Coumarin derivative multifunctional fluorescent probe as well as preparation method and application thereof
The prepared coumarin derivative multifunctional fluorescent probe is used to connect nitrogen-containing atomic groups by using acyl hydrazone bonds, which solves the problems of complex synthesis and low sensitivity of existing copper and nickel ion probes, and achieves simultaneous detection and visual distinction detection with high selectivity and high sensitivity.
Patent Information
- Application Number
- CN202510393303.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-31
- Publication Date
- 2025-07-04
AI Technical Summary
The existing fluorescent probes for detecting copper and nickel ions have problems such as cumbersome synthesis steps, low selectivity and sensitivity, and fewer probes are detected at the same time.
A multifunctional fluorescent probe of coumarin derivatives was prepared by condensation reaction of 7-(diethylamine)coumarin-3-formylhydrazide and 6-phenyl-2-pyridine formaldehyde under liquid phase conditions. The nitrogen-containing atomic groups were connected by acyl hydrazone bonds to achieve the fluorescence "on-off" detection of copper ions and nickel ions.
The prepared probe is simple to synthesize, low cost, high selectivity and high sensitivity, can detect copper and nickel ions simultaneously in ethanol solution, and has strong anti-interference ability, realizing visual distinction detection.
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Figure CN120247887A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of analytical detection, and particularly relates to a coumarin derivative multifunctional fluorescent probe, a preparation method thereof, and an application thereof. Background Art
[0002] Copper is the third most essential trace element in the human body after zinc and iron, and plays an important role in life activities, such as participating in sugar metabolism, the formation of hemoglobin, and the synthesis of catecholamines. When the content of copper ions in the human body is too high or too low, a series of genetic diseases or metabolic diseases will occur in the life system, such as Menkes syndrome, Wilson's disease, obesity, and diabetes. In addition, the widespread use of copper ions in agriculture and industry also makes it one of the key pollutants in the environment. Nickel is also an essential trace element in the human body, which affects DNA synthesis, RNA replication, and protein synthesis. When the content of nickel ions in the human body is too high, diseases such as asthma, acute pneumonia, dermatitis, and nasopharyngeal carcinoma will be caused. In addition, as one of the heavy metals, nickel ions will also cause environmental pollution. Therefore, the detection of copper ions and nickel ions is of great significance for protecting human health and the natural environment.
[0003] At present, the methods for detecting copper ions and nickel ions mainly include atomic absorption spectrometry, electrochemical analysis, inductively coupled plasma mass spectrometry, etc. Although these methods are outstanding in detecting copper ions and nickel ions, their applications are limited due to factors such as expensive equipment and cumbersome operations. The fluorescence probe detection method has been widely used in the analysis and detection of metal ions due to its advantages of high sensitivity, simple operation, and rapid response. In recent years, although some fluorescence probes for detecting copper ions and nickel ions have been reported, there are still few single probes that can simultaneously detect copper ions and nickel ions, and most of them have problems such as complex synthesis steps and low sensitivity. Therefore, it is of great significance to develop a fluorescence probe with high sensitivity, high selectivity, simple synthesis, and capable of simultaneously detecting copper ions and nickel ions.
[0004] Coumarin fluorophores can be used for the fluorescence detection of metal ions due to their advantages of stable optical properties, high quantum yield, and easy modification of the structure. The present invention uses coumarin as the fluorescent group, introduces a nitrogen atom-containing group into the coumarin structure through an acylhydrazone bond as the linking group, and synthesizes a coumarin derivative multifunctional fluorescent probe. The probe structure contains multiple metal ion coordination sites, and can realize the fluorescence "on-off" detection of copper ions and nickel ions in an ethanol solution, and has the advantages of high selectivity, high sensitivity, and strong anti-interference ability. Using the coumarin derivative multifunctional fluorescent probe as a test paper, the visual discrimination detection of copper ions and nickel ions can be realized, indicating that the probe has certain practical value in the environmental field. Summary of the Invention
[0005] The present invention aims to solve the deficiencies of existing fluorescent probes for detecting copper ions and nickel ions, such as cumbersome synthesis steps, low selectivity and sensitivity, and provides a coumarin derivative multifunctional fluorescent probe for detecting copper ions and nickel ions, its preparation method and application.
