Method for detecting fluoride ions and applications thereof

Abstract

The application discloses a fluorine ion detection method and application, and proposes application of a compound of formula I in fluorine ion detection. The compound of formula I can specifically recognize fluorine ions in an aqueous solution through deprotonization of hydroxyl groups and amide bonds by fluorine ions, and a color change recognizable by naked eyes occurs when the fluorine ions are detected; the fluorine ions can significantly enhance the fluorescence emission peak intensity of the compound of formula I, so that hyperchromic effect is generated on an absorption peak of the compound of formula I at 378 nm, and hypochromic effect is generated on absorption peaks at 414 nm and 434 nm.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of substance detection, in particular to a detection method of fluoride ions and application. BACKGROUND

[0002] Drinking water is the largest single contributor to daily fluoride intake in some remote areas. Fluoride naturally infiltrates water supply systems due to the solubilization of fluorine-containing minerals such as fluorapatite, cryolite and fluorite. It is estimated that more than ten million people regularly drink water containing fluoride, which is derived from groundwater and has a concentration exceeding the limit recommended by the World Health Organization, which is harmful to the human body. However, the common fluoride ion detection methods have the disadvantages of complex procedures, high cost, poor timeliness, etc., so it is of great significance to develop a new type of rapid detection method. SUMMARY

[0003] The present application aims to at least solve one of the above technical problems in the prior art. To this end, the purpose of the present application is to provide a detection method of fluoride ions and application.

[0004] In order to achieve the above-mentioned purpose, the technical solution adopted by the present application is:

[0005] In a first aspect of the present application, the application of a compound of formula I in fluoride ion detection is proposed:

[0006]

[0007] The compound of formula I is N'-[(1E)-(2-hydroxynaphthalen-1-yl)methylidene]benzohydrazide, also known as o-hydroxynaphthaldehyde condensation nicotinic hydrazine.

[0008] In some embodiments of the present application, the fluoride ion detection includes at least one of visual recognition detection, fluorescence detection, and ultraviolet light detection.

[0009] In some embodiments of the present application, the application is for non-disease diagnosis or treatment purposes.

[0010] In a second aspect of the present application, a detection method of fluoride ions is proposed,

[0011] The method includes using a compound of formula I as an ion probe to identify fluoride ions;

[0012] According to whether the color change recognizable by the naked eye occurs before and after the solution of the compound of formula I is added to the test product, whether the test product contains fluoride ions is identified; and / or,

[0013] According to whether the fluorescence emission spectrum changes before and after the solution of the compound of formula I is added to the test product, whether the test product contains fluoride ions is identified; and / or,

[0014] Whether the UV-visible absorption spectrum of the solution of the compound of the formula I changes before and after the addition of the test product to identify whether the test product contains fluoride ions.

[0015] In some embodiments of the present application, when the test product makes the solution of the compound of the formula I become a light yellow / colorless which can be recognized by naked eyes, and / or, under UV light, when the test product makes the solution of the compound of the formula I become a cyan / green / cyan-green which can be recognized by naked eyes, the test product contains fluoride ions.

[0016] In some embodiments of the present application, when the test product enhances the fluorescence intensity of the solution of the compound of the formula I at 450nm-600nm, the test product contains fluoride ions.

[0017] In some embodiments of the present application, the excitation wavelength is set to 300nm-400nm, when the test product enhances the fluorescence intensity of the solution of the compound of the formula I at 450nm-600nm, the test product contains fluoride ions.

[0018] In some embodiments of the present application, the excitation wavelength is 350nm-370nm.

[0019] In some embodiments of the present application, when the test product enhances the UV absorption intensity of the solution of the compound of the formula I at 365nm-380nm, and / or, reduces the UV absorption intensity at 400nm-440nm, the test product contains fluoride ions.

[0020] In some embodiments of the present application, the concentration of fluoride ions in the test product is not less than 0.1μM, such as not less than 0.13μM, not less than 10.0μM, not less than 1.0μM.

[0021] In some embodiments of the present application, the molar ratio of fluoride ions to the compound of the formula I in the test product is 1:0.1-10, such as 1:0.5-5. In the present application, the use of too much compound of the formula I will also increase the detection cost.

