CN111289502A - Application of a kind of aminobenzofuranone in fluoride ion detection - Google Patents

Abstract

The invention belongs to the technical field of ion detection, in particular to the application of an aminobenzofuranone in fluoride ion detection. The invention provides an application of aminobenzofuranone in fluoride ion detection. The aminobenzofuranone provided by the present invention contains a fluoride ion detection group, a chromophore group and a connecting group. The test results of the examples show that the aminobenzofuranone provided by the present invention can confirm the existence of fluoride ions in different organic solvents through naked-eye detection in the detection of fluoride ions; the detection limit of fluoride ions can be as low as 5× ^10-7 mol /L, high sensitivity; when one or more non-fluoride ion anions appear in the solution to be tested, the color of the mixed system adding the aminobenzofuranone will not change, but once fluoride ions appear in the solution to be tested, The color of the mixed system to which the aminobenzofuranone is added can be found to be significantly changed, and the selectivity to fluoride ions is high.

Description

Application of a kind of aminobenzofuranone in fluoride ion detection

This research was supported by the National Natural Science Foundation of China Youth Science Foundation Project (No.: 21805151), the General Project of Shandong Natural Science Foundation (No.: ZR2018MB024), the Shandong Youth Taishan Project (No.: 201909120) and the Shaanxi University of Science and Technology. Scientific research project (No.: SLGPT2019KF01-01, SLG1901) funding.

technical field

The invention belongs to the technical field of ion detection, in particular to the application of an aminobenzofuranone in fluoride ion detection.

Background technique

Fluoride ion is the smallest and most electronegative anion with high charge density and has special functions in chemical industry, organic synthesis, military field, medical treatment and biochemistry. It can not only exist in the water environment, but also appear It is widely used and exists in organic media such as pesticides and organic waste liquids.

At present, the determination of fluoride ion content mainly adopts colorimetric method and fluorine electrode method. Among them, the conventional colorimetric method is based on the characteristics of sodium alizarin sulfonate (alizarin red s) reacting with zirconium salt to form a red-purple complex in an acidic solution. The ion action generates a more stable colorless zirconium oxyfluoride complex, and within a certain concentration range, the decrease of solution chromaticity conforms to Beer's law. Considering that fluoride ions can exist in various organic solutions during chemical synthesis, the qualitative or quantitative detection of fluoride ions in organic solutions has always been the focus of fluoride ion detection. At present, many studies in colorimetry focus on the detection of fluoride ions in a single organic solution. For example, when the single solvent is tetrahydrofuran, acetonitrile or chloroform, the qualitative or quantitative detection of fluoride ions in solution cannot provide a solution in different organic solutions. A fluoride ion detection method with high selectivity, high sensitivity, and easy naked-eye detection that can show different color changes in the solvent.

SUMMARY OF THE INVENTION

In view of this, the object of the present invention is to provide a kind of application of aminobenzofuranone in fluoride ion detection, described aminobenzofuranone is applied to the detection of fluoride ion in organic solvent, can realize in different organic solvents Showing different color changes, it has the characteristics of high selectivity, high sensitivity, and easy naked-eye detection.

In order to realize the purpose of the above invention, the present invention provides the following technical solutions:

The invention provides an application of aminobenzofuranone in fluoride ion detection.

Preferably, the aminobenzofuranone has the following structure:

Preferably, the application includes the following steps:

Add the liquid to be tested into the organic solution of the aminobenzofuranone, let it stand for at least 30min after mixing, and observe the color of the mixed system. If the color is inconsistent with the organic solution of the aminobenzofuranone, it indicates that the liquid to be tested is not consistent Contains fluoride ions; if the color is consistent with the organic solution of aminobenzofuranone, it means that the liquid to be tested does not contain fluoride ions; the organic solvent in the liquid to be tested is the same as the organic solution of the aminobenzofuranone. The organic solvent in the solution is the same;

When the liquid to be tested contains fluorine ions, measure the ultraviolet-visible light absorption spectrum of the mixed system, obtain the absorbance of the mixed system according to the ultraviolet-visible light absorption spectrum, and obtain the absorbance according to the absorbance and a predetermined standard curve. The concentration of fluoride ions in the liquid to be tested is determined, and the standard curve is the linear relationship between the absorbance value and the concentration of fluoride ions.

Preferably, the organic solvent in the organic solution of aminobenzofuranone includes n-hexane, carbon tetrachloride, toluene, benzene, chloroform, dichloromethane, chloroform, tetrahydrofuran, acetone, N,N-dimethylform formamide or dimethyl sulfoxide.

