A method for quickly identifying organic fluorides in oral care products and their raw materials

Abstract

This solution provides a method for rapidly identifying organic fluorides in oral care products and their raw materials. The raw materials referred to in this solution are raw materials of organic fluorine sources, such as orotate fluoride raw materials, etc. Through the pretreatment of the object to be tested and the setting of liquid chromatography-tandem mass spectrometry conditions, rapid qualitative and quantitative detection of organic fluorides such as hydrofluoric acid salts and non-salt forms of 3-pyridinemethanol hydrogen fluoride, bis(hydroxyethyl)aminopropyl hydroxyethyl hexadecylamine, bis(hydroxyethyl)aminopropyl hydroxyethyl oleylamine, bis(hydroxyethyl)aminopropyl hydroxyethyl stearylamine, hexadecylamine, diclofluride, and stearylamine is achieved, and the content of organic fluoride ions can be indirectly obtained, filling the blank in the detection of organic fluorides in the field of oral care products.

Description

Technical Field

[0001] The present invention relates to the field of chemical detection, and particularly to a method for rapidly identifying organic fluorides in oral care products and their raw materials. Background Art

[0002] Tooth decay, gingivitis, pulpitis, etc. are common oral health problems worldwide, which affect people's daily life and physical health to varying degrees. As is well known, fluorides have a caries-preventive effect and can promote the remineralization of dental hard tissues and inhibit demineralization. For many years, the use of fluorides in different forms and different application scenarios has reduced the prevalence of tooth hard tissue loss caused by tooth decay. Fluorides play an important role in toothpaste addition for preventing tooth decay, strengthening teeth, and inhibiting bacteria and sterilization.

[0003] With the development of the industry, the fluorides added to fluorinated toothpaste on the market are no longer limited to inorganic fluorides such as sodium fluoride, sodium monofluorophosphate, and stannous fluoride. Organic fluorides represented by olaflur and dectaflur have been allowed to be added to oral care products such as toothpaste and mouthwash, and the maximum allowable addition amount is 0.15% (calculated as fluorine).

[0004] Different from the random distribution of inorganic fluorides in the oral cavity, organic fluorides have better stability and persistence, and show weak acidity after dissolution, so they have better caries-preventive effects. At present, anti-caries toothpastes on the market add different concentration levels of organic fluorides such as olaflur and dectaflur to oral care products for children of different ages. However, at present, there are few research reports on the detection methods of organic fluorides such as 3-pyridinemethanol hydrogen fluoride, dectaflur, and cetylamine hydrofluoride in oral care products. Most detection methods still use ion chromatography, fluoride electrode method, etc. to determine fluoride ions, and this method of detecting fluoride ions cannot identify whether its source is organic fluoride or inorganic fluoride. This situation brings many problems: on the one hand, it is difficult for the quality inspection department to accurately evaluate the actual content and efficacy of organic fluorides in oral care products, thus affecting product quality control and R & D optimization; on the other hand, it leads to the fact that the addition of organic fluorides in some oral care products on the market is not standardized and difficult to be discovered, thus causing harm to consumers. Summary of the Invention

[0005] The purpose of the present invention is to provide a method for rapidly identifying organic fluorides in oral care products and their raw materials, which can identify organic fluorides with different carbon chain lengths and different degrees of saturation and their fluoride ion contents, and has the advantages of simplicity, rapidity, high efficiency, and accurate quantification.

[0006] To achieve the above purpose, the present technical solution provides a method for rapidly identifying organic fluorides in oral care products and their raw materials, including the following steps:

[0007] Obtain the object to be measured;

[0008] Dissolve the object to be measured ultrasonically with water to obtain a first solution, and perform secondary pretreatment on the first solution to obtain a solution to be measured. When the object to be measured is an oral care product raw material, mouthwash, or spray, the first solution is gradually diluted with water and methanol to obtain the solution to be measured; when the object to be measured is a toothpaste-type oral care product, the first solution is diluted with water to obtain an analysis solution, the solid-phase extraction cartridge is activated with methanol and water in sequence, the analysis solution is passed through the cartridge for purification to obtain a purified solution, after rinsing with purified water, it is eluted with methanol and collected to obtain the solution to be measured;

