs4PbX6 by in situ growth in NH2-MIL-53 for ratiometric fluorescence detection of 4-bromophenoxybenzene

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Abstract

A molecularly imprinted ratiometric fluorescent sensor was synthesized for the detection of 4-bromophenoxybenzene (BDE-3) based on perovskite quantum dots and metal organic framework. First, aspartic acid (Asp) was introduced during the synthesis of perovskite CsPbX3 for the formation of a core-shell structure of CsPbX3@Asp-Cs4PbX6. Due to the protection of the shell layer Cs4PbX6, the stability of the core CsPbX3 was improved significantly. Compared to CsPb(BrI)3, the ultraviolet and thermal stabilities of CsPb(BrI)3@Asp-Cs4Pb(BrI)6 were increased by 26 times and 32 times, respectively, and, compared to CsPbBr3, these stabilities of CsPbBr3@Asp-Cs4PbBr6 were increased by 3 times and 13 times, respectively. The water stabilities of CsPb(BrI)3@Asp-Cs4Pb(BrI)6 and CsPbBr3@Asp-Cs4PbBr6 were greatly improved too. Then, a ratiometric fluorescence sensor was constructed by in situ growth of CsPb(BrI)3@Asp-Cs4Pb(BrI)6 in metal organic framework (NH2-MIL-53) for the detection of BDE-3, in which the orange fluorescence of CsPb(BrI)3@Asp-Cs4Pb(BrI)6 (614 nm) was regarded as the reference signal and the cyan fluorescence of NH2-MIL-53 (494 nm) was used as the fluorescence response signal. To improve the selectivity of the sensor, the molecular imprinting polymer (MIP) was modified on the NH2-MIL-53 and an imprinting factor of 3.17 was obtained. Under 365 nm light excitation, the fluorescent response signal at 494 nm was quenched gradually by BDE-3 in the range 11.4 to 68.5 nmol/L, while the reference signal at 614 nm remained unchanged. The limit of detection and limit of quantification were 3.35 and 11.2 nmol/L, respectively, and the fluorescent color of the sensor changed gradually from cyan to green to orange, which illustrated that the developed sensor has an ability to recognize BDE-3 specifically, a good anti-interference ability, and a sensitively visual detection ability. Moreover, the sensor was successfully applied to the BDE-3 detection in polyethylene terephthalate plastic bottle, polyvinyl chloride plastic bag, and circuit board with satisfactory recoveries (96.3–108.1%) and low relative standard deviations (5%).

Graphical abstract

The preparation processes of NH2-MIL-53, NH2-MIL-53-CsPb(BrI)3@Asp-Cs4Pb(BrI)6, and the MIP-NH2-MIL-53-CsPb(BrI)3@Asp-Cs4Pb(BrI)6 composites.

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Acknowledgments

This work was supported by the Guangdong Basic and Applied Basic Research Foundation (No. 2019A1515012169, No. 2021A1515011513) and the National Natural Science Foundation of China (No. 81573678).

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Authors and Affiliations

  1. School of Pharmacy, Guangdong Pharmaceutical University, Guangzhou, 510006, China

    Xiaoyu Fang, Jianping Ye, Ding Duan, Xin Cai & Kang Li

  2. Department of Ultrasound, Guangzhou Red Cross Hospital, Medical College, Jinan University, Guangzhou, 510220, China

    Xinmin Guo

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Fang, X., Ye, J., Duan, D. et al. Aspartic acid assisted one-step synthesis of stable CsPbX3@Asp-Cs4PbX6 by in situ growth in NH2-MIL-53 for ratiometric fluorescence detection of 4-bromophenoxybenzene. Microchim Acta 188, 204 (2021). https://doi.org/10.1007/s00604-021-04863-5

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