Preferably, the concentration of the organic solution of aminobenzofuranone is 1.0×10 ^-6 mol/L to 1.0×10 ^-4 mol ^/ L.

Preferably, the method for obtaining the standard curve comprises the following steps:

Prepare an organic solution of aminobenzofuranone;

A fluoride ion standard solution of gradient concentration is prepared, and the organic solvent in the fluoride ion standard solution is the same as the organic solvent in the organic solution of the aminobenzofuranone;

Add the fluoride ion standard solution of the gradient concentration to the organic solution of the aminobenzofuranone respectively, let stand for at least 30min after mixing, observe the color before and after the mixed system, and measure the ultraviolet/visible light absorption spectrum of the mixed system ;

A standard curve is obtained by performing linear fitting between the absorbance value in the spectrogram and the corresponding fluoride ion concentration.

Preferably, the solute in the fluoride ion standard solution with gradient concentration is tetrabutylammonium fluoride; the concentration of the fluoride ion standard solution with gradient concentration is 5.0×10 ^-7 mol/L～2.0×10 ^-5 mol /L.

Preferably, the molar equivalent ratio of the fluoride ion standard solution to the aminobenzofuranone organic solution is 0 to 4.5, and the fluoride ion standard solution is calculated as fluoride ions, and the aminobenzofuranone organic solution Based on aminobenzofuranone.

Preferably, the standard curve is a linear relationship between the absorbance value corresponding to the maximum absorption wavelength of the absorption peak in the UV-Vis absorption spectrum and the fluoride ion concentration;

When the organic solution is tetrahydrofuran, the maximum absorption wavelengths are 640nm and 485nm;

When the organic solution is dimethyl sulfoxide, the maximum absorption wavelengths are 675nm and 475nm;

When the organic solvent is N,N-dimethylformamide, the maximum absorption wavelengths are 662nm and 471nm;

When the organic solvent is acetone, the maximum absorption wavelength is 636nm;

When the organic solvent is dichloromethane, the maximum absorption wavelength is 626nm;

When the organic solvent is chloroform, the maximum absorption wavelength is 628 nm.

Preferably, the organic solvent is tetrahydrofuran, and when the concentration of the organic solution of the aminobenzofuranone is 1.0×10 ^-5 mol/L, the standard curve includes:

When the fluoride ion concentration is between 5×10 ^-7 mol/L and 1.7×10 ^-6 mol/L, the difference between ln(A ₆₄₀ /A ₄₈₅ ×10) and the fluoride ion concentration in the UV/Vis spectrum of fluoride ion detection The linear relationship is: y=-0.56837x+3.31294;

When the fluoride ion concentration is 1.7×10 ^-6 mol/L～1.1×10 ^-5 mol/L, the difference between ln(A ₆₄₀ /A ₄₈₅ ×10) of the UV/Vis spectrum detected by fluoride ion and the fluoride ion concentration The linear relationship is: y=-0.15702x+2.60246;

When the fluoride ion concentration is 1.1×10 ^-5 mol/L～2.0×10 ^-5 mol/L, the difference between ln(A ₆₄₀ /A ₄₈₅ ×10) of the UV/Vis spectrum detected by fluoride ion and the fluoride ion concentration The linear relationship is: y=-0.02035x+1.08111;

x is ln(A ₆₄₀ /A ₄₈₅ ×10), y is the concentration of fluoride ion, the unit is mol/L;

The A ₆₄₀ is the ultraviolet-visible absorption spectrum of fluoride ion detection, and the wavelength is the absorbance value corresponding to 640 nm, and the A ₄₈₅ is the ultraviolet-visible absorption spectrum of fluorine ion detection, and the wavelength is the absorbance value corresponding to 485 nm.

The invention provides an application of aminobenzofuranone in fluoride ion detection. The aminobenzofuranone of the present invention is a dark blue dye, and has good optical stability and unique solvatochromic properties, wherein, as the core structural unit, benzodifurandione is an aminobenzofuranone The chromophore group of furanone, because the color that the aminobenzofuranone presents in different organic solvents is significantly different from the color that the aminobenzofuranone presents after reacting with fluoride ions, so different Detection of fluoride ions in organic solvents; the amino structural unit at the end of the molecule can be deprotonated in an organic solution containing fluoride ions, and the color change can be detected by naked eyes; the benzene ring is used as a connecting group to ensure that the aminobenzo The furanone is structurally stable; the aminobenzofuranone of the present invention is soluble in the most common organic solutions, has a high extinction coefficient, and has obvious discoloration after reacting with fluoride ions, so the aminobenzofuranone has a high resistance to fluoride ions. Highly sensitive, but insensitive to other anions, with high selectivity to fluoride ions.