[0009] The solution to be measured is detected by liquid chromatography-tandem mass spectrometry in the MRM mode to obtain a chromatogram. The chromatographic column for liquid chromatography uses an Athena C4 or C8 analytical column. When using an Athena C4 analytical column, mobile phase A is methanol and mobile phase B is 0.1% formic acid in water. When using a C8 analytical column, mobile phase A is methanol and mobile phase B is a 5-10 mmol / L ammonium acetate solution containing 0.1% formic acid, and the elution method is gradient elution;

[0010] Qualitative and quantitative analysis of organic fluorides is carried out through qualitative and quantitative ion pairs.

[0011] It should be noted that regardless of whether the object to be measured is an oral care product raw material, mouthwash, spray, or toothpaste-type oral care product, the concentration of the solution to be measured needs to be controlled within the linear range of the target compound. The objects to be measured applicable to this solution, that is, the target compounds are any one or combination of seven organic fluorides: 3-pyridinemethanol hydrogen fluoride, bis(hydroxyethyl)aminopropyl hydroxyethyl hexadecylamine, bis(hydroxyethyl)aminopropyl hydroxyethyl oleylamine, bis(hydroxyethyl)aminopropyl hydroxyethyl octadecylamine, hexadecylamine, dequalinium fluoride, and octadecylamine.

[0012] It should be noted that the oral care product raw materials referred to in this solution are raw materials of organic fluorine sources, such as orafluor raw materials, etc.

[0013] Regarding the analyte of this solution, the pyridine ring structure of 3-pyridinemethanol hydrogen fluoride gives it certain antibacterial properties, which can help inhibit the growth of harmful bacteria in the oral cavity, reduce problems such as bad breath and dental caries caused by bacterial growth. At the same time, the released fluoride ions can react with the minerals on the tooth surface, enhancing the acid resistance of tooth enamel and preventing dental caries; bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl hexadecylamine, bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl oleylamine, and bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl stearylamine are all orafluor non-salt structures and their analogues; hexadecylamine, as an organic fluoride, can react with hydroxyapatite in teeth with the fluoride ions slowly released in the oral environment to form fluoroapatite that is more insoluble in acid, enhancing the acid erosion resistance of teeth and effectively preventing dental caries; difluorohexyldecane can not only provide fluoride ions to prevent dental caries, but also form a protective film on the tooth surface due to its long-chain unsaturated structure, preventing acidic substances, bacteria, etc. in the oral cavity from contacting the teeth and reducing the risk of dental caries; the fluoride ions released by the hydrofluorides of hexadecylamine and octadecylamine can enhance the anti-caries ability of teeth and maintain oral health. Therefore, these seven organic fluorides may all be added to oral care products and their organic fluoride source raw materials, and this solution can detect these organic fluoride sources by liquid chromatography-tandem mass spectrometry.

[0014] In some embodiments, the mass spectrometry conditions for liquid chromatography-tandem mass spectrometry detection of the analyte solution are: ion source ESI+, ion source voltage 5500, curtain gas 35 psi, ion source temperature 500 °C, nebulizing gas GS1 50 psi, auxiliary heating gas GS2 50 psi.

[0015] The mass spectrometry parameters of the organic fluorides in this solution are shown in Table 1 below:

[0016] Table 1 Mass spectrometry parameter table of organic fluorides

[0017] 。

[0018] Pretreatment of the analyte of this solution:

[0019] When the analyte is an oral care product raw material, mouthwash, or spray, the first solution is gradually diluted with water and methanol to obtain the analyte solution, where the first solution is diluted with water to no more than 10 ppm and with methanol to 1 - 500 ppb.

[0020] When the analyte is a toothpaste-type oral care product, it is dissolved in water to obtain an analytical solution. Take 1 - 3 ml of the analytical solution and pass it through a column for purification. Activate the HLB solid-phase extraction column for purification with methanol and water that are 1 - 3 times the analytical sample loading solution in sequence, wash it with purified water that is 1 - 3 times the analytical sample loading solution, elute and collect with methanol that is 1 - 5 times the volume, and make it up to volume with methanol to obtain the analyte solution.