[0006] In order to achieve the above object, the present invention adopts the following technical solutions:
[0007] A coumarin derivative multifunctional fluorescent probe, the molecular structural formula of the described coumarin derivative multifunctional fluorescent probe is:
[0008]
[0009] The synthesis route of the above coumarin derivative multifunctional fluorescent probe is as follows:
[0010]
[0011] The preparation method of the coumarin derivative multifunctional fluorescent probe for detecting copper ions and nickel ions in the present invention includes the following steps: 7-(diethylamino)coumarin-3-carbohydrazide and 6-phenyl-2-pyridinecarboxaldehyde are subjected to a condensation reaction under liquid phase conditions to prepare the coumarin derivative multifunctional fluorescent probe.
[0012] Preferably, in the preparation step, the molar ratio of 7-(diethylamino)coumarin-3-carbohydrazide to 6-phenyl-2-pyridinecarboxaldehyde is (1-2):(1-2); the solvent used for the liquid phase conditions is ethanol, and the concentration of 7-(diethylamino)coumarin-3-carbohydrazide in ethanol is 0.05 mmol / mL - 0.1 mmol / mL.
[0013] The application of the coumarin derivative multifunctional fluorescent probe of the present invention in the quantitative and qualitative detection of copper ions and nickel ions.
[0014] Preferably, the solvent for dissolving the probe when the fluorescent probe detects copper ions and nickel ions is ethanol.
[0015] Furthermore, at an excitation wavelength of 420 nm, after the fluorescent probe recognizes copper ions, the fluorescence intensity at 456 nm is reduced by 24 times, the fluorescence quenching rate reaches 96%, and the solution color turns orange-red; after the fluorescent probe recognizes nickel ions, the fluorescence intensity at 482 nm is reduced by 76 times, the fluorescence quenching rate reaches 99%, and the solution color turns yellow.
[0016] Furthermore, during quantitative detection, the detection concentration ranges of the fluorescent probe for copper ions and nickel ions are both 0 - 5 μmol / L.
[0017] Furthermore, the detection limits of the fluorescent probe for copper ions and nickel ions are 2.4×10 -9 mol / L and 2.5×10-9 mol / L.
[0018] Furthermore, the complexation ratio of the fluorescent probe with copper ions and nickel ions is both 2:1.
[0019] A test paper for detecting copper ions and nickel ions, the test paper contains the above-mentioned coumarin derivative multifunctional fluorescent probe. Specifically, the test paper is soaked in an ethanol solution of the coumarin derivative multifunctional fluorescent probe with a concentration of 1.0×10 -4 ~1.0×10 -6 mol / L for 5 to 15 h, and then taken out and air-dried naturally.
[0020] Principle of the present invention:
[0021] In the multifunctional fluorescent probe of coumarin derivative prepared in the present invention, the coumarin fluorophore is connected to the pyridine structure through a hydrazone bond. The lone pair electrons of the hydrazone nitrogen atom will generate a strong photoinduced electron transfer (PET) process. Therefore, the probe generates a strong fluorescence emission. When copper ions or nickel ions are added to the system, due to the paramagnetism of copper ions and nickel ions and the coordination between the lone pair electrons of the hydrazone nitrogen atom and copper ions and nickel ions, the effective transfer of electrons and energy is hindered, which makes the PET process blocked. Therefore, the fluorescence quenching phenomenon appears, thus realizing the detection of copper ions and nickel ions.
[0022] Compared with the prior art, the present invention has the following beneficial effects:
[0023] (1) The multifunctional fluorescent probe of coumarin derivative prepared in the present invention has simple synthesis steps, low cost, high purity, and has certain market competitiveness.
[0024] (2) The multifunctional fluorescent probe of coumarin derivative prepared in the present invention can simultaneously detect copper ions and nickel ions in an ethanol test solvent, avoiding the interference of other metal ions during the detection process, and has high selectivity and strong anti-interference ability.
[0025] (3) The multifunctional fluorescent probe of coumarin derivative prepared in the present invention has high sensitivity for the detection of copper ions and nickel ions, and the detection limit is as low as 2.4×10 -9 mol / L and 2.5×10 -9 mol / L, and trace detection of copper ions and nickel ions can be realized.