The test results of the examples show that the aminobenzofuranone provided by the present invention can confirm the existence of fluoride ions in different organic solvents through naked eye detection in the detection of fluoride ions; the detection limit of fluoride ions can be as low as 5×10 ^-7 mol /L, high sensitivity; when one or more non-fluoride ion anions appear in the solution to be tested, the color of the mixed system added with the aminobenzofuranone will not change, but once fluoride ions appear in the solution to be tested , the color of the mixed system adding the aminobenzofuranone can be found to be significantly changed, and the selectivity to fluoride ions is high.

Description of drawings

Fig. 1 is the detection result graph of the extinction coefficient of ABDF in tetrahydrofuran to fluoride ion among the embodiment 1;

Figure 2 is a graph showing the relationship between the 10-fold ratio (A ₆₄₀ /A ₄₈₅ × 10) of the absorption peaks at 640 nm and 485 nm of the mixed system of Example 1 to the fluoride ion concentration (F ^- ), wherein the block diagram is the mixed system at 640 nm and 485 nm. The graph of the relationship between the natural logarithm (ln(A ₆₄₀ /A ₄₈₅ × 10)) of the 10-fold ratio of the absorption peak at the fluoride ion concentration (F ^- );

Fig. 3 is the ultraviolet-visible light absorption spectrogram of embodiment 1～6 gained;

Fig. 4 is the color change situation diagram of the mixed system of embodiment 1～6;

5 is a graph showing the color change of the mixed system of Comparative Examples 1 to 5 after standing and the color change of the mixed system after introducing fluoride ions into the mixed system of Comparative Examples 1 to 5, wherein (1) is the tetrahydrofuran solution of ABDF, (2) add fluoride ion to the tetrahydrofuran solution of ABDF, (3) add chloride ion to the tetrahydrofuran solution of ABDF, (4) add bromide ion to the tetrahydrofuran solution of ABDF, (5) add iodine to the tetrahydrofuran solution of ABDF Ion, (6) is adding nitrate ion to the tetrahydrofuran solution of ABDF, (7) is adding sulfate ion to the tetrahydrofuran solution of ABDF, (8) is adding thiocyanate ion to the tetrahydrofuran solution of ABDF, (9) is ABDF Add perchlorate ion to the tetrahydrofuran solution of (10) add acetate ion to the tetrahydrofuran solution of ABDF, (11) add phosphate ion to the tetrahydrofuran solution of ABDF, (12) add chloride ion to the tetrahydrofuran solution of ABDF , bromide ion, iodide ion, nitrate ion, sulfate ion, thiocyanate ion, perchlorate ion, acetate ion, sulfate ion and thiocyanate ion, (13) add chloride ion to the tetrahydrofuran solution of ABDF , bromide ion, iodide ion, nitrate ion, sulfate ion, thiocyanate ion, perchlorate ion, acetate ion, sulfate ion and thiocyanate ion and then add fluoride ion.

Detailed ways

The invention provides an application of aminobenzofuranone in fluoride ion detection.

In the present invention, the aminobenzofuranone preferably has the following structure:

(denoted as ABDF).

The source of the ABDF is not particularly limited in the present invention, and it can be prepared by a method well known to those skilled in the art. In the present invention, the ABDF preferably refers to the document "Zhang, H.C., Ghasimi, S., Tieke, B., Spange, A., and Schade, S. (2014). Aminobenzodione-based polymers with lowbandgaps and solvatochromic behavior. It was prepared by the method described in "S. Polym. Chem. 5, 3817-3823. doi: 10.1039/C3PY01702H".

In the present invention, the application preferably comprises the following steps:

The liquid to be tested is added to the organic solution of the aminobenzofuranone, and the mixture is kept at rest for at least 30min, and the color of the mixed system is observed. If the color is inconsistent with the organic solution of the aminobenzofuranone, it indicates that the liquid to be tested is in the Contains fluoride ions; if the color is consistent with the organic solution of aminobenzofuranone, it means that the liquid to be tested does not contain fluoride ions; the organic solvent in the liquid to be tested is the same as the organic solution of aminobenzofuranone The organic solvent in the same;

When the liquid to be tested contains fluorine ions, measure the ultraviolet-visible light absorption spectrum of the mixed system, obtain the absorbance of the liquid to be tested according to the ultraviolet-visible light absorption spectrum, and obtain the absorbance according to the absorbance and a predetermined standard curve. The concentration of fluoride ions in the liquid to be tested, and the standard curve is the linear relationship between the absorbance value and the concentration of fluoride ions.

