A solid-phase microextraction probe for highly selective enrichment of perfluoro, polyfluoroalkyl sulfonic acid and its substitutes, and a preparation method and application thereof

Abstract

This invention discloses a solid-phase microextraction probe for highly selective enrichment of perfluorinated and polyfluoroalkyl sulfonic acids (PFAS) and their substitutes, along with its preparation method and applications. The invention aims to improve solid-phase microextraction technology, enabling efficient and selective enrichment of PFAS and their substitutes, and achieving direct mass spectrometry analysis. To this end, this invention prepares a surface-modified coating through in-situ polymerization of a solid matrix, exhibiting highly selective adsorption capacity for enriching PFAS and their substitutes. This coating is simple to prepare, inexpensive, and exhibits good stability, avoiding cross-contamination issues. This method utilizes fluorine-fluorine interactions, hydrophobic interactions, and electrostatic interactions to efficiently enrich PFAS and their substitutes in complex biological samples, and is expected to play an important role in environmental analysis and biological sample detection.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of analytical testing technology, and particularly relates to a solid-phase microextraction probe for highly selective enrichment of perfluoro, polyfluoroalkyl sulfonic acid and its substitutes, and a preparation method and application thereof. BACKGROUND

[0002] Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are a class of organic compounds containing perfluoroalkyl chains, which are widely used in industry and daily life, such as waterproof agents, antifouling agents, fire-fighting foams, etc. Perfluorooctyl sulfonic acid (PFOS) is a substance controlled by the Stockholm Convention on Persistent Organic Pollutants, and perfluoro and polyfluoro compounds have been listed in the List of Key Controlled New Pollutants (2023 edition). Measures taken for these fluorine-containing compounds are to prohibit production and processing use. Regulatory actions for these compounds include prohibition of production and use. These strict regulations have prompted people to explore substitutes, and newly emerging short-chain perfluoroalkanes may have greater toxicity and dispersibility, becoming an environmental problem. Due to the characteristics of perfluoro and polyfluoro compounds, such as high thermal stability, high chemical inertness and biological inertness, they are difficult to degrade in the environment and organisms, leading to environmental pollution and biological accumulation worldwide. Perfluoro and polyfluoro compounds have been proven to have adverse effects on human and animal health, such as endocrine disruption, liver damage, immune system suppression, etc. Therefore, it is of great significance to rapidly, accurately and sensitively detect perfluoro, polyfluoroalkyl sulfonic acid and its substitutes in environmental and biological samples.

[0003] Currently, the detection methods of perfluorinated and polyfluorinated compounds mainly include liquid chromatography-tandem mass spectrometry (LC-MS / MS), gas chromatography-tandem mass spectrometry (GC-MS / MS) and direct mass spectrometry (DI-MS). Among them, direct mass spectrometry has the advantages of simple operation, fast analysis speed, high sensitivity, etc., but also has the disadvantages of high sample complexity, many interfering components, low detection efficiency, etc. In recent years, ambient ionization mass spectrometry (AI-MS) has become an important technology for mass spectrometry analysis, and has been widely used in food and drug detection, environmental monitoring and molecular imaging fields. Electrospray ionization mass spectrometry is a branch of ambient mass spectrometry (AMS), which uses electrospray ionization mechanism, analyzes by direct ionization strategy, and uses tungsten needle, glass rod, paper, wood tip and other solid substrates. Various atmospheric pressure ionization technologies have emerged, including desorption electrospray ionization (DESI), direct analysis in real time (DART) and paper spray ionization (PSI). The ionization process is realized in an open atmospheric environment, with few or no sample processing steps, and has the advantages of real-time, convenience, speed and high throughput. In order to improve the detection effect of direct mass spectrometry, the sample needs to be pretreated to remove unnecessary components and enrich the target analyte. Common pretreatment methods include liquid-liquid extraction (LLE), solid phase extraction (SPE) and solid phase microextraction (SPME). Among them, solid phase microextraction has the advantages of simple operation, less solvent consumption and less sample loss, and is an ideal pretreatment method. The key to solid phase microextraction is to select a suitable solid phase microextraction probe to achieve efficient enrichment of the target analyte. At present, some solid phase microextraction probes have been used for the enrichment of perfluorinated and polyfluorinated compounds, such as polydimethylsiloxane (PDMS), polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP). However, these solid phase microextraction probes have low selectivity for perfluorinated and polyfluorinated compounds, and are easily interfered by other components, resulting in low enrichment efficiency. Persistent organic pollutants, especially PFAS and their substitutes, have caused environmental problems that cannot be ignored. Based on the above technical defects, it is of great significance to develop a new type of solid phase microextraction (SPME) probe with high selectivity for perfluorinated, polyfluorinated alkyl sulfonic acid and its substitutes, and to develop a method that can realize ambient open electrospray direct mass spectrometry. SUMMARY