[0026] (4) The multifunctional fluorescent probe of coumarin derivative prepared in the present invention can be made into a test paper for use, realizing the visual discrimination detection of copper ions and nickel ions, and making the application of the probe have a broader prospect. Description of the Drawings
[0027] Figure 1 Multifunctional Fluorescent Probe of Coumarin Derivative 1 1H NMR spectrum
[0028] Figure 2 Multifunctional Fluorescent Probe of Coumarin Derivative 13 13C NMR spectrum
[0029] Figure 3 Fluorescence spectra and solution color changes after adding different metal ions to the solution of multifunctional fluorescent probe of coumarin derivative
[0030] Figure 4 UV absorption spectra of the solution of multifunctional fluorescent probe of coumarin derivative after adding different metal ions
[0031] Figure 5 Effect of different metal ions on the fluorescence intensity of the detection system of copper ions by multifunctional fluorescent probe of coumarin derivative
[0032] Figure 6 Effect of different metal ions on the fluorescence intensity of the detection system of nickel ions by multifunctional fluorescent probe of coumarin derivative
[0033] Figure 7 Fluorescence spectra of the solution of multifunctional fluorescent probe of coumarin derivative after adding different concentrations of copper ions
[0034] Figure 8 Fluorescence spectra of the solution of multifunctional fluorescent probe of coumarin derivative after adding different concentrations of nickel ions
[0035] Figure 9 Linear relationship diagram between the fluorescence intensity of multifunctional fluorescent probe of coumarin derivative at 476 nm and the concentration of copper ions
[0036] Figure 10 Linear relationship diagram between the fluorescence intensity of multifunctional fluorescent probe of coumarin derivative at 476 nm and the concentration of nickel ions
[0037] Figure 11 Job's plot curve diagram of multifunctional fluorescent probe of coumarin derivative and copper ions
[0038] Figure 12 Job's plot curve diagram of multifunctional fluorescent probe of coumarin derivative and nickel ions
[0039] Figure 13 HRMS diagram of multifunctional fluorescent probe of coumarin derivative after complexing with copper ions
[0040] Figure 14 HRMS diagram of multifunctional fluorescent probe of coumarin derivative after complexing with nickel ions
[0041] Figure 15 Color change diagrams of the coumarin derivative multifunctional fluorescent probe under ultraviolet light and daylight. Detailed implementation mode
[0042] The following will give a detailed description of the embodiments of the present invention. The following embodiments are implemented on the premise of the technical solution of the present invention, and detailed implementation schemes and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.
[0043] Example 1: Preparation method of the coumarin derivative multifunctional fluorescent probe, which is carried out according to the following steps:
[0044] Take compound 7-(diethylamino)coumarin-3-carbohydrazide (0.325 g, 1.19 mmol) in a 50 mL eggplant-shaped flask, add 15 mL of absolute ethanol to dissolve it, then add 6-phenyl-2-pyridinecarboxaldehyde (0.218 g, 1.19 mmol) to the system. After heating under reflux for 6 h, cool to room temperature, filter, wash with hot ethanol at 50 - 60 °C, and dry at room temperature to constant weight (dry at room temperature for about 15 hours) to obtain the yellow solid coumarin derivative multifunctional fluorescent probe (0.449 g, 1.02 mmol), and the yield is 85.7%. The molecular structure is:
[0045]
[0046] m.p. 204.3 - 205.6 °C; 1 H NMR (400 MHz, CDCl3) δ: 12.09 (s, 1H), 8.85 (s, 1H), 8.39 (s, 1H), 8.20 (d, J = 7.7 Hz, 1H), 8.04 (d, J = 7.4 Hz, 2H), 7.80 (t, J = 7.8 Hz, 1H), 7.73 (d, J = 7.7 Hz, 1H), 7.56 - 7.38 (m, 4H), 6.67 (dd, J = 9.0, 2.4 Hz, 1H), 6.51 (d, J = 2.3 Hz, 1H), 3.47 (q, J = 7.1 Hz, 4H), 1.25 (t, J = 7.1 Hz, 6H) ppm; 1313C NMR (100 MHz, CDCl3) δ: 162.83, 160.23, 158.00, 157.08, 153.19, 153.16, 149.40, 138.99, 137.17, 131.58, 129.20, 128.87, 126.98, 121.00, 119.67, 110.40, 108.91, 108.69, 96.71, 45.32, 12.55 ppm; FT-IR (KBr) ν = 3240, 2974, 2927, 1700, 1617, 1582, 1474, 1420, 1352, 1188, 1134, 1078, 923, 764, 692, 474 cm -1 ; ESI-MS m / z 441.1 ([M+H] + ); ESI-HRMS calcd for C 26 H 25 N4O3 ([M+H] + ): 441.1927, found 441.1915. 1 1H NMR spectra and 13 13C NMR spectra are as Figure 1 and 2 shown.