[0022] In some embodiments of the present application, the solvent used in the solution of the compound of the formula I includes at least one of water, methanol, ethanol, such as a mixture of methanol and water, and the volume fraction of methanol in the mixture is 20%-99.9%. Generally speaking, the hydration energy of fluoride ions is large, and it is difficult to effectively detect fluoride ions in an aqueous system. The existing fluoride ion detection system is usually a pure organic solvent, and in the present application, the solution of the compound of the formula I can contain water, which can solve the problem of difficulty in detecting fluoride ions in aqueous solution due to the large hydration energy of fluoride ions.

[0023] In some embodiments of the present application, the sample to be tested comprises any one of water, food, biological sample, and medicine.

[0024] In some embodiments of the present application, the method for detecting fluoride ion comprises the following steps:

[0025] S1: mixing fluoride ion standard with the compound of formula I to obtain a standard control sample;

[0026] S2: mixing the sample to be tested with the compound of formula I to obtain a sample to be tested;

[0027] S31: detecting the fluorescence intensity of the standard control sample and the sample to be tested at 450nm-600nm, respectively; and / or,

[0028] S32: detecting the ultraviolet absorption intensity of the standard control sample and the sample to be tested at 365nm-380nm and / or 400nm-440nm, respectively.

[0029] In some embodiments of the present application, the S32 is: setting the excitation wavelength to 300nm-400nm, and detecting the fluorescence intensity of the standard control sample and the sample to be tested at 450nm-600nm, respectively.

[0030] In a third aspect of the present application, a device for detecting fluoride ion is provided, comprising a compound of formula I and a solvent, wherein the solvent comprises at least one of water, methanol, and ethanol, such as a mixture of methanol and water, and the volume ratio of methanol to water is 50-95:5-50.

[0031] In some embodiments of the present application, the device for detecting fluoride ion is a detection kit.

[0032] In some embodiments of the present application, the device for detecting fluoride ion comprises a detection test paper, and the detection test paper is loaded with the compound of formula I.

[0033] In some embodiments of the present application, the device for detecting fluoride ion further comprises a spectrometer.

[0034] In some embodiments of the present application, the device for detecting fluoride ion further comprises an excitation light source.

[0035] In some embodiments of the present application, the spectrometer comprises a fluorescence spectrometer and / or an ultraviolet-visible light spectrometer.

[0036] The present application has the following advantages:

[0037] The compound of formula I of the present application can specifically recognize fluoride ion in aqueous solution (especially 90% methanol aqueous solution) through the deprotonation of fluoride ion to hydroxyl and amide bond, and the addition of 1 equivalent of fluoride ion can make the fluorescence emission peak intensity of the probe compound of formula I at 488 nm increase by 10 times.

[0038] The compound of formula I of the present application has a naked-eye recognizable color change when detecting fluoride ion, which is convenient for qualitative and rapid identification of fluoride ion and is suitable for on-site identification of fluoride ion.

[0039] The compound of formula I of the present application has an absorption peak at 378 nm which is increased by fluoride ion when detecting fluoride ion, and the absorption peaks at 414 nm and 434 nm are decreased.

[0040] Through ion selectivity and ion anti-interference experiments, it is shown that the probe also has the advantages of good selectivity, high sensitivity and strong anti-interference ability, and through calculation, the detection limit is as low as 0.13 μM. The comprehensive performance of the probe compound of formula I is excellent and has good application potential. Therefore, the probe compound of formula I is a fluorescence enhancement type fluoride ion probe with good selectivity, high sensitivity and good water solubility. BRIEF DESCRIPTION OF DRAWINGS

[0041] Figure 1 It is the nuclear magnetic resonance hydrogen spectrum of the compound of formula I of the present application.

[0042] Figure 2 It is the nuclear magnetic resonance carbon spectrum of the compound of formula I of the present application.

[0043] Figure 3 It is the ESI-MS mass spectrum of the compound of formula I of the present application.

[0044] Figure 4 It is the change of fluorescence intensity of the compound of formula I at 488 nm in different volume ratios of water-methanol mixed system in Example 1 of the present application.

[0045] Figure 5 It is the change rule graph of fluorescence emission spectrum of the compound of formula I in the presence of different concentrations of fluoride ion in Example 2 of the present application.

[0046] Figure 6 It is the fluorescence intensity-concentration relationship curve graph of the compound of formula I in Example 2 of the present application.

[0047] Figure 7 It is the color change of the compound of formula I under 365 nm ultraviolet lamp after adding F - 0.0 μM (left) and 20.0 μM (right).

[0048] Figure 8Fluorescence emission spectra of the probe compound of formula I in Example 3 of the present application. - Linear fitting plot of the concentration change.