[0004] In order to overcome the shortcomings of the prior art and achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0005] The preparation method of the solid phase microextraction probe for high-selectivity enrichment of perfluorinated, polyfluorinated alkyl sulfonic acid and its substitutes comprises the following steps:

[0006] (1) soaking the solid substrate containing active hydroxyl or amino into organic solvent containing coupling agent, heating under inert atmosphere, making coupling agent react with the surface of solid substrate, washing, vacuum drying, forming solid substrate containing active double bond radical;

[0007] (2) transferring the solid substrate containing active double bond radical obtained in step (1) into solvent containing monomer A and monomer B, heating under inert atmosphere, making monomer A and monomer B in-situ polymerize with the radical, forming in-situ modified coating, washing, drying to obtain a solid phase microextraction probe for high selective enrichment of perfluoro, polyfluoro alkyl sulfonic acid and its substitutes.

[0008] Further, the solid substrate containing active hydroxyl or amino in step (1) is hard metal material or wooden material with sharp tip after surface chemical etching roughening treatment.

[0009] Further, the diameter of the sharp tip is 0.5-10 μm.

[0010] Further, the solid substrate containing active hydroxyl or amino in step (1) is tungsten needle after surface chemical etching roughening treatment.

[0011] Further, in step (1), the coupling agent is 3-(trimethoxysilyl) methyl propyl methacrylate; the organic solvent is one or more of anhydrous toluene, N,N-dimethylformamide, acetonitrile, methanol or dichloromethane.

[0012] Further, in step (1), the inert atmosphere is one or more of argon, nitrogen; the heating temperature is 80-120 ℃; the reaction time is 10-24 h; the washing reagent is one or more of anhydrous ethanol, methanol and ultrapure water.

[0013] Further, in step (2), the monomer A is 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadeca (fluoro) propyl acrylate; the monomer B is dimethylaminoethyl acrylate quaternary ammonium salt; the solvent is one or more of chloroform, acetonitrile; the molar ratio of monomer A to monomer B is 1:1-1:2.

[0014] Further, in step (2), the inert atmosphere is one or more of argon, nitrogen; the heating temperature is 50-80 ℃; the reaction time is 12-24 h; the washing reagent is anhydrous ethanol or methanol.

[0015] The application provides a solid phase microextraction probe for high selective enrichment of perfluoro, polyfluoro alkyl sulfonic acid and its substitutes prepared by any one of the above preparation methods.

[0016] The application provides application of the high-selectivity solid-phase microextraction probe for enriching perfluoro, polyfluoro alkyl sulfonic acid and substitutes thereof in qualitative and / or quantitative detection of perfluoro, polyfluoro alkyl sulfonic acid and substitutes thereof.

