A novel flavonol-based colorimetric and turn-on fluorescent probe for rapid determination of hydrazine in real water samples and its bioimaging <i>in vivo</i> and<i>in vitro</i>

doi:10.1007/s11705-022-2171-1

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (1) : 24-33 https://doi.org/10.1007/s11705-022-2171-1

RESEARCH ARTICLE

A novel flavonol-based colorimetric and turn-on fluorescent probe for rapid determination of hydrazine in real water samples and its bioimaging in vivo andin vitro

Ahui Qin¹, Yan Zhang¹, Shuai Gong¹, Mingxin Li¹, Yu Gao¹, Xu Xu¹, Jie Song², Zhonglong Wang¹(

), Shifa Wang¹(

)

¹. Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China
². Department of Natural Sciences, University of Michigan-Flint, Flint, MI 48502, USA

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Abstract

Hydrazine is extremely toxic and causes severe harm to human body. Herein, a novel fluorescent probe 4-oxo-2-styryl-4H-chromen-3-yl thiophene-2-carboxylate (FHT) was synthesized for detecting hydrazine by using natural cinnamaldehyde as starting material. This probe exhibited significantly enhanced fluorescence response towards hydrazine over various common metal ions, anions, and amine compounds. The detection limit of probe FHT for hydrazine was as low as 0.14 μmol·L^–1, significantly lower than that of the threshold value of 0.312 μmol·L^–1, imposed by the Environmental Protection Agency. Moreover, the proposed probe was able to detect hydrazine within wide pH (5–10) and linear detection ranges (0–110 μmol·L^–1). This probe was employed for determining trace hydrazine in different environmental water samples. The probe FHT-loaded filter paper strips were able to conveniently detect hydrazine of low concentration through distinct naked-eye and fluorescent color changes. Importantly, the probe FHT with low cytotoxicity was successfully applied to visualize hydrazine in living Hela cells and zebrafish.

Keywords cinnamaldehyde 3-hydroxychromone derivative hydrazine fluorescent probe

Corresponding Author(s): Zhonglong Wang,Shifa Wang

About author:

Changjian Wang and Zhiying Yang contributed equally to this work.

Online First Date: 28 July 2022 Issue Date: 21 February 2023

Cite this article:

Ahui Qin,Yan Zhang,Shuai Gong, et al. A novel flavonol-based colorimetric and turn-on fluorescent probe for rapid determination of hydrazine in real water samples and its bioimaging in vivo andin vitro[J]. Front. Chem. Sci. Eng., 2023, 17(1): 24-33.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2171-1
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I1/24

Scheme1 Synthesis of probe FHT.

Fig.1 (a) UV?vis absorption spectra of probeFHT (10 μmol·L^–1) with and without addition of N₂H₄ (200 μmol·L^–1). Inset: The solution color change of probe FHT before and after the addition of N₂H₄ under daylight. (b) The fluorescence spectra of probe FHT (10 μmol·L^–1) in the absence and presence of N₂H₄ (200 μmol·L^–1). Inset: The solution fluorescence change of FHT before and after the addition of N₂H₄ under 365 nm UV lamp (λ_ex = 440 nm).

Fig.2 (a) UV?vis absorption spectra and (b) fluorescence spectra of probeFHT (10 μmol·L^–1) with hydrazine (0–200 μmol·L^–1) in DMSO/PBS buffer solution (v/v = 4/6, 10 mmol·L^–1, pH = 7.4); (c) the plot of absorption intensity ratio (A_{445 nm}/A_{345 nm}) against the concentrations of hydrazine (0–200 μmol·L^–1); (d) the plot of fluorescence emission intensity (F_{445 nm}) against the concentrations of hydrazine (0–200 μmol·L^–1). λ_ex = 440 nm.

Fig.3 (a) Fluorescence spectra of probe FHT (10 μmol·L^–1) upon addition of different analytes (200 μmol·L^–1) in DMSO/PBS buffer solution (v/v = 4/6, 10 mmol·L^–1, pH = 7.4); (b) fluorescence intensity of probe FHT (10 μmol·L^–1) at 540 nm in the presence of N₂H₄ (200 μmol·L^–1) and different species (200 μmol·L^–1): (1) Na⁺, (2) Ag⁺, (3) Ca²⁺, (4) Cr³⁺, (5) Cs⁺, (6) Hg²⁺, (7) Ce⁴⁺, (8) NH₄⁺, (9) F^–, (10) HCO₃^–, (11) HPO₄^2–, (12) NO₂^–, (13) SO₃^2–, (14) SCN^–, (15) Br^–, (16) ClO^–, (17) I^–, (18) Cl^–, (19) methylamine, (20) ethylenediamine, (21) hydroxylamine, (22) salicylhydrazine, (23) phenylhydrazine, (24) formylhydrazine, and (25) 2,4-dinitrophenylhydrazine. λ_ex = 440 nm.

Fig.4 (a) Effect of pH value on the fluorescence intensity of probe FHT (10 μmol·L^–1) at 540 nm in the absence and presence of N₂H₄ (200 μmol·L^–1); (b) effect of time on the fluorescence intensity of probe FHT (10 μmol·L^–1) at 540 nm in the absence and presence of N₂H₄ (200 μmol·L^–1).

Fig.5 The ¹H NMR spectra of probe FHT alone and probe FHT with N₂H₄ in DMSO-d₆.

Scheme2 The proposed response mechanism of probe FHT to hydrazine.

Fig.6 DFT calculation and frontier molecular orbitals of probe FHT and compound 3-HF.

Fig.7 Color changes of FHT-coated filter paper after adding different concentrations of hydrazine (0, 20, 40, 60, 80, 100, 120, 150 μmol·L^–1) under 360 nm UV light and daylight.

Tab.1 Determination results of FHT towards N₂H₄ in three kinds of water samples

Fig.8 (a) The fluorescence intensity of FHT at 540 nm after adding different concentrations of N₂H₄ in different water samples; the linear plots between the fluorescence intensity of FHT and different concentrations of N₂H₄ in (b) distilled water, (c) tap water, and (d) Xuanwu Lake water.

Fig.9 Fluorescence microscope images of HeLa cells. (a) the cells incubated with probe FHT (10 μmol·L^–1) for 1 h; (b–d) incubated with FHT (10 μmol·L^–1) for 1 h, and followed by the addition of N₂H₄ (30, 60, 100 μmol·L^–1) for 0.5 h (the excitation wavelength: 408 nm; the collected fluorescence wavelength: 450?650 nm).

Fig.10 Fluorescence microscope images of zebrafish. (a–c) the zebrafish incubated with probe FHT (10 μmol·L^–1) for 2 h; (d–f) incubated with FHT (10 μmol·L^–1) for 2 h followed by the addition of N₂H₄ (100 μmol·L^–1) for 1 h; (I–II) corresponding 3D surface plots (the excitation wavelength: 408 nm; the collected fluorescence wavelength: 450?650 nm).

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