CN112316929A - Covalent organic framework material, solid-phase microextraction probe, and preparation method and application thereof - Google Patents
Covalent organic framework material, solid-phase microextraction probe, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a covalent organic framework material, a solid-phase microextraction probe, and a preparation method and application thereof. The covalent organic framework material comprises 2,3,5, 6-tetrafluoro-p-benzaldehyde and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine repeating structural units which take imine bonds as connecting modes. The solid phase microextraction probe prepared by the material has high selectivity and high enrichment capacity for perfluoro and polyfluoroalkyl compounds, can be directly used with a nano-liter electrospray ion source for mass spectrometry after sampling and extraction, has extremely high sensitivity, and can be used for rapid, accurate and sensitive analysis of trace perfluoro and polyfluoroalkyl compounds in complex environments and biological samples.
Description
Technical Field
The invention belongs to the field of chemistry, and particularly relates to a covalent organic framework material, a solid-phase microextraction probe, and a preparation method and application thereof.
Background
Perfluoro and polyfluoroalkyl compounds (PFASs) are a class of Persistent Organic Pollutants (POPs) that are widely present in the environment and organisms. Several studies have shown that PFASs have liver, reproductive development and immunotoxicity and have potential carcinogenic effects. Perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) are the two most widely used PFASs, listed by stockholm convention in 2009 and 2015. In order to clearly understand the environmental behavior and biotoxicity of pfas, the amount and composition of pfas in the environment and in vivo needs to be monitored.
Mass spectrometry is the method of choice for analyzing pfas in complex samples. However, the PFASs exist in low concentration in environment and biological medium, which makes the traditional liquid chromatography-mass spectrometry method need a lot of sample pretreatment when used for analysis, and the whole analysis process becomes complicated, tedious and time-consuming. Therefore, there is a need to develop new analytical methods to achieve rapid, accurate and highly sensitive analysis of trace amounts of PFASs in complex environments and biological samples. Atmospheric Mass Spectrometry (AMS) is a new mass spectrometry technology developed in the beginning of the 21 st century that can directly analyze samples without or with little sample pretreatment, without chromatographic separation, under atmospheric pressure and open conditions. However, the high sensitivity analysis of trace chemicals in complex samples using atmospheric ambient ionization mass spectrometry remains a significant challenge. To overcome this problem, a technique of Solid Phase Microextraction (SPME) coupled with atmospheric ambient ionization mass spectrometry was developed. Currently, SPME has been implemented in conjunction with a variety of atmospheric ambient ionization techniques such as desorption electrospray ionization (DESI), direct analysis in real time (DART), Dielectric Barrier Discharge (DBDI), and Low Temperature Plasma (LTP). In addition, SPME probe direct ionization techniques, such as surface modified wood-label electrospray, surface modified probe nanoliter electrospray and the like, are also successfully applied to analysis of trace compounds in a complex system, such as high sensitivity and low matrix effect analysis.
The sensitivity of the solid phase microextraction-mass spectrometry combined method is closely related to the enrichment capacity of the SPME coating. In recent years, many new functional materials, such as zeolites, Carbon Nanotubes (CNTs), Molecularly Imprinted Polymers (MIPs), metal oxides, metal-organic frameworks (MOFs), and the like, have been widely used and developed for SPME coatings with high adsorption performance. Covalent Organic Frameworks (COFs), an emerging microporous material, have a structure composed of covalently linked organic subunits, show great potential in many fields such as gas adsorption, catalysis, energy collection, sensing and pollutant removal, and benefit from their high specific surface area, chemical stability, adjustable pore size, and easily customizable functionality. However, relatively few reports have been made of SPME probes fabricated using COFs in combination with atmospheric ambient ionization mass spectrometry to achieve rapid and highly sensitive analysis of trace contaminants in complex matrices.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a covalent organic framework material for high-selectivity adsorption of perfluoro and polyfluoroalkyl compounds, a preparation method thereof and application of the covalent organic framework material in manufacturing a biocompatible solid-phase microextraction probe. The prepared probe has high selectivity and high enrichment capacity for perfluoro and polyfluoroalkyl compounds, can be directly used with a nanoliter electrospray ion source for mass spectrometry after sampling and extraction, has extremely high sensitivity, and can be used for rapid, accurate and sensitive analysis of trace perfluoro and polyfluoroalkyl compounds in complex environments and biological samples.