[0017] The application further provides a detection method for perfluoro, polyfluoro alkyl sulfonic acid and substitutes thereof by directly performing mass spectrum analysis on perfluoro, polyfluoro alkyl sulfonic acid and substitutes thereof in a complex biological sample by using the high-selectivity solid-phase microextraction probe for enriching perfluoro, polyfluoro alkyl sulfonic acid and substitutes thereof obtained by the preparation method, and the detection method comprises the following steps:

[0018] (1) inserting the solid-phase microextraction probe obtained by the preparation method into a complex biological sample (such as serum, urine, tissue, etc.), so that the solid-phase microextraction probe is in full contact with the sample, and stirring or oscillation is performed;

[0019] (2) taking out the solid-phase microextraction probe obtained in step (1) from the sample and cleaning;

[0020] (3) connecting the solid-phase microextraction probe obtained in step (2) with a mass spectrometer, and performing mass spectrum analysis on perfluoro, polyfluoro alkyl sulfonic acid and substitutes thereof enriched on the solid-phase microextraction probe by an electrospray ion source (ESI) or other ion source;

[0021] (4) determining the types and contents of perfluoro, polyfluoro alkyl sulfonic acid and substitutes thereof according to the intensity and mass-to-charge ratio of the mass spectrum signal.

[0022] Further, the reagent used for cleaning in step (2) is anhydrous ethanol.

[0023] Further, the mass spectrum analysis in step (3) is atmospheric open mass spectrum analysis, and the specific operation of the atmospheric mass spectrum analysis comprises the following steps:

[0024] After extraction is completed, the cleaned solid-phase microextraction probe is fixed by using a three-dimensional moving platform, the tip of the solid-phase microextraction probe is aligned with a mass spectrum inlet, a nanoliter electrospray needle is installed on the three-dimensional moving table together with the probe, and after a high-voltage electric field is applied, nanoliter electrospray ionization is induced by desorption solvent to enter the mass spectrometer for analysis.

[0025] Further, the distance between the tip of the solid-phase microextraction probe and the mass spectrum inlet is 5-15 mm, the desorption solvent is a methanol / acetonitrile solution containing an internal standard, the volume of the desorption solvent is 5-10 μL, and the voltage of the high-voltage electric field is 2.5-4 kv.

[0026] The application has the following beneficial effects:

[0027] (1) The present application modifies the surface of the solid substrate, and in-situ polymerization is used to prepare an in-situ modified coating with high selective adsorption capacity for perfluoro, polyfluoro alkyl sulfonic acid and its substitutes, which has the characteristics of simple preparation, low price, good stability and avoidance of cross contamination.

[0028] (2) The present application uses the fluorine-fluorine interaction between the alkyl chain in the in-situ modified coating and perfluoro, polyfluoro alkyl sulfonic acid and its substitutes, as well as the hydrophobic interaction and electrostatic interaction between the alkyl chain and, to realize efficient extraction and enrichment of perfluoro, polyfluoro alkyl sulfonic acid and its substitutes in complex biological samples, prevent other interfering ions from being adsorbed, and improve the simultaneous enrichment capacity of perfluoro, polyfluoro alkyl sulfonic acid and its substitutes.

[0029] (3) The present application first contacts a sample solution containing a target analyte with a solid-phase microextraction probe with a surface modified coating, so that the target analyte is enriched on the solid-phase microextraction probe from the sample solution; then the solid-phase microextraction probe is placed in the ion source of a mass spectrometer, and ionization methods such as electrospray ionization or atmospheric pressure chemical ionization are used to desorb and ionize the target analyte enriched on the solid-phase microextraction probe and perform mass spectrometry analysis, obtaining the mass spectrum signal of the target analyte. The advantage of the present application is that by directly analyzing the surface modified coating solid-phase microextraction probe in-situ, the chromatographic separation step in the traditional method is avoided, the operation process is simple, the analysis time is short, and the analysis sensitivity and accuracy are improved.

[0030] (4) Compared with existing invention patents, the modification method of the present application has simple preparation process, shortened reaction time, does not need to use template molecules, and the solid-phase microextraction probe modified under the metal tungsten needle substrate has good adsorption effect. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 The preparation principle diagram of the solid-phase microextraction probe for high selective enrichment of perfluoro, polyfluoro alkyl sulfonic acid and its substitutes according to the present application.

[0032] Figure 2 The electron microscope characterization diagram of the surface of the solid-phase microextraction probe according to the present application.