[0021] Liquid chromatography conditions for this solution:

[0022] The chromatographic column for the liquid chromatography conditions of this solution uses Athena C4 or C8, with a specification size of 2.1×100 mm, 5 µm; the flow rate is set at 0.3 - 0.5 ml / min, the column temperature is 35°C, and the elution conditions for gradient elution are as follows: 80% methanol from 0 to 0.5 min; 80% - 95% methanol from 0.5 to 4 min; 80% methanol from 4.1 to 5.5 min.

[0023] When qualitative identification of organic fluorides is required, take 7 organic fluoride standards and dissolve them with methanol solution to obtain the standard working solution of organic fluoride source. Take the standard working solution of organic fluoride source and perform detection under the same liquid chromatography and mass spectrometry conditions. Qualitatively analyze by comparing the retention time of the chromatogram of the test solution with that of the standard working solution of organic fluoride source, and the abundance ratio of the characteristic ions in the test solution to the characteristic ions in the corresponding concentration of the standard working solution of organic fluoride source. If the relative deviation of the retention time is not more than 5%, and the abundance of the characteristic ions in the test solution and the abundance of the characteristic ions in the standard working solution of organic fluoride source are within the allowable deviation, then the corresponding organic fluoride is considered to be identified, where the relative abundance is consistent with that of the standard working solution of organic fluoride source, and the relative abundance deviation does not exceed the provisions in Table 2:

[0024] Table 2 Allowable deviation table of relative ion abundance for qualitative confirmation (unit: percentage)

[0025]

[0026] When quantitative detection of 7 organic fluorides is required, take 7 organic fluoride standards and dissolve them with methanol to obtain standard working solutions with different concentrations. The standard working solutions are respectively detected under the same chromatographic and mass spectrometry conditions. Based on the detection results, plot the external standard curve of standard substance concentration - response intensity. The external standard curve of standard substance concentration - response intensity records the relationship between the concentration of organic fluoride and the response intensity. According to the response intensity of the test solution in the liquid chromatograph, obtain the content of the corresponding organic fluoride based on the external standard curve of standard substance concentration - response intensity.

[0027] Specifically, inject a series of standard working solutions of organic fluoride source with increasing concentrations (not less than 5 concentration points) in sequence. Plot the external standard curve of standard substance concentration - response intensity according to the standard substance concentration - response intensity. When the content of organic fluoride in the test solution exceeds the linear range, further dilute the test solution and then inject it for analysis to ensure that its concentration is within the calibration curve range.

[0028] In some embodiments, the concentration of the standard working solution of organic fluoride source is 1 - 500 µg / L.

[0029] In addition, the content of organic fluoride in the solution to be measured (calculated based on the structure without hydrofluoric acid salts) is calculated according to the following formula:

[0030] ;

[0031] where X i : the content of organic fluoride, mg / g; C i is the measured concentration of organic fluoride, μg / L; F is the dilution factor; v is the final volume of constant volume, mL; m is the weighed sample mass of the object to be measured, g.

[0032] Compared with the prior art, the present technical solution has the following characteristics and beneficial effects:

[0033] This solution uses liquid chromatography - tandem mass spectrometry detection combined with targeted pretreatment of the object to be measured, and can qualitatively analyze 7 organic fluorides such as 3 - pyridylmethanol hydrogen fluoride, bis(2 - hydroxyethyl)aminopropyl hydroxyethyl hexadecylamine, bis(2 - hydroxyethyl)aminopropyl hydroxyethyl oleylamine, bis(2 - hydroxyethyl)aminopropyl hydroxyethyl stearylamine, difluorohexylexamidine, hexadecylamine and stearylamine in oral care products and their raw materials, accurately identify the organic fluorine source, solve the problem that the quality inspection department is difficult to accurately evaluate the actual content of organic fluorine in oral care products, and is conducive to product quality control and R & D optimization. Description of the Drawings

[0034] Figure 1 is the total ion chromatogram obtained using a pentafluorophenyl column with methanol and 0.1% formic acid in water as the mobile phase.