The covalent organic framework material comprises 2,3,5, 6-tetrafluoro-p-benzaldehyde and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine repeating structural units which take imine bonds as a connecting mode.
The invention also provides a preparation method of the covalent organic framework material, which comprises the following steps:
a. mixing 2,3,5, 6-tetrafluoro-p-benzaldehyde and 2,4,6- (4-aminophenyl) -1,3, 5-triazine monomer;
b. adding a solvent, ultrasonically dissolving and uniformly mixing; the solvent is a mixed solvent of N, N-dimethylformamide, o-dichlorobenzene and acetonitrile;
c. adding an acetic acid aqueous solution, fully mixing, and then reacting for 48-72 h;
d. separating and purifying to obtain the covalent organic framework material.
Preferably, the mixing of step a is carried out by mixing 2,3,5, 6-tetrafluoro-p-benzaldehyde and 2,4,6- (4-aminophenyl) -1,3, 5-triazine monomer in a mass ratio of 3:2 and mixing.
Preferably, the acetic acid aqueous solution of the step c is acetic acid aqueous solution with the concentration of 12 mol/L; the separation and purification of the step d specifically comprises the following steps: the precipitate was obtained by centrifugation, washed with acetonitrile and dried under vacuum at 120 ℃.
The invention also provides a solid phase microextraction probe which contains the covalent organic framework material coating.
The invention also provides a preparation method of the solid phase microextraction probe, which comprises the following steps:
a. taking a stainless steel needle as a probe substrate, ultrasonically cleaning the stainless steel needle by using acetone, water and methanol in sequence, then soaking the stainless steel needle in 35-50 ℃ aqua regia for 1-3 min, continuously washing an etching probe by using deionized water until the pH value reaches 7, and drying the probe at room temperature in a nitrogen atmosphere to obtain the etched stainless steel needle;
b. dispersing neutral silicone sealing glue in toluene to prepare an adhesive, dipping an etched stainless steel needle with the adhesive, then rotating in covalent organic framework material powder to form a uniform coating, and curing at 120-150 ℃ for 2-5 h to obtain a probe with the uniform covalent organic framework material coating;
c. immersing the probe into a chitosan acetic acid aqueous solution, carrying out ultrasonic treatment for 15-30 min, then transferring the probe into a sodium tripolyphosphate aqueous solution, and standing to carry out a crosslinking reaction; this step was repeated three times;
d. and washing the obtained probe with methanol and deionized water, and drying in vacuum to obtain the solid-phase microextraction probe.
The chitosan acetic acid aqueous solution in the step c is an acetic acid aqueous solution with the volume fraction of 2% and the final concentration of 4.0mg/mL of chitosan; the sodium tripolyphosphate aqueous solution in the step c is 1.0mg/mL of sodium tripolyphosphate aqueous solution, and the standing in the step c is 30 min.
The invention also provides an application of the solid phase micro-extraction probe.
Preferably, the application is the application in the qualitative and quantitative analysis of perfluoro and polyfluoroalkyl compounds in environmental and biological samples.
Preferably, the application comprises the following steps:
a. directly sampling an environment and/or biological sample by using a solid-phase microextraction probe;
b. inserting the sampled probe into a nano-liter electrospray needle added with desorption/spray solvent, desorbing the target compound in a capillary of the nano-liter electrospray needle, then placing the nano-liter electrospray needle containing the solid phase microextraction probe on a bracket for fixing, aligning the tip of the nano-liter electrospray needle to a mass spectrum inlet and keeping the distance between the tip of the nano-liter electrospray needle and the mass spectrum inlet at 5-15mm, applying a high-voltage electric field on the probe, and directly carrying out nano-liter electrospray mass spectrum analysis under the condition of normal pressure opening.