[0033] Figure 3 The adsorption effect diagram of the solid-phase microextraction probe according to the present application using different solvents.

[0034] Figure 4 The mass spectrum obtained by the solid-phase microextraction probe according to the present application for extracting perfluoro, polyfluoro alkyl sulfonic acid and its substitutes in pure water.

[0035] Figure 5 The effect comparison diagram of the surface modified probe according to the present application and other probes. DETAILED DESCRIPTION

[0036] The following examples are further illustrations of the application and are not intended to limit the same.

[0037] Example 1

[0038] 1. A method for preparing a perfluoro, polyfluoroalkyl sulfonic acid and its substitutes solid phase microextraction probe, comprising the following steps:

[0039] Preparation of perfluoro, polyfluoroalkyl sulfonic acid and its substitutes and high selective enrichment solid phase microextraction probe: stainless steel needle is selected as the probe body material, the diameter is 0.1 mm, the tip part is 1 μm, and the length is 3 cm. Then, the cleaned stainless steel needle is ultrasonically cleaned, and the surface is hydroxylated by using Otocinclus Vertebralis washing solution to obtain a hydroxylated rough surface. 50 mL of N,N dimethylformamide is added, and then 2.5 mL of 3-(trimethoxysilyl) methyl methacrylate reagent is added. Under the protection of nitrogen, the reaction is heated to 80 °C and refluxed for 10 h. After the reaction is completed, the reaction solution is washed with methanol and ultrapure water for several times, and is placed in an oven at 50 °C for drying for 2 h to obtain a probe with a surface rich in methacryloyloxy groups. 1 mmoL of dimethylaminoethyl acrylate quaternary ammonium salt and 0.5 mmoL of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadeca(fluoro)propyl acrylate are added to 20 mL of acetonitrile, which is placed in a magnetic stirrer and stirred at 200 rpm at room temperature for 10 min to obtain a uniform solution. Under the protection of nitrogen, the solution is placed in an oil bath at 60 °C for polymerization for 24 h. After the polymerization is completed, the solution is washed with methanol for several times to clean the unreacted compounds. The solution is placed in an oven at 50 °C for drying for 2 h to obtain the solid phase microextraction probe.

[0040] Example 2

[0041] The present example provides a determination of the performance of different preparation processes of a perfluoro, polyfluoroalkyl sulfonic acid and its substitutes solid phase microextraction probe

[0042] (1) The tungsten steel probe is modified by surface silanization. 3-(trimethoxysilyl) methyl methacrylate is dissolved in different reaction solvents, and the ratio of reactant to reaction solvent is 10%. The reaction solvents include toluene, N,N-dimethylformamide, acetonitrile, and methanol, which are ultrasonically mixed and treated uniformly, and are used to soak the tungsten needle treated by surface hydroxylation. The reaction is carried out under the protection of nitrogen at a reaction temperature of 80 °C for 10 h to complete the modification of the surface rich in methacryloyloxy groups. After the reaction is completed, the reaction solution is washed with anhydrous ethanol and deionized water for several times and is dried in an oven at 60 °C to obtain the tungsten steel probe with a surface silanization.

[0043] (2) The dimethylaminoethyl acrylate quaternary ammonium salt and 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadeca (fluoro) acrylate are added in a ratio of 1:1 to an organic solvent acetonitrile, ultrasonic is used to make them fully dissolved, and then the surface silane modified tungsten probe is added for polymerization reaction, the reaction temperature is 60°C, the reaction time is 24h, and the solid matrix surface is attached with a coating layer with high selective adsorption capacity for perfluoro, polyfluoro alkyl sulfonic acid and its substitutes. After the modification is completed, the adsorption capacity of the surface modified probe is determined, and the results show that Figure 3 different reaction solvents have good adsorption capacity for the target object.

