A Novle Quinoline Hydrazone-Based Fluorescent Probe for Sequential Determination of Cu2+/Glyphosate and Its Applications

doi:10.6023/cjoc202203009

Abstract

A novel quinoline hydrazone-based fluorescent probe L was designed and synthesized using quinoline-2-carboxylic acid and 7-(diethylamino)coumarin-3-carbaldehyde as raw materials. The spectral properties of probe L were studied by UV-Vis/fluorescence spectrophotometry. The results showed that probe L had obvious ON-OFF fluorescence response to Cu²⁺ in the tetrahydrofuran (THF)/H₂O [V:V=3:7, 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid (HEPES) 10 mmol/ L, pH=7.4] solution, and it displayed efficiency, high specificity and sensitivity. Job’s plot and high resolution mass spectrometry showed that the stoichiometry of L-Cu²⁺ complex was estimated to be 1:1. Meanwhile, complex L-Cu²⁺ showed high selectivity and good anti-interference ability towards glyphosate through the significant fluorescence enhancement, and the detection limit of complex L-Cu²⁺ to glyphosate could reach 5.6×10^–8 mol/L (9.5×10^–3 mg/L). In addition, complex L- Cu²⁺ was able to sense glyphosate by “naked-eye” according to the color change, and applied to glyphosate detection in the actual water samples.

Key words: quinoline hydrazone, fluorescent probe, Cu2+, glyphosate, sequential recognition

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Mianyuan Wu, Jun You, Yanchao Yu, Wenju Wu. A Novle Quinoline Hydrazone-Based Fluorescent Probe for Sequential Determination of Cu²⁺/Glyphosate and Its Applications[J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2559-2567.

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Fig. & Tab. 12

Scheme 1. Synthetic route of probe L

Figure 1. Fluorescence emission spectra (a) and UV-Vis absorption spectra (b) of probe L (10 μmol/L) interacted with different ions (10 μmol/L) (λex=450 nm) The fluorescence changes of probe L (100 μmol/L) without and with Cu2+(100 μmol/L) under a portable UV lamp 365 nm

Figure 2. Fluorescence intensity of probe L (10 μmol/L) without and with Cu2+ (10 μmol/L) in the presence of various ions (10 μmol/L) at 530 nm 1: Cu2+, 2: Co2+, 3: Zn2+, 4: Ca2+, 5: Cr3+, 6: K+, 7: Ni2+, 8: Al3+, 9: Fe3+, 10: Mg2+, 11: Pb2+, 12: Na+, 13: Sr3+, 14: Ce3+, 15: Ag+, 16: Li+, 17: Cd2+, 18: Hg2+, 19: $\text{SO}_{4}^{2}$, 20: F–, 21: SCN–, 22: Br–, 23: ${{\text{S}}_{2}}\text{O}_{3}^{2}$, 24: ${{\text{H}}_{2}}\text{PO}_{4}^{}$, 25: $\text{HPO}_{4}^{2}$, 26: $\text{NO}_{2}^{}$, 27: I–, 28: $\text{HCO}_{3}^{}$, 29: $\text{CO}_{3}^{2}$, 30: Cl–, 31: CH3COO–

Figure 3. (a) Fluorescence spectra of probe L (10 μmol/L) toward varying concentrations of Cu2+ (0~12 μmol/L) and (b) linear relationship between the concentration of Cu2+ (0~8 μmol/ L) and the fluorescence intensity at 530 nm of probe L (10 μmol/L) The photo shows the color change of probe L (10 μmol/L) with the addition of Cu2+ (0~12 μmol/L) under natural light; Dot diagram of the fluorescence responses of probe L (10 μmol/L) toward varying concentrations of Cu2+ (0~12 μmol/L) at 530 nm

Figure 4. Job's plot of probe L and Cu2+ ([L]+[Cu2+]=10 μmol/L)

Figure 5. Fluorescence emission spectra (a) and UV-Vis absorption spectra (b) of complex L-Cu2+ (10 μmol/L) interacted with organophosphorus pesticides, metal ions or anions (10 μmol/L) (λex=450 nm) The fluorescence changes of probe L (100 μmol/L), complex L-Cu2+ (100 μmol/L) and complex L-Cu2+ (100 μmol/L) with GLY (100 μmol/L) under a portable UV lamp 365 nm

Figure 6. Fluorescence intensity of complex L-Cu2+(10 μmol/L) without and with GLY (10 μmol/L) in the presence of various Ops, metal ions or anions (10 μmol/L) at 530 nm 1: GLY, 2: Trichlorfon, 3: Phosmet, 4: Dichlorvos, 5: Malathion, 6: Omethoate, 7: Dimethoate, 8: Ethoprophos, 9: Fenitrothion, 10: Parathion methyl, 11: Parathion, 12: Glufosinate, 13: $\text{SO}_{4}^{2}$, 14: F–, 15: SCN–, 16: Br–, 17: ${{\text{S}}_{2}}\text{O}_{3}^{2}$, 18: $\text{HPO}_{4}^{2}$, 19: ${{\text{H}}_{2}}\text{PO}_{4}^{}$, 20: $\text{NO}_{2}^{}$, 21: I–, 22: $\text{HCO}_{3}^{}$, 23: $\text{CO}_{3}^{2}$, 24: Cl–, 25: CH3COO–, 26: Co2+, 27: Zn2+, 28: Ca2+, 29: Cr3+, 30: K+, 31: Ni2+, 32: Al3+, 33: Fe3+, 34: Mg2+, 35: Pb2+, 36: Na+, 37: Sr3+, 38: Ce3+, 39: Ag+, 40: Li+, 41: Cd2+, 42: Hg2+

Figure 7. (a) Fluorescence spectra of complex L-Cu2+ (10 μmol/L) toward varying concentrations of GLY (0~18 μmol/L) and (b) linear relationship between the concentration of GLY (2~12 μmol/L) and the fluorescence intensity at 530 nm (λex=450 nm) of complex L-Cu2+ (10 μmol/L) The photo shows the color change of complex L-Cu2+ (10 μmol/L) with the addition of GLY (0~15 μmol/L) under natural light; Dot diagram of the fluorescence responses of complex L-Cu2+ (10 μmol/L) toward varying concentrations of GLY (0~18 μmol/L) at 530 nm

Figure 8. Job's plot of complex L-Cu2+and GLY ([L-Cu2+]+[GLY]=10 μmol/L)

Scheme 2. Possible sequential recognition mechanism of probe L with Cu2+ and glyphosate

Figure 9. Fluorescence response of probe L (10 μmol/L) to Cu2+ (10 μmol/L) and GLY (10 μmol/L) at various pH

Sample	Add/(μmol•L^–1)	Found/(μmol•L^–1)	Recovery/%	RSD/% (n=3)
City water	3.00	2.72	90.67	0.92
	5.00	5.79	115.80	2.14
	7.00	7.27	103.86	2.31
	9.00	9.46	105.11	6.37
	11.00	11.14	101.27	2.42
Songhua River water	3.00	3.70	123.23	0.16
	5.00	5.16	103.20	1.06
	7.00	7.09	101.29	2.82
	9.00	9.43	104.78	0.78
	11.00	11.15	101.36	1.70

Table 1. Determination of GLY in actual water samples

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一种基于喹啉酰腙的接力识别Cu²⁺和草甘膦的荧光探针及其应用

A Novle Quinoline Hydrazone-Based Fluorescent Probe for Sequential Determination of Cu²⁺/Glyphosate and Its Applications

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一种基于喹啉酰腙的接力识别Cu2+和草甘膦的荧光探针及其应用