[0047] Example 2: The fluorescence recognition performance of the coumarin derivative multifunctional fluorescent probe for various metal ions is carried out according to the following steps:
[0048] Dissolve the coumarin derivative multifunctional fluorescent probe in absolute ethanol to prepare a stock solution with a concentration of 1.0×10 -3 mol / L. Dilute the stock solution with absolute ethanol to a probe solution with a concentration of 1.0×10 -5 mol / L, which is used as the test solution. The nitrates, chlorides or acetates of metal ions are dissolved in distilled water to prepare a solution with a concentration of 1.0×10 -2 mol / L for standby.
[0049] Spectral performance test conditions: The scanning range of the fluorescence spectrometer is 200 - 700 nm, the excitation wavelength λ ex = 420 nm, and the excitation slit and emission slit are 2.5×2.5 nm; the wavelength scanning range of the ultraviolet spectrum is 210 - 650 nm.
[0050] Take 3 mL of 1.0×10 -5 mol / L coumarin derivative multifunctional fluorescent probe solution in a cuvette, and sequentially add 15 μL of 1.0×10 -2 mol / L metal ions (Ni2+ , Cu 2+ , Fe 2+ , Al 3+ , Ag + , Hg 2+ , Cr 3+ , Ba 2+ , Ca 2 + , Zn 2+ , Cs + , Mg 2+ , Mn 2+ , K + , Na + , Pb 2+ ), aqueous solution. Fluorescence spectrum test was carried out, and the results are as Figure 3 shown. The coumarin derivative multifunctional fluorescent probe showed a strong fluorescence emission peak at 476 nm. After adding copper ions and nickel ions, fluorescence quenching occurred. In addition, after adding copper ions, the emission wavelength of the coumarin derivative multifunctional fluorescent probe shifted from 476 nm to 456 nm, showing an obvious blue shift, and the fluorescence intensity of the system decreased from the original 4743 to 198, the fluorescence intensity decreased by 24 times, and the fluorescence quenching rate was 96%. The color changed from bright green to orange-red. After adding nickel ions, the emission wavelength of the coumarin derivative multifunctional fluorescent probe was slightly red-shifted to 482 nm, and the fluorescence intensity of the system decreased to 62, the fluorescence intensity decreased by 76 times, and the fluorescence quenching rate was 99%. The color changed from bright green to yellow. After adding lead ions, although the fluorescence intensity of the system also decreased, the decrease amplitude was not large, only decreased by 1.7 times. After adding other metal ions, the fluorescence intensity of the system remained basically unchanged. The research shows that the coumarin derivative multifunctional fluorescent probe can achieve "naked eye" recognition of copper ions and nickel ions, and has strong selective recognition ability.
[0051] Example 3: The ultraviolet recognition performance of the coumarin derivative multifunctional fluorescent probe for various metal ions was carried out according to the following steps:
[0052] Take 3 mL of 1.0×10 -5 mol / L coumarin derivative multifunctional fluorescent probe solution in a cuvette, and sequentially add 15 μL of metal ions with a concentration of 1.0×10 -2 mol / L (Ni 2+ , Cu 2+ , Fe 2+ , Al 3+ , Ag + , Hg 2+ , Cr 3+ , Ba 2+ , Ca 2 + , Zn2+ , Cs + , Mg 2+ , Mn 2+ , K + , Na + , Pb 2+ ) aqueous solution. Ultraviolet spectrum test was carried out, and the results are as Figure 4 shown. After adding copper ions and nickel ions, new ultraviolet absorption peaks were formed at 474 nm and 458 nm in the system respectively, while the ultraviolet absorption peak of the coumarin derivative multifunctional fluorescent probe itself at 438 nm disappeared, and the addition of other metal ions did not cause changes in the absorption peak. The experiment shows that the coumarin derivative multifunctional fluorescent probe has specific ultraviolet recognition performance for copper ions and nickel ions.