[0044] Example 3

[0045] This example provides a morphology characterization of the solid phase microextraction probe prepared in Example 1 for detecting perfluoro, polyfluoro alkyl sulfonic acid and its substitutes. The specific method is as follows:

[0046] The surface morphology of the tungsten probe before modification and the tungsten probe after modification is observed by using a focused ion beam field emission scanning electron microscope. The surfaces of the two probes are fixed on the sample table with conductive glue, the sample's area of interest is accurately positioned under the magnetic lens of the FIB-SEM using the microscope system positioning tool. The primary image of the sample is obtained by adjusting the electron beam using the electron microscope, and observation is carried out at different magnifications. Working parameters: 5kV Bi 8.64WD9

[0047] The morphology of the unmodified blank tungsten probe and the tungsten probe after surface coating modification is characterized by scanning electron microscopy (SEM). As can be clearly observed from the figure, the morphology of the tungsten probe after surface modification has changed significantly. Figure 2 The left side of the figure shows the scanning electron microscope image of the tungsten probe before modification. The surface of the tungsten probe before modification is smooth and uniform. Figure 2 The right side of the figure shows the scanning electron microscope image of the tungsten probe after modification by in-situ modification method. Compared with the tungsten probe before modification, the surface of the tungsten probe after modification has a regular polymer coating, and the surface is rough. After in-situ modification, the polymer coating is uniformly modified on the surface of the tungsten probe, changing the original smooth morphology of the tungsten probe, providing more binding sites for selective adsorption of perfluoro, polyfluoro alkyl sulfonic acid and its substitutes, and being conducive to the enrichment and analysis of the target object.

[0048] Example 4

[0049] This example provides a method for detecting perfluoro, polyfluoro alkyl sulfonic acid and its substitutes based on the solid phase microextraction probe prepared in Example 1, which comprises the following steps:

[0050] Preparation of perfluoro, polyfluoroalkyl sulfonic acid and its substitutes and high selective enrichment solid phase microextraction probe: stainless steel metal needle is selected as the probe body material, with a diameter of 0.1 mm, a tip part of 1 μm, and a length of 3 cm. Then, the cleaned stainless steel metal needle is ultrasonically cleaned, and a hydrosilylation treatment is performed on the surface of the needle using a piranha solution to obtain a hydroxylated rough surface. 50 mL of N,N dimethylformamide is added, followed by the addition of 2.5 mL of 3-(trimethoxysilyl) methyl propyl methacrylate reagent. Under nitrogen protection, the reaction is heated to 80°C and refluxed for 10 h. After the reaction is completed, the needle is washed several times with methanol and ultrapure water, and is dried in an oven at 50°C for 2 h to obtain a probe with a surface rich in methacryloxy groups. 1 mmoL of dimethylaminoethyl acrylate quaternary ammonium salt and 0.5 mmoL of 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadeca (fluoro) propyl acrylate are added to 20 mL of acetonitrile, which is placed in a magnetic stirrer and stirred at 200 rpm at room temperature for 10 min to obtain a uniform solution. Under nitrogen protection, the solution is placed in an oil bath at 60°C for 24 h of polymerization reaction. After the polymerization reaction is completed, the needle is washed several times with methanol to clean the unreacted compounds. The needle is dried in an oven at 50°C for 2 h to obtain the solid phase microextraction probe.

[0051] Solid phase microextraction: the prepared solid phase microextraction probe is placed in the operation handle holder, and the probe surface is washed with acetonitrile before extraction to clean the contaminants on the probe surface. The solid phase microextraction probe is inserted into the sample to ensure that the solid phase microextraction probe is in full contact with the sample. The enrichment extraction is performed for 30 min, the solid phase microextraction probe is taken out of the sample, and the solid phase microextraction probe is fixed in the operation rod and loaded in front of the mass spectrometer for analysis by atmospheric open electrospray mass spectrometry.