In the present invention, the organic solvent preferably includes n-hexane, carbon tetrachloride, toluene, benzene, chloroform, dichloromethane, chloroform, tetrahydrofuran (THF), acetone, N,N-dimethylformamide or Dimethyl sulfoxide.

In the present invention, the concentration of the organic solution of aminobenzofuranone is preferably 1.0×10 ^-6 mol/L to 1.0×10 ^-4 mol/L.

In the present invention, the method for obtaining the standard curve preferably includes the following steps:

Prepare an organic solution of aminobenzofuranone;

A fluoride ion standard solution of gradient concentration is prepared, and the organic solvent in the fluoride ion standard solution is the same as the organic solvent in the organic solution of the aminobenzofuranone;

Add the fluoride ion standard solution of the gradient concentration to the organic solution of the aminobenzofuranone respectively, let stand for at least 30min after mixing, observe the color before and after the mixed system, and measure the ultraviolet/visible light absorption spectrum of the mixed system ;

A standard curve is obtained by performing linear fitting between the absorbance value in the spectrogram and the corresponding fluoride ion concentration.

The present invention prepares the organic solution of aminobenzofuranone. In the present invention, the organic solvent in the organic solution of aminobenzofuranone preferably includes n-hexane, carbon tetrachloride, toluene, benzene, chloroform, dichloromethane, chloroform, tetrahydrofuran (THF), acetone, N,N-dimethylformamide or dimethylsulfoxide. In the present invention, the concentration of the organic solution of aminobenzofuranone is preferably 1.0×10 ^-5 mol/L to 2.0×10 ^-5 mol/L. The present invention does not specifically limit the preparation method, and a preparation method well known to those skilled in the art can be used.

The present invention prepares a fluoride ion standard solution with a gradient concentration, and the organic solvent in the gradient concentration fluoride ion standard solution is the same as the organic solvent in the organic solution of the aminobenzofuranone. In the present invention, the solute in the fluoride ion standard solution with gradient concentration is preferably tetrabutylammonium fluoride. In the present invention, the concentration of the fluoride ion standard solution with gradient concentration is preferably 5.0×10 ^-7 mol/L to 2.0×10 ^-5 mol/L. The present invention does not specifically limit the preparation method, and a preparation method well known to those skilled in the art can be used.

After obtaining the organic solution of aminobenzofuranone and the fluoride ion standard solution of gradient concentration, the present invention respectively adds the fluoride ion standard solution of gradient concentration to the organic solution of aminobenzofuranone, and after mixing, at least let stand 30min, observe the color before and after the mixed system, and measure the ultraviolet-visible light absorption spectrum of the mixed system. In the present invention, the volume of the organic solution of aminobenzofuranone and the standard solution of fluoride ion is preferably 1:1. In the present invention, the molar equivalent ratio of the fluoride ion standard solution to the organic solution of the aminobenzofuranone is preferably 0 to 4.5, and the fluoride ion standard solution is calculated as fluoride ions, and the aminobenzofuranone The organic solution is calculated as aminobenzofuranone. In the present invention, the mixing method is preferably stirring; the present invention does not limit the speed of the stirring, and the stirring speed well-known to those skilled in the art can be used.

After the ultraviolet-visible light absorption spectrum is obtained, the present invention performs linear fitting according to the absorbance value in the ultraviolet-visible light absorption spectrum and the corresponding fluoride ion concentration to obtain a standard curve. In the present invention, the standard curve is preferably a linear relationship between the absorbance value corresponding to the maximum absorption wavelength of the absorption peak in the UV-Vis absorption spectrum and the fluoride ion concentration. In the present invention, the method for obtaining the relationship curve between fluoride ion concentration and extinction coefficient from the ultraviolet-visible light absorption spectrogram is:

According to the obtained ultraviolet-visible light absorption spectrum data of the mixed system under different fluoride ion concentrations, it can be obtained that after adding different fluoride ion concentrations, the maximum absorption wavelength of the absorption peak in the ultraviolet-visible light absorption spectrum of the mixed system corresponds to The relationship curve between the absorbance value and the fluoride ion concentration is further obtained by fitting according to the relationship curve obtained above to obtain a fitting standard curve between the absorbance value and the corresponding fluoride ion concentration in the UV-Vis absorption spectrum.