[0035] Figure 2 is the ion chromatogram of some organic fluorides obtained using a pentafluorophenyl column with methanol and 0.1% ammonium formate solution as the mobile phase.

[0036] Figure 3 is the total ion chromatogram obtained using a C4 column with methanol and 0.1% ammonium formate as the mobile phase.

[0037] Figure 4 is the ion chromatogram of each organic fluoride obtained using a C4 column with methanol and 0.1% ammonium formate as the mobile phase.

[0038] Figure 5 is the total ion chromatogram of organic fluorides obtained using a C4 column with methanol and 0.1% formic acid in water as the mobile phase.

[0039] Figure 6 is the total ion chromatogram of a toothpaste sample obtained using a C4 column with methanol and 0.1% formic acid in water as the mobile phase. Detailed Embodiments

[0040] The following will elaborate on multiple specific embodiments of the present invention. It should be noted that these embodiments are only examples, aiming to more clearly show the technical concept and implementation method of the present invention, and should not be construed as a limitation on the protection scope of the present invention. In actual applications, adjustments and changes can be made according to specific requirements.

[0041] In the process of implementing the present invention, the specific operating conditions, parameters, etc. of each step can be reasonably changed within a certain range. As long as the purpose and technical effects of the present invention can be achieved, these modified embodiments all fall within the protection scope of the present invention. The specific numerical values given in the following embodiments are only for illustrative purposes and are not the only limitation on the parameter range.

[0042] Example 1: Elution effect of pentafluorophenyl column

[0043] Example 1.1: Gradient elution of pentafluorophenyl column

[0044] Take 7 organic fluoride standards and directly dissolve them in methanol solution to obtain the standard working solution of organic fluoride source. Analyze the standard working solution of organic fluoride source by machine. The liquid chromatography conditions are set as follows: Mobile phase A is methanol, mobile phase B is 0.1% formic acid in water for gradient elution. The chromatographic column is a pentafluorophenyl column, and gradient elution is used. The elution conditions are: 0 - 0.5 min, 85% methanol; 0.5 - 2 min, 100% methanol, hold for 2 min; 4.1 - 6 min, 85% methanol. The ion chromatogram of the solution to be measured is as Figure 1 shown, Figure 1 where NO.1 represents 3 - pyridinemethanol hydrogen fluoride, NO.5 represents hexadecylamine, NO.6 represents difluprednate, and NO.7 represents octadecylamine. It can be seen that bis(2 - hydroxyethyl)aminopropyl 2 - hydroxyethyl hexadecylamine, bis(2 - hydroxyethyl)aminopropyl 2 - hydroxyethyl oleylamine, and bis(2 - hydroxyethyl)aminopropyl 2 - hydroxyethyl octadecylamine cannot be eluted under these liquid chromatography conditions.

[0045] Example 1.2: Gradient elution of pentafluorophenyl column

[0046] Take the organic fluoride reference standard and directly dissolve it with methanol solution to obtain the standard working solution of the organic fluorine source. Analyze the standard working solution of the organic fluorine source by machine. Set the liquid chromatography conditions as follows: mobile phase A is methanol, mobile phase B is 0.1% ammonium acetate formate solution (5 - 10 mmol / L), gradient elution, chromatographic column Athena C18, gradient elution is adopted, and the elution conditions are: 0 - 0.5 min, 85% methanol; 0.5 - 2 min, 100% methanol, hold for 2 min; 4.1 - 6 min, 85% methanol. Obtain the ion chromatogram of the solution to be measured. This liquid chromatography condition can elute 7 kinds of organic fluorides, but the peak shapes of bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl hexadecylamine, bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl oleylamine, and bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl octadecylamine show obvious tailing, which is not conducive to quantitative analysis. Figure 2 It is the ion chromatogram of NO.2 - NO.4. NO.2 represents bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl hexadecylamine, NO.3 represents bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl oleylamine, and NO.4 represents bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl octadecylamine.