[0049] Figure 9 Fluorescence emission spectra of the probe compound of formula I in Example 4 of the present application after adding different anions to the solution.

[0050] Figure 10 Fluorescence emission spectra of the probe compound of formula I in Example 5 of the present application after adding F - (20.0 μΜ) and other anions (20.0 μΜ) to the solution.

[0051] Figure 11 UV-Vis absorption spectra of the probe compound of formula I in Example 6 of the present application after gradually adding F - (0-180.0 μΜ) to the solution.

[0052] Figure 12 Color change of the probe compound of formula I in Example 6 of the present application under natural light after adding F - 0.0 μΜ (left) and 60.0 μΜ (right).

[0053] Figure 13 Fluorescence color change of the fluorescent detection test paper containing the probe compound of formula I in Example 7 of the present application before (left) and after (right) being immersed in a solution containing fluoride ions.

[0054] Figure 14 Fluorescence color change of the fluorescent detection test paper containing the probe compound of formula I in Example 7 of the present application before (left) and after (right) being immersed in a solution containing fluoride ions. DETAILED DESCRIPTION

[0055] The content of the present application is further described in detail below through specific examples. The raw materials, reagents or devices used in the examples and comparative examples can be obtained from conventional commercial channels, or can be obtained by existing technical methods, unless otherwise specified. Unless otherwise specified, the test or test method is a conventional method in the art.

[0056] Experimental instruments:

[0057] Hitachi FL-4600 fluorescence spectrophotometer.

[0058] Shimadzu UV-2700 UV-Vis spectrophotometer.

[0059] Varian NMR Systems 600 MHz spectrometer.

[0060] Sartorius BSA124S-CW vacuum electronic balance.

[0061] Bruker SolanX 70FT-MS high-resolution mass spectrometer.

[0062] In the following examples, the compound of formula I may be derived from commercially available sources or prepared by the following methods:

[0063] Reagents and chemicals: 2-hydroxynaphthaldehyde (Bailinwei Company), 3-pyridinecarboxylhydrazide (Bailinwei Company), anhydrous methanol, anhydrous ethanol, and glacial acetic acid. All reagents were of analytical grade.

[0064]

[0065] Weigh 0.1723 g (approximately 1.0 mmol) of 3-pyridinecarboxylhydrazine into a round-bottom flask and add 6.0 mL of anhydrous ethanol, stirring until completely dissolved. Next, weigh 0.1371 g (approximately 1.0 mmol) of 2-hydroxynaphthaldehyde and dissolve it in 6.0 mL of anhydrous ethanol. Then, add this solution dropwise to the anhydrous ethanol solution of 3-pyridinecarboxylhydrazine, followed by approximately 1.0 mL of glacial acetic acid as a catalyst. Keep the mixture stirred and heat to 80 °C, then reflux for approximately 2 hours. Stop heating when the yellow precipitate in the mixture no longer increases. After the reaction mixture cools to room temperature, filter using a vacuum pump. Wash the filter cake at least three times with 20.0 mL of anhydrous ethanol and dry it in a vacuum drying oven to obtain 0.2039 g of yellow powder, with a yield of 70%.

[0066] Compound I 1 The chemical shifts (δ) of H NMR (600 MHz, DMSO-d6) were: 12.60 (s, 1H), 12.36 (s, 1H), 9.47 (s, 1H), 9.15 (s, 1H), 8.82 (d, J = 3.9 Hz, 1H), 8.35–8.32 (m, 1H), 8.31 (d, J = 8.5 Hz, 1H), 7.96 (d, J = 8.9 Hz, 1H), 7.92 (d, J = 7.9 Hz, 1H), 7.66–7.63 (m, 1H), 7.63 (dd, J = 5.2, 3.1 Hz, 1H), 7.45–7.41 (m, 1H), and 7.26 (d, J = 8.9 Hz, 1H). 13 C NMR (151MHz, DMSO-d6) δ 161.62, 158.57, 153.06, 149.06, 147.88, 135.90, 133.48, 132.07, 129.48, 129.03, 128.37, 128.34, 124.24, 124.09, 121.35, 119.33, 109.00. ESI-MS (m / z): Theoretical calculation (C 17 H 13 N3O2[1+H+ The relative molecular mass of the compound of formula I is 292.1080, and the actual test result is 292.1085.