In the present invention, when the organic solution is tetrahydrofuran, the maximum absorption wavelengths are 640 nm and 485 nm;

When the organic solution is dimethyl sulfoxide, the maximum absorption wavelengths are 675nm and 475nm;

When the organic solvent is N,N-dimethylformamide, the maximum absorption wavelengths are 662nm and 471nm;

When the organic solvent is acetone, the maximum absorption wavelength is 636nm;

When the organic solvent is dichloromethane, the maximum absorption wavelength is 626nm;

When the organic solvent is chloroform, the maximum absorption wavelength is 628 nm.

Taking the organic solvent as tetrahydrofuran as an example, according to the obtained ultraviolet-visible light absorption spectrogram data of the mixed system under different fluoride ion concentrations, it can be obtained that after adding different fluoride ion concentrations, the mixed system is at 640nm and 485nm. The relationship between the 10-fold ratio of absorption peaks (A ₆₄₀ /A ₄₈₅ × 10) versus fluoride ion concentration (F ^- ), and the natural logarithm of the 10-fold ratio of the absorption peaks at 640 nm and 485 nm for the mixed system (ln(A ₆₄₀ /A ₄₈₅ × 10)) versus fluoride ion concentration (F ^- ), and then according to the obtained relationship curve, the absorbance value in the UV-Vis absorption spectrum and the corresponding fluoride ion can be obtained by fitting Fitted standard curve of concentrations.

In the present invention, taking the organic solvent as tetrahydrofuran and the organic solution concentration of ABDF as 1.0×10 ^-5 mol/L as an example, the relationship between the fluoride ion concentration and the extinction coefficient is preferably as follows: when the fluoride ion concentration is 5×10 -5 mol ^/ L From ⁷ mol/L to 1.7×10 ^-6 mol/L, the linear relationship between ln(A ₆₄₀ /A ₄₈₅ ×10) and fluoride ion concentration (F ^- ) in the UV/Vis spectrum detected by fluoride ions is: y=-0.56837x+3.31294;

When the fluoride ion concentration is 1.7×10 ^-6 mol/L～1.1×10 ^-5 mol/L, the ln(A ₆₄₀ /A ₄₈₅ ×10) and fluoride ion concentration (F ^- ), the linear relationship is: y=-0.15702x+2.60246;

When the fluoride ion concentration is 1.1×10 ^-5 mol/L～2.0×10 ^-5 mol/L, the ln(A ₆₄₀ /A ₄₈₅ ×10) and fluoride ion concentration (F ^- ), the linear relationship is: y=-0.02035x+1.08111;

x is ln(A ₆₄₀ /A ₄₈₅ ×10), y is the concentration of fluoride ion, the unit is mol/L;

Wherein, the A ₆₄₀ and A ₄₈₅ respectively represent the absorbance values A ₆₄₀ and A ₄₈₅ corresponding to the wavelength of 640 nm and the wavelength of 485 nm in the ultraviolet/visible absorption spectrum of fluoride ion detection.

In the present invention, the liquid to be tested is added to the organic solution of the aminobenzofuranone, and after mixing, it is allowed to stand for 30 minutes, the color of the mixed system is observed, and the color change is used to qualitatively determine whether there is fluoride ion in the liquid to be tested; The organic solvent in the liquid is the same as the organic solvent in the organic solution of the aminobenzofuranone. In the present invention, when the color of the mixed system is consistent with the color of the organic solution of aminobenzofuranone, it means that the ion to be tested does not contain fluoride ions; when the color of the mixed system is the same as the color of the organic solution When the color of the organic solution of aminobenzofuranone is inconsistent, it means that the ion test liquid contains fluoride ions, and the naked eye observation result can be used to qualitatively determine whether the ion test liquid contains fluoride ions. When the color of the mixed system is inconsistent with the color of the organic solution of aminobenzofuranone, it means that the ion to be tested contains fluorine ions, and the ultraviolet-visible absorption spectrum of the mixed system can be further determined by the present invention Figure, and quantitatively determine the fluoride ion content in the ion test liquid according to the fluoride ion concentration and absorbance relationship curve. In the present invention, the volume ratio of the liquid to be tested to the organic solution of aminobenzofuranone is preferably 1:1.