Preferably, the desorption/spray solvent is methanol. The volume of the desorption/spray solvent is 2 mu L.
The covalent organic framework materials of the invention have a size of
The ordered pore structure and the rough spherical shape with the diameter of 500nm can carry out high-selectivity adsorption on perfluoro and polyfluoroalkyl compounds through size selection effect, hydrophobic interaction, electrostatic interaction, fluorine-fluorine bond interaction and hydrogen bond interaction. The covalent framework material can be used for preparing a solid phase micro-extraction probe, and is combined with an open type nanoliter electrospray mass spectrum to perform qualitative and quantitative analysis on trace perfluoro and polyfluoro compounds in complex environments and biological samples.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a covalent organic framework material of the present invention;
FIG. 2 is a Fourier transform infrared spectrum, X-ray powder diffraction pattern, X-ray photoelectron spectrum, water contact angle pattern, thermogravimetric spectrum and scanning electron microscopy of a covalent organic framework material of the present invention;
FIG. 3 is a schematic representation of ordered channels of a covalent organic framework material of the present invention;
FIG. 4 is a schematic diagram of the process for preparing a biocompatible solid-phase microextraction probe made of the covalent organic framework material according to the present invention;
FIG. 5 is a graph of the adsorption capacity of a biocompatible solid-phase microextraction probe made of a covalent organic framework material according to the present invention;
FIG. 6 is a schematic diagram of a process for analyzing perfluoro and polyfluoroalkyl compounds by using a solid phase microextraction probe made of covalent organic framework material of the present invention in combination with an open nanoliter electrospray mass spectrometry;
FIG. 7 is a mass spectrum obtained by analyzing perfluoro and polyfluoro compounds in environmental water and blood by using a solid phase microextraction probe made of covalent organic framework material of the present invention in combination with an open nanoliter electrospray mass spectrometry.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof.
Example 1: preparation of perfluoro and polyfluoroalkyl compound high-selectivity adsorption covalent organic framework material
A process for preparing the covalent organic frame material with high-selectivity adsorption of perfluoro-or polyfluoroalkyl compound (see figure 1) includes such steps as mixing raw material with solvent, adding catalyst, forming imine product under a certain condition, and post-treating. The method comprises the following specific steps:
first, 2,3,5, 6-tetrafluoro-p-benzaldehyde and 2,4,6- (4-aminophenyl) -1,3, 5-triazine monomer are mixed in a stoichiometric ratio of 3:2, wherein the amount of 2,3,5, 6-tetrafluoro-p-benzaldehyde is 61.8mg and the amount of 2,4,6- (4-aminophenyl) -1,3, 5-triazine is 70.9 mg; then adding 3.5mL of N, N-dimethylformamide, carrying out ultrasonic treatment until the reactant is completely dissolved, sequentially adding 15mL of acetonitrile and 35mL of o-dichlorobenzene, and carrying out ultrasonic treatment until the reactants are uniformly mixed; then adding 2mL of acetic acid aqueous solution with the concentration of 12mol/L as a catalyst for reaction; immediately carrying out violent shaking on the reaction system for 1 min; then, standing the system for 72 hours at room temperature (the temperature is 25 ℃, and the reaction pressure is 1atm), and continuously precipitating yellow precipitates in the process; finally, the system was transferred to a glass centrifuge tube and centrifuged to remove the supernatantAnd washing the precipitate with acetonitrile (6mL multiplied by 5 times) and vacuum-drying at 120 ℃ for 12 hours to obtain 68.5-82.4 mg of light yellow powdery solid, namely the target covalent organic framework material, with the yield of 56.2-67.6%. The obtained materials were characterized by fourier transform infrared spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, contact angle measurement, thermogravimetric analysis and scanning electron microscopy, respectively, and the results are shown in fig. 2(a) - (f), respectively. Fig. 3 is a schematic view of the ordered channels of the resulting covalent organic framework material. The covalent organic framework material has a size of
The ordered pore structure and the rough spherical shape with the diameter of 500nm can carry out high-selectivity adsorption on perfluoro and polyfluoroalkyl compounds through size selection effect, hydrophobic interaction, electrostatic interaction, fluorine-fluorine bond interaction and hydrogen bond interaction.