[0047] Example 1.3 Gradient elution with pentafluorophenyl column:

[0048] Take the organic fluoride reference standard and directly dissolve it with methanol solution to obtain the standard working solution of the organic fluorine source. Analyze the standard working solution of the organic fluorine source by machine. Set the liquid chromatography conditions as follows: mobile phase A is acetonitrile, mobile phase B is 0.1% ammonium acetate formate solution (5 - 10 mmol / L), gradient elution, chromatographic column Athena C18, gradient elution is adopted, and the elution conditions are: 0 - 0.5 min, 85% methanol; 0.5 - 2 min, 100% methanol, hold for 2 min; 4.1 - 6 min, 85% methanol. Obtain the ion chromatogram of the solution to be measured. This liquid chromatography condition can only elute 3-pyridinemethanol hydrogen fluoride, and the other 6 kinds of organic fluorides cannot be eluted. It can be seen that acetonitrile is not suitable for mass spectrometry ionization.

[0049] Example Two Elution effect of C4 chromatographic column:

[0050] Example 2.1 Gradient elution with C4 chromatographic column:

[0051] Take 7 organic fluoride standards and directly dissolve them in methanol solution to obtain the standard working solution of the organic fluoride source. Analyze the standard working solution of the organic fluoride source by machine. Among them, the liquid chromatography conditions are set as follows: Mobile phase A is methanol, mobile phase B is 0.1% formic acid ammonium acetate (5 - 10 mmol / L) for gradient elution. The chromatographic column is Athena C4, with a specification size of 2.1×100 mm, 5 µm. Gradient elution is adopted, and the elution conditions are as follows: 80% methanol from 0 to 0.5 min; 80% - 95% methanol from 0.5 to 4 min; 80% methanol from 4.1 to 5.5 min. The total ion chromatogram of the test solution is as Figure 3 shown, and the ion chromatograms of each organic fluoride extracted are as Figure 4 shown, where NO.1 represents 3-pyridinemethanol hydrogen fluoride, NO.2 represents bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl hexadecylamine, NO.3 represents bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl oleylamine, NO.4 represents bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl stearylamine, NO.5 represents hexadecylamine, NO.6 represents difluprednate, and NO.7 represents stearylamine. It can be seen that 7 organic fluorides can be eluted under this condition, but the ion peaks of bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl hexadecylamine and bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl oleylamine are split peaks.

[0052] Example 2.2 Gradient elution with C4 chromatographic column:

[0053] Take 7 organic fluoride standards and directly dissolve them in methanol solution to obtain the standard working solution of the organic fluoride source. Analyze the standard working solution of the organic fluoride source by machine. Among them, the liquid chromatography conditions are set as follows: Mobile phase A is methanol, mobile phase B is 0.1% formic acid water for gradient elution. The chromatographic column is Athena C4, with a specification size of 2.1×100 mm, 5 µm. Gradient elution is adopted, and the elution conditions are as follows: 80% methanol from 0 to 0.5 min; 80% - 95% methanol from 0.5 to 4 min; 80% methanol from 4.1 to 5.5 min. The total ion chromatogram of the test solution is as Figure 5 shown, where NO.1 represents 3-pyridinemethanol hydrogen fluoride, NO.2 represents bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl hexadecylamine, NO.3 represents bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl oleylamine, NO.4 represents bis(2-hydroxyethyl)aminopropyl 2-hydroxyethyl stearylamine, NO.5 represents hexadecylamine, NO.6 represents difluprednate, and NO.7 represents stearylamine. It can be seen that 7 organic fluorides can be eluted under this condition, and the peak shapes of the target peaks of each organic fluoride are good, which is more conducive to the quantitative analysis of each organic fluoride.