In the present invention, wherein the concentration of aminobenzofuranone is 1.0×10 ^-5 mol/L in toluene, chlorobenzene, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, dimethylmethylene The organic solution of aminobenzofuranone obtained in sulfone is shown as light blue, blue, light blue, dark blue, cyan and dark blue respectively, the gradient concentration of tetrabutylammonium fluoride in toluene, chlorine The standard solutions of fluoride ions in benzene, dichloromethane, tetrahydrofuran, N,N-dimethylformamide and dimethyl sulfoxide are all transparent and colorless. As shown in Figure 4, 3 mL of fluoride ion standard solution with a concentration of 2.0 × 10 ^-5 mol/L was added to 3 mL of the organic solution of aminobenzofuranone corresponding to the same solvent in turn, and the mixture was placed for at least 30 min. The colors change to colorless, yellow, light yellow, orange, orange, and red in turn.

In the present invention, the ion test solution is preferably tested by using a diluent, a stock solution or a concentrated solution; the present invention does not limit the dilution or concentration of the diluent or concentrated solution, and the dilution or concentration well-known to those skilled in the art is adopted. That's it. Considering the minimum detection limit, the present invention obtains the concentration content of fluoride ions in the ion test solution by combining the detection results with the dilution ratio or the concentration ratio.

It should be pointed out that the application of the aminobenzofuranone of the present invention is affected by the type or content ratio of the organic solvent. In the present invention, the colors of the mixed system are not exhaustive.

In order to further illustrate the present invention, the application of an aminobenzofuranone provided by the present invention in the detection of fluoride ions is described in detail below with reference to the examples, but they cannot be construed as limiting the protection scope of the present invention.

Example 1

Mix ABDF and tetrahydrofuran (THF) to prepare a THF solution of ABDF with a concentration of 1×10 ^-5 mol/L;

Mix tetrabutylammonium fluoride and THF to prepare a gradient concentration of fluoride ion standard solution, wherein the concentration of the gradient concentration of fluoride ion standard solution is 3 × 10 ^-6 mol/L, 6 × 10 ^-6 mol/L, respectively. 9×10 ^-6 mol/L, 1.2×10 ^-5 mol/L, 1.5×10 ^-5 mol/L, 1.8×10 ^-5 mol/L, 2.1×10 ^-5 mol/L, 2.4×10 ^-5 mol/L, 2.7×10 ^-5 mol/L, 3×10 ^-5 mol/L, 3.5×10 ^-5 mol/L, 3.6×10 ^-5 mol/L, 3.9×10 ^-5 mol/L, 4.5 ×10 ^-5 mol/L;

Add 3 mL of fluoride ion standard solution with gradient concentration to 3 mL of ABDF in THF solution, stir and let stand for 30 min, observe the color before and after the mixed system, and measure the extinction coefficient of ABDF in THF in the mixed system. ,see picture 1.

Add the liquid to be tested containing fluorine ions into the organic solution of the aminobenzofuranone, keep still for 30 min after mixing, observe the color before and after the mixed system, and determine the liquid to be tested containing fluorine ions according to the ultraviolet/visible light absorption spectrum. Fluoride ion content; the organic solvent in the fluoride ion-containing solution to be tested is the same as the organic solvent in the organic solution of aminobenzofuranone.

As can be seen from Figure 1, after stirring for 30min, the color of the mixed system changed from dark blue to yellow, and the absorption peak at the wavelength of 640nm in the ultraviolet/visible light absorption spectrum of the mixed system gradually disappeared, while the absorption peak at the wavelength of 485nm gradually disappeared. enhanced.

In the ABDF solution, the 10-fold ratio of the absorption peaks at 640nm and 485nm of the mixed solution containing fluoride ions at different concentrations is compared. After the fluoride ions are dropped into the THF solution of ABDF, the mixed system absorbs at 640nm and 485nm. The natural logarithm of the 10-fold ratio of peak intensities versus fluoride ion concentration is shown in the box in Figure 2. It can be seen from the block diagram in Figure 2 that the ratio and the concentration of fluoride ions have a linear relationship. The equation of the standard curve is: when the concentration of fluoride ions is between 5×10 ^-7 mol/L and 1.7×10 ^-6 mol/L, the detection rate of fluoride ions is The linear relationship between ln (A ₆₄₀ /A ₄₈₅ × 10) and fluoride ion concentration (F ^- ) in the UV/Vis spectrum is: y=-0.56837x+3.31294;

When the fluoride ion concentration is between 1.7×10 ^-6 mol/L and 1.1×10 ^-5 mol/L, the ln(A ₆₄₀ /A ₄₈₅ ×10) and fluoride ion concentration (F ^- ) The linear relationship is: y=-0.15702x+2.60246;