Example 2: preparation of biocompatible solid-phase microextraction probe based on perfluoro and polyfluoroalkyl compound high-selectivity adsorption covalent organic framework material
A biocompatible solid-phase microextraction probe based on perfluoro and polyfluoroalkyl compounds for selectively adsorbing the covalent organic frame material is prepared through directly coating the probe carrier on the carrier, etching the probe carrier, coating adhesive on the etched carrier, adhering the covalent organic frame material powder to the probe carrier, solidifying adhesive, modifying the biocompatible coating and post-treating the probe.
Firstly, taking a 304 stainless steel needle (with the diameter of 0.5mm and the length of 3cm), and sequentially and respectively carrying out ultrasonic cleaning in acetone, ultrapure water and methanol for 30min to remove surface impurities; then, the stainless steel needle was immersed in aqua regia (immersion depth 1.5cm) at 50 ℃ for 1min, taken out after immersion and etching, continuously washed with ultrapure water until the pH of the washing solution became 7, and blow-dried with nitrogen gas at room temperature to obtain an etched stainless steel needle. Meanwhile, 1.2g of neutral silicone sealant was dispersed in 1.5mL of toluene to make the adhesive, the etched stainless steel needle was quickly immersed in the adhesive (immersion depth 1cm) and then quickly removed, the excess adhesive on the needle was carefully wiped off with a dust-free paper to get a uniform coating, the etched stainless steel needle coated with adhesive was rotated back and forth in the grinding powder of the covalent organic framework material to ensure that the adhesive coating was completely covered by the material; and (3) flicking the probe to enable the material powder with weak surface adhesion to fall off, and then curing for 5h at 120 ℃ to obtain the probe with uniform covalent organic framework material coating. Immersing the obtained probe into 4mg/mL chitosan acetic acid aqueous solution (the molecular weight of the chitosan is 32670Da, and the chitosan is dissolved in 2% by volume of the acetic acid aqueous solution) for ultrasonic treatment for 15min, then immersing the probe into 1mg/mL sodium tripolyphosphate aqueous solution, standing for 30min for crosslinking reaction, and repeating the process for three times; obtaining a covalent organic framework material solid phase micro-extraction probe coated with a biocompatible protective coating; washing the obtained probe with methanol and deionized water respectively, vacuum drying at 120 ℃, and finally storing in a nitrogen atmosphere at room temperature for later use; thus, a solid phase microextraction probe (COFs-SPME) was obtained.
Example 3: study of adsorption Capacity of COFs-SPME
Under the optimized experimental conditions, analyzing a series of perfluorooctane sulfonate (PFOS) pure water standard-adding solutions with concentration by adopting COFs-SPME and an open-type nanoliter electrospray ionization mass spectrum, and researching the adsorption capacity of the COFs-SPME probe.
The adsorption saturation concentration of the COFs-SPME probe to PFOS was observed to be 50 ng/. mu.L experimentally (see FIG. 5). Then, under the same experimental conditions, the perfluorooctane sulfonic acid standard solution in the methanol solution was analyzed by nanoliter electrospray mass spectrometry, and the concentration at which the same signal intensity as that produced by the saturation extraction was found to be 1.2. mu.g/. mu.L. As the analysis process adopts 2 mu L of methanol for desorption, the perfluorooctane sulfonate with the adsorption capacity of 2.4 mu g of the COFs-SPME probe is calculated.