[0067] The nuclear magnetic resonance hydrogen spectrum (deuterated dimethyl sulfoxide) of the compound of formula I is shown in the following figure. Figure 1

[0068] The nuclear magnetic resonance carbon spectrum (deuterated dimethyl sulfoxide) of the compound of formula I is shown in the following figure. Figure 2

[0069] The ESI-MS mass spectrum of the compound of formula I is shown in the following figure. Figure 3

[0070] Example 1

[0071] A method for detecting fluoride ions, the specific process is as follows:

[0072] S1: Dissolve the powder of the compound of formula I in anhydrous methanol to prepare a stock solution with a concentration of 5.0 mM for standby;

[0073] S2: Take the 5.0 mM stock solution of the compound of formula I prepared in S1, keep the probe concentration unchanged at 20.0 μM, change the volume ratio of anhydrous methanol to deionized water, prepare test solutions with a volume fraction of anhydrous methanol changing from 0% to 100%, then add fluoride ions to different test solutions, and compare the fluorescence emission spectrum changes before and after adding fluoride ions.

[0074] The results are shown in the following figure. Figure 4

[0075] When one equivalent of fluoride ions is added to the probe solution (20.0 μM) of different volume ratios of methanol and water, the emission spectrum of the compound of formula I will show a relatively obvious fluorescence intensity enhancement phenomenon at 488 nm, especially when the solvent is 90.0% methanol, the fluorescence enhancement effect and water-soluble characteristics are best.

[0076] In the following examples, the stock solution of the compound of formula I in S1 is prepared using 90.0% methanol aqueous solution as the solvent, and the concentration of the compound of formula I is 20.0 μM.

[0077] Example 2

[0078] A method for detecting fluoride ions, the specific process is as follows:

[0079] S1: Dissolve the powder of the compound of formula I in anhydrous methanol to prepare a stock solution with a concentration of 5.0 mM for standby;

[0080] ​​​​S2: Take 5.0 mM of the compound of formula I prepared in S1, dilute it with 90.0% methanol solution to 20.0 μM of the compound of formula I test solution, add fluoride ion (0.0 μM-30.0 μM) in concentration gradient, take 365 nm as the fluorescence excitation wavelength, test the fluorescence emission spectrum of the probe with the increasing amount of F - at 385 nm-710 nm; or observe the color change of the test solution under the irradiation of 365 nm wavelength ultraviolet lamp.

[0081] The change rule of the fluorescence emission spectrum of the compound of formula I in the presence of different concentrations of fluoride ion is shown in Figure 5 The solution of the probe compound of formula I alone shows very weak fluorescence emission, which may be due to the photoinduced electron transfer effect, the free electron in the nitrogen atom is transferred to the naphthalene ring, resulting in fluorescence quenching, and with the increasing concentration of fluoride ion, the fluorescence emission peak of the probe compound of formula I at 488 nm is continuously enhanced, which may be due to the deprotonation of phenolic hydroxyl and amide bond, the strong electron-donating group is exposed, which enhances the conjugation effect of the molecule, and increases the charge density of the naphthalene ring.

[0082] Take the fluorescence intensity value at 488 nm as the Y axis and the concentration of added fluoride ion as the X axis to plot, and the results are shown in Figure 6 When the concentration of added fluoride ion is 0.0-20.0 μM, the fluorescence intensity of the probe compound of formula I at 488 nm shows a good positive correlation with the concentration of fluoride ion, and when the concentration of fluoride ion reaches 20.0 μM, the emission peak intensity of the probe compound of formula I tends to be flat.

[0083] The color change of the test solution under the irradiation of 365 nm wavelength ultraviolet lamp after adding F - 0.0 μM and 20.0 μM is shown in Figure 7 It can be seen that the solution of the probe compound of formula I changes from colorless to greenish after adding fluoride ion.

[0084] Example 3

[0085] A method for detecting fluoride ion, the specific process is:

[0086] The detection limit is an important performance indicator of the sensitivity of the fluorescent probe, and the calculation formula is: Limit = 3S / k. In this probe system, S corresponds to the standard deviation of the fluorescence intensity of the blank probe solution (20.0 μM) at 488 nm, and k is the slope of the fitting curve of the concentration of fluoride ion and the maximum fluorescence emission peak intensity. The standard deviation S = 2.129 is obtained by testing the fluorescence values of 6 groups of blank probes. The fitting curve results are shown in Figure 8The results show that the fitting obtained k = 49.03, and the calculated detection limit of the probe compound of formula I for detecting fluoride ions is 0.13 μM, while the maximum limit of fluoride ions in drinking water is set by the World Health Organization as 1.50 mg / L (79.0 μmol / L), and the detection limit of the probe for F - is much lower than the specified standard, and therefore has practical application value.