[0054] Example 2.3 Gradient elution with C4 chromatographic column:

[0055] Dissolve the toothpaste to be tested with 30 mL of pure water, ultrasonic for 10 - 20 min, then make up the volume to 50 mL. Take 200 μL - 1 mL and dilute it to 10 mL with ultrapure water. Activate the HLB solid-phase extraction column with 1 - 5 mL of methanol and water in turn. After purification is completed, take 1 - 3 mL of the diluted solution and pass it through the column for purification. Wash it with 3 - 5 mL of purified water, and finally elute and collect with 3 - 5 mL of methanol. Make up the volume to 10 mL with methanol, mix well, filter through a membrane and then analyze it on the machine. Analyze the solution to be tested on the machine. The set liquid chromatography conditions are as follows: Mobile phase A is methanol, mobile phase B is 0.1% formic acid water for gradient elution. The chromatographic column is Athena C4, with a specification size of 2.1×100 mm, 5 μm. Gradient elution is used, and the elution conditions are: 0 - 0.5 min, methanol 80%; 0.5 - 4 min, methanol 80% - 95%; 4.1 - 5.5 min, methanol 80%. The total ion chromatogram of the solution to be tested is as Figure 6 shown.

[0056] Example 3 Influence of matrix effect

[0057] Taking toothpaste samples as an example, equal amounts of organic fluorides are respectively made up with methanol solvent and methanol solvent added with a certain amount of matrix (matched with the sample amount and the fixed volume for column loading and purification). More than two parallel determinations are carried out, and the calibration curves of the standard samples made up with methanol solution are corrected respectively. The results are the average values of the parallel samples, and the matrix effect determination results are shown in Table 3 below:

[0058] Table 3 Matrix effect determination results table (toothpaste samples)

[0059] .

[0060] It can be seen that except for hexadecylamine, dicloflur, and octadecylamine, the other 4 organic fluorides all have significant matrix inhibition effects.

[0061] Example 4 Influence of solid-phase extraction column on recovery rate

[0062] To reduce the matrix effect, the research team of this application selected C4 column, C18 column, and HLB column for comparison of purification effect and recovery rate. The toothpaste sample without added fluoride was used as a blank, and 7 organic fluorides with a certain concentration were added as test substances to investigate the recovery rate. The results are shown in Table 4 and Table 5.

[0063] Table 4 Recovery rate during methanol elution (%)

[0064] .

[0065] Table 5 Recovery rate during 0.1% formic acid methanol elution (%)

[0066] .

[0067] As can be seen from Table 4 and Table 5, when eluting with methanol, the recoveries of 3-pyridinemethanol hydrogen fluoride, hexadecylamine, dicloflurane, and octadecylamine by the C18 solid-phase extraction cartridge are all relatively low. However, when eluting with formic acid-methanol, the recovery of dicloflurane is significantly improved. Compared with methanol as the eluent, formic acid-methanol has no significant effect on the recoveries of the C4 and HLB cartridges. However, the recovery of 3-pyridinemethanol hydrogen fluoride by the C4 cartridge is relatively low, and the recoveries of each target compound by the HLB cartridge can reach over 60% when eluting with methanol.

[0068] Those skilled in the art should understand that the technical features of the above embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered to be within the scope described in this specification.

[0069] The above embodiments only represent several implementation manners of the present application. The description is relatively specific and detailed, but it should not be understood as a limitation on the scope of the present application. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several modifications and improvements can still be made, and these all belong to the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the appended claims.

Claims

1. A method for rapidly identifying organic fluorides in oral care products and their raw materials, characterized in that: The following steps are involved: Obtaining an object to be tested, wherein the object to be tested is any one or a combination of seven organic fluorides of 3-pyridinemethanol hydrogen fluoride, bishydroxyethylaminopropylhydroxyethylhexadecylamine, bishydroxyethylaminopropylhydroxyethyloleylamine, bishydroxyethylaminopropylhydroxyethyloctadecylamine, hexadecylamine, diketafur and octadecylamine; The object to be tested is ultrasonically dissolved with water to obtain a first solution, and the first solution is pre-treated twice to obtain a solution to be tested, wherein when the object to be tested is an oral care product raw material, mouthwash and spray, the first solution is diluted with water and methanol step by step to obtain a solution to be tested; when the object to be tested is a toothpaste-type oral care product, the first solution is diluted with water to obtain an analysis solution, and a solid phase extraction column is activated with methanol and water in sequence, and the analysis solution is purified through the column to obtain a purified solution, which is washed with purified water and then eluted with methanol to collect the solution to be tested; The solution to be tested is detected by liquid chromatography-tandem mass spectrometry in MRM mode to obtain a chromatogram, wherein the chromatographic column of the liquid chromatography is an Athena C4 or C8 analytical column, wherein when the Athena C4 analytical column is used, the mobile phase A is methanol, and the mobile phase B is 0.1% formic acid water, and when the C8 analytical column is used, the mobile phase A is methanol, and the mobile phase B is a 5-10 Mmol / L ammonium acetate solution containing 0.1% formic acid, and the elution method is gradient elution; The quantitative or qualitative analysis of organic fluoride can be performed through qualitative and quantitative ion pairs.