[0053] Example 4: The anti-interference of the coumarin derivative multifunctional fluorescent probe to detect copper ions and nickel ions was carried out according to the following steps:
[0054] Take 3 mL of 1.0×10 -5 mol / L coumarin derivative multifunctional fluorescent probe solution in a cuvette, and successively add 15 μL of metal ions (Fe -2 with a concentration of 1.0×10 2+ , Al 3+ , Ag + , Hg 2+ , Cr 3+ , Ba 2+ , Ca 2+ , Zn 2+ , Cs + , Mg 2+ , Mn 2+ , K + , Na + , Pb 2+ ) aqueous solution. At an excitation wavelength of 420 nm, the fluorescence intensity was measured. Then 15 μL of aqueous solution of copper ions or nickel ions with a concentration of 1.0×10 -2 mol / L was added respectively, and the fluorescence intensity was measured again. The results are as Figure 5 and 6 shown. The fluorescence intensity showed fluorescence quenching after adding copper ions or nickel ions to various metal ion solutions of the coumarin derivative multifunctional fluorescent probe, indicating that the presence of other metal ions does not interfere with the detection of copper ions and nickel ions by the probe. The research shows that the coumarin derivative multifunctional fluorescent probe has strong anti-interference ability for the detection of copper ions and nickel ions.
[0055] Example 5: The detection limit of the coumarin derivative multifunctional fluorescent probe for copper ions and nickel ions was carried out according to the following steps:
[0056] To study the detection limits of the coumarin derivative multifunctional fluorescent probe for copper ions and nickel ions, fluorescence titration experiments were carried out. 3 mL of 1.0×10 -5 mol / L coumarin derivative multifunctional fluorescent probe solution was taken in a cuvette, and aqueous solutions of copper ions and nickel ions with concentrations of 0 - 10 μmol / L were added respectively, and the fluorescence intensity was measured. The results are as shown in Figure 7 and 8 . With the addition of copper ions and nickel ions, the fluorescence intensity of the system gradually decreased. When the concentrations of copper ions and nickel ions were 5 μmol / L, the fluorescence intensity of the system tended to be stable. From Figure 9 and 10 , it can be seen that when the concentrations of copper ions and nickel ions were in the range of 0 - 5 μmol / L, the relationship between the fluorescence intensity of the system and the concentrations of copper ions and nickel ions was approximately linear. By data fitting, the two linear equations obtained were y = 6254.24 - 1226.63x, R 2 = 0.999, y = 6124.90 - 1211.63x, R 2 = 0.999. According to the detection limit calculation formula LOD = 3δ / k (δ is the standard deviation of the blank solution, measured 10 times for the blank, k represents the slope of the straight line), the detection limits of the coumarin derivative multifunctional fluorescent probe for copper ions and nickel ions were calculated to be 2.4×10 - 9 mol / L and 2.5×10 -9 mol / L respectively. This indicates that the coumarin derivative multifunctional fluorescent probe has high sensitivity for the detection of copper ions and nickel ions and can achieve trace detection of copper ions and nickel ions.
[0057] Example 6: The complexation ratio of the coumarin derivative multifunctional fluorescent probe with copper ions and nickel ions was carried out according to the following steps:
[0058] To explore the complexation ratio of the coumarin derivative multifunctional fluorescent probe with copper ions and nickel ions, Job's plot experiments were carried out. 1.0×10 -5 mol / L coumarin derivative multifunctional fluorescent probe solution and 1.0×10 -3 mol / L aqueous solutions of copper ions and nickel ions were taken respectively. In the experiment, the total concentrations of the probe with copper ions and the probe with nickel ions were both 10 μmol / L, and the concentration ratios of the probe with copper ions and the probe with nickel ions were changed. The results are as shown in Figure 11 and 12 . It can be seen from the figure that the inflection point of [Cu 2+ / ([probe] + [Cu 2+ ) appears at 0.32, and [Ni 2+ / ([probe] + [Ni2+ ) The inflection point appears at 0.35, indicating that the complexation ratio of the coumarin derivative multifunctional fluorescent probe with copper ions and nickel ions is both 2:1.