[0052] Atmospheric open mass spectrometry analysis: 5 μL of a resolving solvent containing an internal standard is injected into a nanoliter electrospray capillary using a microsyringe, the tungsten probe after extraction is loaded into the nanoliter electrospray needle, and the tip of the probe is placed in the nanoliter electrospray needle for desorption of the target compound, with a desorption time of 30 s. The solid phase microextraction probe is installed on a three-dimensional moving table together with the nanoliter electrospray needle, and the probe tip is aligned with and 5-15 mm away from the mass spectrometer inlet. After a high voltage of -3.0 kV is applied, the nanoliter electrospray ionization is induced by the desorption solvent to enter the mass spectrometer for analysis.

[0053] Example 5

[0054] The solid phase microextraction probe prepared in Example 1 is placed in 50 mL of spiked water samples containing perfluoro, polyfluoroalkyl sulfonic acid and its substitutes at a concentration of 10-5000 ng / L, and extracted for 30 min under constant temperature conditions. The concentration level of 50 ng / L of perfluoro, polyfluoroalkyl sulfonic acid and its substitutes is used as the detection limit of the method. 13The isotopic internal standard compound of C4-PFOS was configured as an internal standard desorption solvent. After the extraction was completed, the solid-phase microextraction probe was taken out of the sample, washed in pure water for 10 s, and then analyzed by atmospheric open electrospray mass spectrometry according to the method of Example 2 after being naturally air-dried. Figure 4 The mass spectrum obtained by analyzing the solid-phase microextraction probe prepared in Example 1 for extracting perfluoro, polyfluoroalkyl sulfonic acid and its substitutes in the water sample by atmospheric open electrospray mass spectrometry is shown in Figure 2. Figure 4 As can be seen from the analysis results, the solid-phase microextraction probe of the present application has excellent enrichment capacity for perfluoro, polyfluoroalkyl sulfonic acid and its substitutes. Table 1 is a methodological investigation of the solid-phase microextraction probe of the present application for detecting perfluoro, polyfluoroalkyl sulfonic acid and its substitutes for different analytes.

[0055] Table 1

[0056]

[0057] Example 6

[0058] The solid-phase microextraction probe prepared in Example 1 was modified and its performance was compared with the application patent: CN115068977A-Preparation method of a solid-phase microextraction probe for high-selectivity enrichment of perfluorinated compounds and its application. The modification method of Example 3 in “CN115068977A-Preparation method of a solid-phase microextraction probe for high-selectivity enrichment of perfluorinated compounds” was used to silanize the tungsten probe with a surface rich in hydroxyl groups, and through the polymerization reaction of functional monomers and the imprinting effect of template molecules, molecular imprinting polymerization was carried out. Finally, the template molecules were washed away by elution solvent, thereby obtaining a tungsten probe with a molecularly imprinted coating. In order to evaluate the enrichment effect of the two probes for perfluorinated compounds, nanoelectrospray mass spectrometry (nanoESI-MS) was used for analysis. The two probes were respectively placed into 50 mL of water sample containing 100 ng / L of perfluoro, polyfluoroalkyl sulfonic acid and its substitute standard solution, and extracted for 10 min at constant temperature. Then the probes were taken out and placed in pure water for 10 s, and then analyzed by nanoESI-MS after being naturally air-dried. 13 C4-PFOS was added as an internal standard to the desorption solvent, and the probe was installed together with the nanoelectrospray needle on a three-dimensional moving stage, with the tip of the probe aligned with and 5-15 mm away from the mass spectrometry inlet. After applying a high voltage of -3.0 kV, the nanoelectrospray ionization of the desorption solvent was induced into the mass spectrometer for analysis. Figure 5 The extraction efficiency comparison of the two probes for perfluoro, polyfluoroalkyl sulfonic acid and its substitutes is shown, and it can be seen that the probe prepared in Example 1 has higher extraction efficiency, especially for perfluorooctane sulfonic acid (PFOS), perfluorooctyl sulfonic acid and its salt (PFDS), 11-chloro eicosafluoro-3-oxaundecane-1-sulfonic acid potassium, etc. The extraction efficiency is significantly improved. This indicates that the probe prepared in Example 1 has stronger perfluoro recognition ability and higher selectivity.

