Rational Design of ortho-Vinylhydropyridine-Assisted Amino-fluorophore as Hypochlorite Fluorescent Probe

doi:10.6023/cjoc202205019

Abstract

In this paper, a novel fluorescent probe A4 for the detection of hypochlorite ions was designed and synthesized using quinoline as a fluorophore and ortho-vinylhydropyridine auxiliary amino group as a recognition site. Experimental studies show that the fluorescent probe has high selectivity for hypochlorite and extreme sensitivity (response time 1.6 s, limit of detection 77.8 nmol/L). After reacting with hypochlorite, the absorption peak of the UV-vis absorption spectrum at 421 nm was blue-shifted, and the color of the solution changed from yellow to colorless. In the fluorescence emission spectrum, the maximum emission peak at 642 nm was quenched, and the fluorescent color changed from orange red to non-fluorescent. The sensing mechanism was confirmed by liquid chromatograph mass spectrometer (LC-MS) analysis and comparison of UV-vis spectra, which involving the ortho-vinylhydropyridine-assisted amido-to-nitroso oxidation reaction. In addition, the A4-loaded test strip was prepared and applied on the detection of hypochlorite. Moreover, the probe showed moderate aggregation-caused quenching (ACQ) with increasing of water content.

Key words: fluorescent probe, hypochlorite ion, oxidation, detection

Cite this article

Zhihua Chen, Yan Hu, Lili Ma, Ziyi Zhang, Chuanxiang Liu. Rational Design of ortho-Vinylhydropyridine-Assisted Amino-fluorophore as Hypochlorite Fluorescent Probe[J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 718-724.

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Fig. & Tab. 9

Figure 1. Synthetic route of probe A4

Figure 2. (a) UV-selectivity test profiles of probe A4 (20 μmol/ L) with various ions and oxides in CH3CN/PBS (V∶V=3∶7) solutions, and (b) probe A4 (20 μmol/L) UV absorption spectra measured in CH3CN/PBS (V∶V=3∶7) solution with different concentrations of NaClO (0 to 1.5 equiv.) (a) The upper illustration shows the color change of pure probe A4 reacting with various ions and oxides (ClO-, H2O2, $\text{HSO}_{3}^{-}$, SH-, S2-, CN-, SCN-, F-, Cl-, Br-, I-, $\text{HSO}_{4}^{-}$, $\text{ClO}_{4}^{-}$, ${{\text{H}}_{2}}\text{PO}_{4}^{-}$, $\text{BF}_{\text{4}}^{-}$,, AcO-, $\text{NO}_{\text{2}}^{-}$, ONOO-, 1O2, ?OH, Na＋, K＋, Mg2＋, Ca2＋, Zn2＋, Al3＋, Fe3＋, Ba2＋) in a solution of CH3CN/PBS (V∶V=3∶7); (b) the upper right illustration shows the scatter diagram of UV absorption of probe A4 at 421 nm as a function of NaClO concentration

Figure 3. (a) Fluorescence emission spectra of probe A4 (20 μmol/L) with various ions and oxides in CH3CN/PBS (V∶V=3∶7), and (b) fluorescence emission spectra of probe A4 (20 μmol/L) were measured at different concentrations of NaClO (0 to 1.4 equiv.) in CH3CN/PBS (V∶V=3∶7) (a) The upper illustration shows the fluorescence color change of probe A4 reacting with various ions and oxides (ClO-, H2O2, $\text{HSO}_{3}^{-}$, SH-, S2-, CN-, SCN-, F-, Cl-, Br-, I-, $\text{HSO}_{4}^{-}$, $\text{ClO}_{4}^{-}$, ${{\text{H}}_{2}}\text{PO}_{4}^{-}$, $\text{BF}_{\text{4}}^{-}$, AcO-, $\text{NO}_{\text{2}}^{-}$, ONOO-, 1O2, ?OH, Na＋, K＋, Mg2＋, Ca2＋, Zn2＋, Al3＋, Fe3＋, Ba2＋) in CH3CN/PBS (V∶V=3∶7). (b) The upper right inset indicates the relationship chart between fluorescence emission of probe A4 at 642 nm and NaClO concentration (λex=410 nm)

Figure 4. Relationship chart between maximum fluorescence emission of probe A4 (20 μmol/L) at 642 nm in CH3CN/PBS (V∶V=3∶7), and (b) relationship between fluorescence intensity of probe A4 (20 μmol/L) and NaClO (1.5 equiv.) at 642 nm and under different pH conditions (λex=410 nm)

Figure 5. Fluorescence spectra of probe A4 (20 μmol/L) in solutions with different water contents (volume fraction 0~90%) (λex=410 nm)

Figure 6. Mechanism of the probe A4 with hypochlorite ion

Figure 7. Comparison of absorption spectra of probe A4 after reaction with hypochlorite ion and intermediate A3

Figure 8. MS of probe A4 with hypochlorite ion

Figure 9. (a) Color change of the test paper containing probe A4 after reaction with different concentrations of ClO- solution under the illumination of fluorescent lamps, and (b) fluorescence color change of the test paper containing probe A4 after reaction with ClO- solutions of different concentrations under UV light irradiation

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