Example 4: verification of COFs-SPME and open type nanoliter electrospray ionization mass spectrometry combined methodology
FIG. 6 is a schematic diagram of a process for analyzing perfluoro and polyfluoroalkyl compounds using a solid phase microextraction probe made of a covalent organic framework material in combination with an open nanoliter electrospray mass spectrometry. Directly sampling an environment and/or biological sample by using a solid-phase microextraction probe; inserting the sampled probe into a nano-liter electrospray needle added with desorption/spray solvent methanol (1-5 mu L), desorbing the target compound in a capillary of the nano-liter electrospray needle, then placing the nano-liter electrospray needle containing the solid phase microextraction probe on a bracket for fixing, aligning the tip of the nano-liter electrospray needle to a mass spectrum inlet and keeping a distance of 5-15mm from the mass spectrum inlet, applying a high-voltage electric field on the probe, and directly performing nano-liter electrospray mass spectrum analysis under the condition of normal pressure opening.
The experimental method comprises the following steps: PFASs with the concentration range of 0.5-1000ng/L are added into pure water, and the quantitative accuracy of the COFs-SPME and open-type nanoliter electrospray ionization mass spectrometry combined analysis method is researched.
Will be provided with13C4-perfluorooctanesulfonic acid and13C4perfluorooctanoic acid added to the sample solvent as a concentration level of 100ng/L13C4PFOS and 500ng/L concentration levels13C4Isotopically internal standard compounds of PFOA. The use of an internal standard compound for error calibration of the analytical process can greatly improve the reproducibility of the method.
The results show that the method of the invention has a good linear relationship and the correlation coefficient (r) is not lower than 0.9952 (Table 1). The lowest detection and quantitation limits were 0.02-0.8 ng/L and 0.06-3 ng/L, respectively (determined by the concentration of the peak at signal-to-noise ratios of 3 and 10).
In a repeated experiment, a single probe repeats an extraction experiment for 6 times, a water sample added with 10ng/L perfluorosulfonic acid and 50ng/L perfluorocarboxylic acid is extracted under the same condition, and the result shows that RSD is in the range of 4.1-10.9%. According to experimental results, the solid phase micro-extraction probe can be repeatedly used, and has good repeatability and stability.
Meanwhile, the reproducibility test among different probes is researched, 6 different COFs-SPME probes are prepared by the same invention method, the test result also shows good reproducibility, and RSDs is in the range of 6.5-12.3%.
The recovery rate test shows that the method has good accuracy, and the recovery rate reaches 84-113%.
These results show that the COFs-SPME and the open type nanoliter electrospray ionization mass spectrometry combined analysis method can be applied to the direct quantitative detection of the ultra-trace PFASs.
TABLE 1 COFs-SPME nanoESI-MS method for analyzing the linear equation, range, detection limit, quantitation limit, repeatability and recovery rate of PFASs
aAnalytical pure water was added with 10ng/L perfluorosulfonic acid and 50ng/L perfluorocarboxylic acid
Example 5: COFs-SPME and open type nanoliter electrospray ionization mass spectrometry combined analysis of PFASs in environmental water sample and blood
The established COFs-SPME open type nanoliter electrospray ionization mass spectrometry combined analysis method is applied to detection of PFASs in actual environment and biological samples. In a lake water sample, concentrations of PFOS, PFOA, PFNA, PFDA, PFDoDA, PFTrDA, PFTeDA, PFHxDA and PFODA were found to be 38.6, 29.9, 15.8, 10.9, 5.8, 5.4, 12.5, 8.1 and 12.1ng/L, respectively, with signal-to-noise ratios between 13 and 98 (FIG. 7 a). Then, standard addition experiments were performed using PFASs at 50ng/L, resulting in recoveries ranging from 88.4-108.6%.