2. The method for rapidly identifying organic fluorides in oral care products and raw materials thereof according to claim 1, characterized in that: The flow rate was set at 0.3~0.5 ml / min, the column temperature was 35℃~50℃, and the elution conditions of the gradient elution were: 0~0.5 min, methanol 80%; 0.5~4 min, methanol 80%~95%; 4.1~5.5 min, methanol 80%.

3. The method for rapidly identifying organic fluorides in oral care products and raw materials thereof according to claim 1, characterized in that: When it is necessary to qualitatively identify organic fluorides, take an organic fluoride standard and dissolve it in methanol solution to obtain an organic fluorine source standard solution. The organic fluorine source standard solution is tested under the same liquid chromatography and mass spectrometry conditions. The retention time of the chromatogram of the test solution is compared with the retention time of the chromatogram of the organic fluorine source standard solution, and the characteristic ions are compared with the characteristic ions in the organic fluorine source standard solution of corresponding concentration for qualitative identification. If the relative deviation of the retention time is not greater than 5%, and the abundance of the characteristic ions in the test solution and the abundance of the characteristic ions in the organic fluorine source standard solution are within the allowable deviation, it is considered that the corresponding organic fluoride is identified.

4. The method for rapidly identifying organic fluorides in oral care products and raw materials thereof according to claim 1, characterized in that: When it is necessary to quantitatively detect organic fluorides, an organic fluoride standard is dissolved in a methanol solution to obtain an organic fluorine source standard solution of different concentrations, the organic fluorine source standard solution is detected under the same chromatographic and mass spectrometric conditions, and a standard substance concentration-response intensity external standard method curve is drawn based on the detection results, wherein the standard substance concentration-response intensity external standard method curve records the relationship between the concentration of the organic fluoride and the response intensity, and the corresponding organic fluoride content is obtained based on the standard substance concentration-response intensity external standard method curve according to the response intensity of the solution to be tested in the liquid chromatograph, and the organic fluoride ion content is converted therein.

5. The method for rapidly identifying organic fluorides in oral care products and raw materials thereof according to claim 4, characterized in that: The concentration of the standard working solution of the organic fluorine source is 1~500 µg / L.

6. The method for rapidly identifying organic fluorides in oral care products and raw materials thereof according to claim 1, characterized in that: When the objects to be tested are oral care product raw materials, mouthwashes and sprays, the first solution is diluted stepwise with water and methanol and then passed through a membrane to obtain a test solution, wherein the first solution is diluted with water until the target content in the sample is less than 10 ppm, and is diluted with methanol until the target content is within the linear range of 1-500 ppb.

7. The method for rapidly identifying organic fluorides in oral care products and raw materials thereof according to claim 1, characterized in that: When the object to be tested is a toothpaste-type oral care product, the first solution is diluted and dissolved with purified water to obtain an analysis solution, 1-3 mL of the analysis solution is taken to pass through a column for purification, methanol and water with a volume ratio of 1 to 3 times the analysis solution are used in sequence for solid phase extraction of a small column, the analysis solution is taken to pass through a small column for purification, the solution is rinsed with purified water with a volume ratio of 1 to 3 times the analysis solution, the solution is eluted and collected with methanol with a volume ratio of 1 to 5 times the analysis solution, and the solution to be tested is obtained after constant volume with methanol.

Images