[0059] To further study the interaction ratio of the coumarin derivative multifunctional fluorescent probe with copper ions and nickel ions, high-resolution mass spectrometry studies were carried out, and the results are as Figure 13 and 14 shown. Figure 13 Figure shows the high-resolution mass spectrum of the coumarin derivative multifunctional fluorescent probe + copper ions. The proton peak m / z = 944.3029 in the figure represents the complex [2 probes + Cu 2+ , which is basically consistent with the theoretical value of 944.3060; Figure 14 Figure shows the high-resolution mass spectrum of the coumarin derivative multifunctional fluorescent probe + nickel ions. The proton peak m / z = 939.2922 in the figure represents the complex [2 probes + Ni 2+ , which is basically consistent with the theoretical value of 939.3039. The research results further confirm that the interaction ratio of the coumarin derivative multifunctional fluorescent probe with copper ions and nickel ions is both 2:1.
[0060] Example 7: Detection application of the coumarin derivative multifunctional fluorescent probe as a test paper for copper ions and nickel ions is carried out according to the following steps:
[0061] Using filter paper (3 cm × 1 cm) as the carrier, the coumarin derivative multifunctional fluorescent probe is made into a test paper for the daily detection of copper ions and nickel ions. The test paper is soaked in an ethanol solution of the coumarin derivative multifunctional fluorescent probe with a concentration of 1.0×10 -5 mol / L for 10 h, taken out and air-dried naturally (about 1 mL of the probe solution is absorbed). 50 μL of aqueous solutions of copper ions and nickel ions with a concentration of 1.0×10 -3 mol / L are respectively dropped onto the test paper, and the results are as Figure 15 shown. The coumarin derivative multifunctional fluorescent probe is bright green under ultraviolet light at 365 nm (Figure a1) and light blue under sunlight (Figure a2). The coumarin derivative multifunctional fluorescent probe + copper ions is orange-red under ultraviolet light at 365 nm (Figure b1) and yellowish-brown under sunlight (Figure b2). The coumarin derivative multifunctional fluorescent probe + nickel ions is grass green under ultraviolet light at 365 nm (Figure c1) and light yellow under sunlight (Figure c2). This indicates that the test paper of the coumarin derivative multifunctional fluorescent probe can realize the visual discrimination detection of copper ions and nickel ions and has certain application value in the field of environmental monitoring.
Claims
1. A multifunctional fluorescent probe of coumarin derivative, characterized in that, The molecular structural formula of the fluorescent probe is as follows: 。 2. The preparation method of the coumarin derivative multifunctional fluorescent probe according to claim 1, characterized in that, The preparation process is as follows: 7-(diethylamino)coumarin-3-carbohydrazide and 6-phenyl-2-pyridinecarboxaldehyde are condensed under liquid-phase conditions to prepare a coumarin derivative multifunctional fluorescent probe.
3. The preparation method of the coumarin derivative multifunctional fluorescent probe according to claim 2, characterized in that, The molar ratio of the 7-(diethylamino)coumarin-3-carbohydrazide to the 6-phenyl-2-pyridinecarboxaldehyde is (1~2):(1~2); the solvent used in the liquid-phase condition in the step is ethanol.
4. The application of the coumarin derivative multifunctional fluorescent probe according to claim 1 in the quantitative and qualitative detection of copper ions and nickel ions.
5. The application according to claim 4, wherein The solvent for dissolving the probe when the probe detects copper ions and nickel ions is ethanol.
6. The application according to claim 4, wherein Under an excitation wavelength of 420 nm, when the fluorescent probe recognizes copper ions, the fluorescence intensity decreases at 456 nm and the solution color turns orange-red; when the fluorescent probe recognizes nickel ions, the fluorescence intensity decreases at 482 nm and the solution color turns yellow.
7. Use of a coumarin derivative multifunctional fluorescent probe according to claim 4, characterized in that, During quantitative detection, the detection concentration ranges of the fluorescent probe for copper ions and nickel ions are both 0~5 μmol / L.
8. The application according to claim 4, characterized in that, The complexation ratios of the fluorescent probe with copper ions and nickel ions are both 2:
1.
9. A test paper for detecting copper ions and nickel ions, characterized in that, The test paper contains the coumarin derivative multifunctional fluorescent probe according to claim 1.