In a whole blood sample PFOS, PFDS, PFOA, PFNA, PFDA, PFUnDA, PFDoDA, PFTrDA and PFTeDA were detected at concentrations of 741, 261, 455, 779, 311, 474, 65, 39 and 76ng/L (signal to noise ratio values in the range of 15-422), respectively (FIG. 7 b). Then, standard addition experiments were performed using 500ng/L PFASs, resulting in recoveries in the range of 69.4-91.2%.
Example 6: preparation of perfluoro and polyfluoroalkyl compound high-selectivity adsorption covalent organic framework material
First, 2,3,5, 6-tetrafluoro-p-benzaldehyde and 2,4,6- (4-aminophenyl) -1,3, 5-triazine monomer are mixed in a stoichiometric ratio of 3:2, wherein the amount of 2,3,5, 6-tetrafluoro-p-benzaldehyde is 12.4mg and the amount of 2,4,6- (4-aminophenyl) -1,3, 5-triazine is 14.2 mg; then adding 0.7mL of N, N-dimethylformamide, carrying out ultrasonic treatment until the reactant is completely dissolved, sequentially adding 3mL of acetonitrile and 7mL of o-dichlorobenzene, and carrying out ultrasonic treatment until the reactants are uniformly mixed; then adding 0.8mL of glacial acetic acid aqueous solution with the concentration of 12mol/L as a catalyst for reaction; immediately carrying out violent shaking on the reaction system for 0.5 min; then, standing the system for 48 hours at room temperature (the temperature is 25 ℃, and the reaction pressure is 1atm), and continuously precipitating yellow precipitates in the process; and finally, transferring the system into a glass centrifuge tube, centrifuging to remove supernatant, washing the precipitate with acetonitrile (6mL multiplied by 5 times) and vacuum-drying at 120 ℃ for 12 hours to obtain 13.7-16.5 mg of light yellow powdery solid, namely the target covalent organic framework material, wherein the yield is 56.2-67.6%.
Example 7: preparation of biocompatible solid-phase microextraction probe based on perfluoro and polyfluoroalkyl compound high-selectivity adsorption covalent organic framework material
Firstly, taking a 304 stainless steel needle (with the diameter of 0.5mm and the length of 3cm), and sequentially and respectively carrying out ultrasonic cleaning in acetone, ultrapure water and methanol for 15min to remove surface impurities; then, the stainless steel needle was immersed in 35 ℃ aqua regia (immersion depth 1.5cm), immersed and etched for 3min, taken out, continuously washed with ultrapure water until the pH of the washing solution became 7, and blow-dried with nitrogen gas at room temperature to obtain an etched stainless steel needle. Meanwhile, 0.5g of neutral silicone sealant is dispersed in 1mL of toluene to prepare an adhesive, the etched stainless steel needle is quickly immersed in the adhesive (the immersion depth is 1cm) and then quickly taken out, the excess adhesive on the needle is carefully wiped off by using dust-free paper to obtain a uniform coating, and the etched stainless steel needle coated with the adhesive is rotated back and forth in the grinding powder of the covalent organic framework material to ensure that the adhesive coating is completely covered by the material; and (3) flicking the probe to enable the material powder with weak surface adhesion to fall off, and then curing for 2h at 150 ℃ to obtain the probe with uniform covalent organic framework material coating. Immersing the obtained probe into 4mg/mL chitosan acetic acid aqueous solution (the molecular weight of the chitosan is 32670Da, and the chitosan is dissolved in 2% by volume of the acetic acid aqueous solution) for ultrasonic treatment for 15min, then immersing the probe into 1mg/mL sodium tripolyphosphate aqueous solution, standing for 30min for crosslinking reaction, and repeating the process for three times; obtaining a covalent organic framework material solid phase micro-extraction probe coated with a biocompatible protective coating; washing the obtained probe with methanol and deionized water respectively, vacuum drying at 120 ℃, and finally storing in a nitrogen atmosphere at room temperature for later use; thereby obtaining a solid phase microextraction probe.