[0059] In summary, the solid-phase microextraction probe prepared in Example 1 and the probe described in CN115068977A were used to enrich and analyze perfluorinated compounds. The results showed that the probe prepared in Example 1 has higher extraction efficiency and higher selectivity, and is a high-efficiency perfluorinated compound enrichment method.

[0060] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit the scope of protection of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A method for preparing a solid phase microextraction probe enriched with perfluoroalkylsulfonic acid, polyfluoroalkylsulfonic acid, and alternatives to both, characterized in that, The method comprises the following steps: (1) soaking a solid substrate containing active hydroxyl or amino groups in an organic solvent containing a coupling agent, heating in an inert atmosphere to make the coupling agent react with the surface of the solid substrate, washing and vacuum drying to form a solid substrate containing active double bond radicals; the coupling agent is 3-(trimethoxysilyl) methyl propyl methacrylate; the organic solvent is one or more of anhydrous toluene, N, N-dimethylformamide, acetonitrile, methanol or dichloromethane; (2) transferring the solid substrate containing active double bond radicals obtained in step (1) to a solvent containing monomer A and monomer B, heating in an inert atmosphere to make monomer A and monomer B in-situ polymerize with the radicals to form an in-situ modified coating, washing and drying to obtain a solid phase microextraction probe enriched with perfluoroalkyl sulfonic acid, polyfluoroalkyl sulfonic acid and their substitutes; the monomer A is perfluoro octyl ethyl acrylate; the monomer B is dimethylaminoethyl acrylate quaternary ammonium salt; the solvent is one or more of chloroform and acetonitrile; the molar ratio of monomer A to monomer B is 1:1-1:

2.

2. The method of claim 1, wherein the method is characterized by, In step (1), the solid substrate containing active hydroxyl or amino groups is a hard metal material or a wooden material with a sharp tip after surface chemical etching and roughening treatment.

3. The method of claim 1, wherein the method is characterized by, In step (1), the inert atmosphere is one or more of argon and nitrogen; the heating temperature is 80-120℃; the reaction time is 10-24h; the washing reagent is one or more of anhydrous ethanol, methanol and ultrapure water.

4. The method of claim 1, wherein the method is characterized by, In step (2), the inert atmosphere is one or more of argon and nitrogen; the heating temperature is 50-80℃; the polymerization reaction time is 12-24h; the washing reagent is anhydrous ethanol or methanol.

5. A solid phase microextraction probe enriched with perfluoroalkyl sulfonic acid, polyfluoroalkyl sulfonic acid and their substitutes prepared by the method of any one of claims 1-4.

6. The use of the solid phase microextraction probe enriched with perfluoroalkyl sulfonic acid, polyfluoroalkyl sulfonic acid and their substitutes of claim 5 in the qualitative and / or quantitative detection of perfluoroalkyl sulfonic acid, polyfluoroalkyl sulfonic acid and their substitutes.

7. A method for detecting enrichment of perfluoroalkyl sulfonic acids, polyfluoroalkyl sulfonic acids, and surrogates for both, comprising, The method comprises the following steps: (1) inserting the solid phase microextraction probe of claim 5 into a complex biological sample, allowing it to fully contact the sample, and stirring or oscillating; (2) taking out the solid phase microextraction probe from the sample and washing it; (3) connecting the solid phase microextraction probe to a mass spectrometer, desorbing and ionizing the perfluoroalkyl sulfonic acid, polyfluoroalkyl sulfonic acid and their substitutes enriched on the solid phase microextraction probe by an electrospray ion source or other ion source, and performing mass spectrometric analysis; (4) determining the types and contents of the enriched perfluoroalkyl sulfonic acid, polyfluoroalkyl sulfonic acid and their substitutes according to the intensity and mass-to-charge ratio of the mass spectrometric signals.

8. The method of claim 7, wherein the method is for detecting enrichment of perfluoroalkyl sulfonic acid, polyfluoroalkyl sulfonic acid, and a substitute for each of them. In step (3), the mass spectrometric analysis is atmospheric open mass spectrometric analysis.

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