[0087] Example 4

[0088] A method for detecting fluoride ions, the specific process is:

[0089] Take 5.0 mM stock solution of compound of formula I, dilute it with 90.0% methanol aqueous solution to a concentration of 20.0 μM compound of formula I test solution, add one equivalent of various anions (F - , Cl - , Br - , I - , NO3 - , CH3COO - , ClO4 - , H2PO4 - , HSO4 - , SO4 2- ) respectively, and test its fluorescence emission spectrum, the results are shown in Figure 9 .

[0090] When 20.0 μM of other common anions (such as Cl - , Br - , I - , NO3 - , CH3COO - , ClO4 - , H2PO4 - , HSO4 - , SO4 2- ) are added to the solution of the probe compound of formula I, the fluorescence spectrum of the probe compound of formula I only changes slightly and cannot produce a fluorescence enhancement phenomenon similar to that produced when fluoride ions are added. Therefore, the probe compound of formula I exhibits very high fluorescence selective recognition for fluoride ions.

[0091] Example 5

[0092] A method for detecting fluoride ions, the specific process is:

[0093] Take 5.0 mM stock solution of compound of formula I, dilute it with 90.0% methanol aqueous solution to a concentration of 20.0 μM compound of formula I test solution, add one equivalent (20.0 μM) of F - and one equivalent (20.0 μM) of other anions (Cl - , Br- I - NO3 - CH3COO - ClO4 - H2PO4 - HSO4 - SO4 2- A mixed solution of ) was prepared, and its fluorescence emission spectrum was tested. The results are as follows: Figure 10 As shown.

[0094] The experimental results show that even H2PO4 - The effect on the recognition of fluoride ions by probe-type I compounds is also minimal. Among them, H₂PO₄ - Because the group contains readily ionized active hydrogen, it may easily combine with fluoride ions in the environment to form HF, leading to a decrease in the number of free fluoride ions and thus a slight decrease in fluorescence intensity. Therefore, the probe-type I compound has a certain degree of anti-interference ability and has some application potential.

[0095] Example 6

[0096] A method for detecting fluoride ions, the specific process of which is as follows:

[0097] Take a 5.0 mM stock solution of compound I and dilute it with 90.0% methanol aqueous solution to prepare a 20.0 μM test solution of compound I. Add F in increments of concentration. - (0.0 μM~180.0 μM), and its UV-Vis absorption spectrum was measured, the results are as follows. Figure 11 As shown, the color change of the solution under natural light is as follows: Figure 12 As shown.

[0098] It can be seen that the UV absorption peaks of the probe I compound at 378 nm, 414 nm, and 434 nm showed significant changes. The absorption peak at 378 nm exhibited a hyperchromic effect, while the absorption peaks at 414 nm and 434 nm showed a hypochromic effect, resulting in an isoabsorption point near 385 nm. These results indicate that the probe I compound significantly binds to fluoride ions. Furthermore, the yellow color of the probe I compound solution lightened after the addition of fluoride ions.

[0099] Example 7

[0100] A method for detecting fluoride ions, the specific process of which is as follows:

[0101] The filter paper commonly used in the laboratory is cut into various shapes of filter paper strips for easy operation, and then immersed in a 0.1-2.0 mM DMF solution of the compound of formula I (or other solvent capable of dissolving the compound of formula I) for about 5-20 min to ensure that the filter paper strip is fully wetted. Then, the fully wetted filter paper strip is placed in a vacuum drying oven for drying, thereby obtaining a test paper strip for examination.

[0102] The test paper strip prepared above is immersed in an aqueous solution containing fluoride ions (at a concentration of 1.0 μM-20.0 μM) to be detected (containing 20%-100% methanol), taken out after 10 min, and observed for the change in the fluorescence color of the test paper strip under 365 nm ultraviolet light, as shown in Figure 13 and Figure 14 Figure 13 The fluorescence color change of the test paper containing the compound of formula I immersed in a 60% methanol aqueous solution for detecting 10.0 μΜ fluoride ions; Figure 14 The fluorescence color change of the test paper containing the compound of formula I immersed in pure methanol for detecting 10.0 μΜ fluoride ions. The fluorescence color of the test paper strip soaked in the aqueous solution of fluoride ions has changed significantly from almost colorless to bright green.