Claims (10)
1. A covalent organic framework material comprising recurring structural units of 2,3,5, 6-tetrafluorop-benzaldehyde and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine connected by imine bonds.
2. A method of preparing a covalent organic framework material, comprising the steps of:
a. mixing 2,3,5, 6-tetrafluoro-p-benzaldehyde and 2,4,6- (4-aminophenyl) -1,3, 5-triazine monomer;
b. adding a solvent, ultrasonically dissolving and uniformly mixing; the solvent is a mixed solvent of N, N-dimethylformamide, o-dichlorobenzene and acetonitrile;
c. adding an acetic acid aqueous solution, fully mixing, and then reacting for 48-72 h;
d. separating and purifying to obtain the covalent organic framework material.
3. The method according to claim 2, wherein the mixing of step a is carried out by mixing 2,3,5, 6-tetrafluoro-p-benzaldehyde and 2,4,6- (4-aminophenyl) -1,3, 5-triazine monomer in a mass ratio of 3:2 and mixing.
4. The method according to claim 2, wherein the aqueous acetic acid solution of step c is an aqueous acetic acid solution having a concentration of 12 mol/L; the separation and purification of the step d specifically comprises the following steps: the precipitate was obtained by centrifugation, washed with acetonitrile and dried under vacuum at 120 ℃.
5. A solid phase microextraction probe comprising a coating of the covalent organic framework material of claim 1.
6. A preparation method of a solid phase micro-extraction probe is characterized by comprising the following steps:
a. taking a stainless steel needle as a probe substrate, ultrasonically cleaning the stainless steel needle by using acetone, water and methanol in sequence, then soaking the stainless steel needle in 35-50 ℃ aqua regia for 1-3 min, continuously washing an etching probe by using deionized water until the pH value reaches 7, and drying the probe at room temperature in a nitrogen atmosphere to obtain the etched stainless steel needle;
b. dispersing neutral silicone sealing glue in toluene to prepare an adhesive, dipping an etched stainless steel needle with the adhesive, then rotating in covalent organic framework material powder to form a uniform coating, and curing at 120-150 ℃ for 2-5 h to obtain a probe with the uniform covalent organic framework material coating;
c. immersing the probe into a chitosan acetic acid aqueous solution, carrying out ultrasonic treatment for 15-30 min, then transferring the probe into a sodium tripolyphosphate aqueous solution, and standing to carry out a crosslinking reaction; this step was repeated three times;
d. and washing the obtained probe with methanol and deionized water, and drying in vacuum to obtain the solid-phase microextraction probe.
7. The method of claim 6, wherein the chitosan acetic acid aqueous solution of step c is a volume fraction 2% acetic acid aqueous solution containing chitosan at a final concentration of 4.0 mg/mL; the sodium tripolyphosphate aqueous solution in the step c is 1.0mg/mL of sodium tripolyphosphate aqueous solution, and the standing in the step c is 30 min.
8. Use of the solid phase microextraction probe of claim 5.
9. Use according to claim 8, for the qualitative and quantitative analysis of perfluoro and polyfluoroalkyl compounds in environmental and biological samples.
10. Use according to claim 8, characterized in that it comprises the following steps:
a. directly sampling an environment and/or biological sample by using a solid-phase microextraction probe;
b. inserting the sampled probe into a nano-liter electrospray needle added with desorption/spray solvent, desorbing the target compound in a capillary of the nano-liter electrospray needle, then placing the nano-liter electrospray needle containing the solid phase microextraction probe on a bracket for fixing, aligning the tip of the nano-liter electrospray needle to a mass spectrum inlet and keeping the distance between the tip of the nano-liter electrospray needle and the mass spectrum inlet at 5-15mm, applying a high-voltage electric field on the probe, and directly carrying out nano-liter electrospray mass spectrum analysis under the condition of normal pressure opening.
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