When the fluoride ion concentration is between 1.1×10 ^-5 mol/L and 2.0×10 ^-5 mol/L, the ln(A ₆₄₀ /A ₄₈₅ ×10) of the UV/Vis spectrum detected by fluoride ion is related to the fluoride ion concentration (F ^- ) The linear relationship is: y=-0.02035x+1.08111;

x is ln(A ₆₄₀ /A ₄₈₅ ×10), y is the concentration of fluoride ion, the unit is mol/L;

Wherein, the A ₆₄₀ and A ₄₈₅ respectively represent the absorbance values A ₆₄₀ and A ₄₈₅ corresponding to the wavelength of 640 nm and the wavelength of 485 nm in the ultraviolet/visible absorption spectrum of fluoride ion detection.

It can be seen from Figure 2 that ABDF can quantitatively detect the concentration of fluoride ion solution, and the minimum detection limit can be as low as 5×10 ^{- 7} mol/L, and the sensitivity is high.

Example 2

The organic solvent in Example 1 was replaced by dimethyl sulfoxide (DMSO) from THF, and other operations were the same as in Example 1. It can be found by observation that the color of the mixed system changes from blue to orange-yellow after adding the fluoride ion-containing solution to be tested into the organic solution of the aminobenzofuranone, and after mixing for 30 minutes.

Examples 3 to 6

The organic solvent in Example 1 was replaced by THF with toluene, chlorobenzene, dichloromethane and N,N-dimethylamide respectively, and other operations were the same as in Example 1. The ultraviolet/visible light absorption spectra obtained in Examples 1 to 6 are shown in FIG. 3 . The color changes of the mixed systems of Examples 1 to 6 are shown in Figure 4 . It can be seen from the DMSO curve in Figure 3 that the absorption peak at the wavelength of 673 nm in the ultraviolet/visible light absorption spectrum of the hybrid system gradually disappears, while the absorption peak at the wavelength of 494 nm gradually increases. At the same time, it can be seen from Figure 3 that the color changes of the mixed system are different for different organic solvents. As the polarity of the solvent increases, its UV/visible light absorption spectrum exhibits a red-shift phenomenon, which can determine the polarity of the organic solvent. It can be seen from FIG. 4 that the ABDF provided by the present invention is sensitive to fluoride ions in different organic solvents, and can realize the detection of fluoride ions in different organic solvents.

Comparative Example 1

The tetrabutylammonium fluoride in embodiment 1 is replaced with the substance containing chloride ion, and the THF solution containing chloride ion is prepared;

The THF solution of ABDF was added to the prepared THF solution containing chloride ions, and after stirring, it was allowed to stand for 30 min, and the color of the mixed system was observed. Through observation, the color of the mixed system did not change after standing, and it was still blue.

Comparative Examples 2 to 9

The chloride ions in Comparative Example 1 were replaced by bromide, iodide, nitrate, sulfate, thiocyanate, perchlorate, acetate and phosphate, respectively, and the remaining operations were the same as in Comparative Example 1. Through observation, the color of the mixed system did not change after standing, and all were still blue, as shown in Figure 5.

Comparative Example 10

The chloride ions in Comparative Example 1 were replaced by mixed ions of bromide, iodide, nitrate, sulfate, thiocyanate, perchlorate, acetate and phosphate, and the rest of the operations were the same as in Comparative Example 1.

It can be seen from Comparative Examples 1 to 10 that the color of the mixed system does not change after standing, indicating that ABDF is not sensitive to various non-fluoride anions.

Introducing fluoride ions into the mixed system obtained in Comparative Example 10, it can be found that the color of the obtained mixed system changed significantly, and the color changed from blue to yellow. The color change diagram is shown in Figure 5. It can be seen from Figure 5 that ABDF has a high single selectivity for the detection of fluoride ions without interference from other anions.

The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.

Claims (10)

1. An application of aminobenzofuranone in the detection of fluorine ions.

2. Use according to claim 1, characterized in that the aminobenzofuranone has the following structure:

3. use according to claim 1, characterized in that it comprises the following steps:

adding a liquid to be detected into the organic solution of the aminobenzofuranone, standing for at least 30min after mixing, observing the color of a mixed system, and if the color is inconsistent with the organic solution of the aminobenzofuranone, indicating that the liquid to be detected contains fluorine ions; if the color is consistent with that of the organic solution of aminobenzofuranone, the liquid to be detected does not contain fluorine ions; the organic solvent in the solution to be detected is the same as the organic solvent in the organic solution of aminobenzofuranone;

and when the liquid to be detected contains fluorine ions, measuring an ultraviolet-visible light absorption spectrogram of the mixed system, obtaining the absorbance of the mixed system according to the ultraviolet-visible light absorption spectrogram, and obtaining the concentration of the fluorine ions in the liquid to be detected according to the absorbance and a preset standard curve, wherein the standard curve is a linear relation between the absorbance value and the concentration of the fluorine ions.