[0103] The experimental results show that the compound of formula I is successfully made into a simple test paper strip, which can more conveniently and quickly detect fluoride ions, and can provide a more efficient and convenient detection means for the detection of fluoride ions.

[0104] In summary, the compound of formula I can specifically recognize fluoride ions in a methanol aqueous solution (especially a 90% methanol aqueous solution) through the deprotonation of the hydroxyl group and the amide bond by fluoride ions, and the addition of 1 equivalent of fluoride ions can enhance the fluorescence emission peak intensity of the probe compound of formula I at 488 nm by 10 times. At the same time, through ion selectivity and ion anti-interference experiments, it is shown that the probe also has the advantages of good selectivity, high sensitivity, and strong anti-interference ability, and the detection limit thereof is as low as 0.13 μM through calculation. The probe compound of formula I has excellent comprehensive performance and good application potential. The probe compound of formula I is a fluorescence-enhanced fluoride ion probe with good selectivity, high sensitivity, and good water solubility.

[0105] The above examples are the preferred embodiments of the present application, but the embodiments of the present application are not limited by the above examples, and any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application shall be equivalent replacement modes, and all shall be included in the protection scope of the present application.​

Claims

1. Use of a compound of formula I in the fluorescence detection of fluoride ion: wherein the compound of formula I is dissolved in a mixture of methanol and water, and the volume fraction of methanol in the mixture is 20% to 99.9%; the concentration of the fluoride ion is not less than 0.1 μM; the molar ratio of the fluoride ion to the compound of formula I is 1:0.1 to 10; and the detection is fluorescence emission spectrum detection at 450 nm to 600 nm when the excitation wavelength is 350 nm to 370 nm. ； 2. The method of claim 1, wherein the method comprises using the compound of formula I as an ion probe to identify fluoride ion.

3. The method of claim 1, wherein the test product enhances the fluorescence intensity of the solution of the compound of formula I at 450 nm to 600 nm, and the test product contains fluoride ion.

4. The method of claim 1, wherein the concentration of the fluoride ion in the test product is not less than 0.1 μM.

5. The method of claim 1, wherein the molar ratio of the fluoride ion to the compound of formula I in the test product is 1:0.1 to 10.

2. A method for fluorescent detection of fluoride ions, characterized by:

6. The method of claim 1, wherein the solution of the compound of formula I is dissolved in a mixture of methanol and water, and the volume fraction of methanol in the mixture is 20% to 99.9%.

7. The method of claim 1, wherein the concentration of the fluoride ion in the test product is not less than 0.13 μM.

8. The method of claim 1, wherein the molar ratio of the fluoride ion to the compound of formula I in the test product is 1:0.5 to 5.

9. The method of claim 1, wherein the solution of the compound of formula I is dissolved in a mixture of methanol and water, and the volume ratio of methanol to water in the mixture is 50 to 95:5 to 50.

10. The method of claim 1, wherein the method for detecting the fluoride ion comprises the following steps:

3. The method for fluorescent detection of fluoride ions according to claim 2, characterized in that: S1: mixing a standard fluoride ion-containing product with the compound of formula I to prepare a standard control product; 4. The method for fluorescent detection of fluoride ions according to claim 2, characterized in that: S2: mixing a test product with the compound of formula I to prepare a test sample; 5. The method for fluorescent detection of fluoride ions according to claim 2, characterized in that: S31: detecting the fluorescence intensity of the standard control product and the test sample at 450 nm to 600 nm, respectively.

6. The method for fluorescent detection of fluoride ions according to claim 2, characterized in that:

11. The method of claim 10, wherein the S31 is: setting the excitation wavelength to 300 nm to 400 nm, and detecting the fluorescence intensity of the standard control product and the test sample at 450 nm to 600 nm, respectively.

12. The method of claim 1, wherein the compound of formula I and the solvent are provided, and the solvent is a mixture of methanol and water, and the volume fraction of methanol in the mixture is 20% to 99.9%.

13. The fluoride ion detection device of claim 1, wherein the device at least meets one of the following conditions: (1) the fluoride ion detection device is a detection kit; 7. The method for fluorescent detection of fluoride ions according to claim 6, characterized in that: (2) the fluoride ion detection device further comprises a spectrometer; 8. A fluorine ion fluorescence detection device, characterized by: (3) the fluoride ion detection device further comprises an excitation light source.

9. The fluoride ion fluorescence detection apparatus of claim 8, wherein: ​ ​ ​ ​

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