4. Use according to claim 3, wherein the organic solvent comprises N-hexane, carbon tetrachloride, toluene, benzene, chloroform, dichloromethane, chloroform, tetrahydrofuran, acetone, N-dimethylformamide or dimethyl sulfoxide.

5. Use according to claim 3, characterized in that the concentration of the organic solution of aminobenzofuranone is 1.0X 10^-6mol/L～1.0×10^-4mol/L。

6. The application of claim 3, wherein the method for obtaining the standard curve comprises the following steps:

preparing an organic solution of aminobenzofuranone;

preparing a fluorine ion standard solution with gradient concentration, wherein an organic solvent in the fluorine ion standard solution is the same as an organic solvent in the organic solution of aminobenzofuranone;

respectively adding the fluorine ion standard solution with the gradient concentration into the organic solution of the aminobenzofuranone, standing for at least 30min after mixing, observing the color change of a mixed system, and measuring the ultraviolet-visible light absorption spectrogram of the mixed system;

and performing linear fitting according to the absorbance value in the spectrogram and the corresponding fluoride ion concentration to obtain a standard curve.

7. The use according to claim 6, wherein the solute in the gradient concentration fluoride ion standard solution is tetrabutylammonium fluoride; the concentration range of the fluoride ion standard solution with gradient concentration is 5.0 multiplied by 10^-7mol/L～2.0×10^-5mol/L。

8. The use according to claim 6, wherein the molar equivalent ratio of the fluorine ion standard solution to the organic solution of aminobenzofuranone is 0 to 4.5, the fluorine ion standard solution being calculated as fluorine ions and the organic solution of aminobenzofuranone being calculated as aminobenzofuranone.

9. The use according to claim 4, wherein the standard curve is a linear relationship between an absorbance value corresponding to the maximum absorption wavelength of an absorption peak in the UV-visible absorption spectrum and the fluoride ion concentration;

when the organic solution is tetrahydrofuran, the maximum absorption wavelength is 640nm and 485 nm;

when the organic solution is dimethyl sulfoxide, the maximum absorption wavelengths are 675nm and 475 nm;

when the organic solvent is N, N-dimethylformamide, the maximum absorption wavelength is 662nm and 471 nm;

when the organic solvent is acetone, the maximum absorption wavelength is 636 nm;

when the organic solvent is dichloromethane, the maximum absorption wavelength is 626 nm;

when the organic solvent is chloroform, the maximum absorption wavelength is 628 nm.

10. Use according to claim 6, wherein the organic solvent is tetrahydrofuran and the concentration of the organic solution of aminobenzofuranone is 1.0 x 10^-5At mol/L, the standard curve comprises:

when the fluorine ion concentration is 5X 10^-7mol/L～1.7×10^-6Ln of ultraviolet/visible spectrum chart of fluorine ion detection at mol/L (A)₆₄₀/A₄₈₅X 10) and the fluoride ion concentration is: -0.56837x + 3.31294;

the fluorine ion concentration is 1.7X 10^-6mol/L～1.1×10^-5Ln of ultraviolet/visible spectrum chart of fluorine ion detection at mol/L (A)₆₄₀/A₄₈₅X 10) and the fluoride ion concentration is: -0.15702x + 2.60246;

the fluorine ion concentration is 1.1 × 10^-5mol/L～2.0×10^-5Ln of ultraviolet/visible spectrum chart of fluorine ion detection at mol/L (A)₆₄₀/A₄₈₅X 10) and the fluoride ion concentration is: -0.02035x + 1.08111;

x is ln (A)₆₄₀/A₄₈₅X 10), y is the concentration of fluorinion and the unit is mol/L;

a is described₆₄₀The absorbance value corresponding to the wavelength of 640nm in an ultraviolet-visible absorption spectrogram for detecting fluorine ions is A₄₈₅The absorbance value corresponding to the wavelength of 485nm in an ultraviolet-visible absorption spectrogram for detecting fluorine ions.

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