Extraction head for detecting geraniol compound and detection method using same

Abstract

The invention discloses an extraction head for detecting geraniol, the extraction head is a composite material of polymerized 3-amino-9-ethyl carbazole-pyrrole-IL, and the IL is 1-butyl-3-methylimidazolium hexafluorophosphate. Therefore, after the 3-AN-9-NECA and the PY are copolymerized, the conductivity of the polymerized 3-AN-9-NECA is greatly improved, the copolymerized extraction head coating is relatively thick and compact in structure, and a target substance can be effectively adsorbed for detection. Meanwhile, in order to improve the performance of the extraction head, imidazole IL: 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIm] [PF6]) is doped into the copolymerized 3-AN-9-NECA-PY coating, and the composite coating is prepared and used for headspace extraction of geraniol. The prepared composite coating has good durability and stability. Compared with a common polymerized 3-AN-9-NECA coating and a pyrrole coating, the composite coating has the advantage that the coating modified by adding the ionic liquid also shows higher extraction efficiency.

Description

Technical Field

[0001] This invention relates to the field of cosmetic safety, and more particularly to an extraction head for detecting geraniol compounds and a detection method using the same.

[0002] Geraniol is a colorless to pale yellow oily liquid with an elegant rose scent, and is therefore frequently added as a fragrance to various cosmetics. With the increasing frequency of daily cosmetic use, the allergenicity of cosmetics has also attracted attention. 35% of cosmetic allergies are caused by added fragrances. Therefore, accurate detection of geraniol content in cosmetics is essential. Summary of the Invention

[0003] To address one or more of the above problems, an extraction head for detecting geraniol compounds and a detection method using the same are provided.

[0004] According to one aspect of this application, an extraction head for detecting geraniol is provided, said extraction head being a composite material of polymerized 3-amino-9-ethylcarbazole-pyrrole-IL, wherein IL is 1-butyl-3-methylimidazolium hexafluorophosphate.

[0005] The beneficial effects are as follows: copolymerization of 3-AN-9-NECA and PY significantly improves the conductivity of the polymerized 3-AN-9-NECA. The copolymerized extraction head coating is thicker and more compact, effectively adsorbing target substances for detection. Furthermore, to enhance the extraction head performance, imidazole-based IL: 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIm][PF6]) is incorporated into the copolymerized 3-AN-9-NECA-PY coating to prepare a composite coating for headspace extraction of geraniol. The resulting composite coating exhibits good durability and stability. Compared to conventional polymerized 3-AN-9-NECA and pyrrole coatings, the coating modified with ionic liquids also demonstrates higher extraction efficiency.

[0006] In some embodiments, the method for preparing the extraction head includes: A composite extraction head was prepared by preparing a comonomer of 3-amino-9-ethylcarbazole and pyrrole, with IL being a mixed solution of 1-butyl-3-methylimidazolium hexafluorophosphate. An electrode system was inserted into the mixed solution, and cyclic voltammetry was used. The advantages are: using a dual-monomer copolymer of 3-amino-9-ethylcarbazole and pyrrole allows for the utilization of the advantages of both monomers, effectively overcoming the shortcomings of single-monomer polymer coatings such as low thermal stability, poor film-forming performance, and low extraction capacity.

[0007] In some embodiments, the concentration ratio of 3-amino-9-ethylcarbazole to pyrrole is 3:2.

[0008] Its beneficial effect is that the ratio of these two monomers is conducive to the preparation of extraction heads with higher stability and better sensitivity.

[0009] In some embodiments, the concentration of the ionic liquid IL is 8 μL / mL. The advantages are that the extraction head prepared in this way exhibits high stability and good sensitivity.

[0010] In some embodiments, the electrode system consists of: Ag / AgCl as the reference electrode; platinum wire as the auxiliary electrode; and stainless steel wire as the working electrode. The advantage of this system is its high preparation efficiency.

[0011] According to another aspect of this application, a method for detecting geraniol compounds is provided, comprising the following steps: Geraniol compounds were extracted using the aforementioned composite extraction head-up space extraction method. Gas chromatography-mass spectrometry was constructed, and the extraction head was used to detect geraniol compounds.

[0012] In some embodiments, headspace extraction of geraniol compounds using a composite extraction head includes the following steps: Prepare geraniol standard solution; Prepare geraniol working solution; Perform HS-SPME operation; upon completion, Perform GC-MS operation.

[0013] In some implementations, HS-SPME operation includes the following steps: A saturated sodium chloride solution and a phenol-geraniol standard solution were added to the extraction flask to form the first mixture. The first mixture was heated and stirred in a water bath; Insert the injection device into the headspace extraction vial and expose the extraction head of the injection device above the extraction vial for headspace extraction.

[0014] Its beneficial effect is the resulting higher extraction efficiency.

[0015] In some implementations, GC-MS operation includes the following steps: After the HS-SPME operation steps are completed, Retract the extraction head into the protective sleeve, quickly insert it into the GC-MS injection port, analyze it, and then perform GC-MS separation and detection.

[0016] In some embodiments, the extraction temperature is 40 ℃-80 ℃.

[0017] Its beneficial effects are: the extraction head prepared in this application has a more uniform and dense coating, and the two copolymerized monomers show significant advantages over a single monomer or pyrrole monomer, resulting in better coating performance. Attached Figure Description

[0018] Figure 1 This is the voltammetry diagram of 3-AN-9-NECA in this application; Figure 2 This is the volt-ampere diagram of PY in this application; Figure 3 This is the voltammetry diagram when the concentration ratio of 3-AN-9-NECA to PY in this application is 4:1; Figure 4 This is a voltammetric diagram when the concentration ratio of 3-AN-9-NECA to PY in this application is 3:1; Figure 5 The voltammetry diagram of the 3-AN-9-NECA to PY concentration ratio of 3:2 in this application; Figure 6 This is a voltammetric diagram when the concentration ratio of 3-AN-9-NECA to PY in this application is 1:4; Figure 7 This is a voltammetric diagram when the concentration ratio of 3-AN-9-NECA+PY in this application is 3:2 and the IL concentration is 8 μL / m. Figure 8 This is a SEM image of the 3-AN-9-NECA extraction head in this application; Figure 9 This is a SEM image of the 3-AN-9-NECA extraction head in this application; Figure 10 This is a SEM image of the PY extraction head in this application; Figure 11 This is a SEM image of the PY extraction head in this application; Figure 12 This is a SEM image of the 3-AN-9-NECA:PY=4:1 extraction head in this application; Figure 13 This is a SEM image of the 3-AN-9-NECA:PY=4:1 extraction head in this application; Figure 14 This is a SEM image of the 3-AN-9-NECA:PY=3:2 extraction head in this application; Figure 15 This is a SEM image of the 3-AN-9-NECA:PY=3:2 extraction head in this application; Figure 16 This is a SEM image of the 3-AN-9-NECA:PY=2:3 extraction head in this application; Figure 17 This is a SEM image of the 3-AN-9-NECA:PY=1:4 extraction head in this application; Figure 18This is a SEM image of the 3-AN-9-NECA:PY=1:4 extraction head in this application; Figure 19 This is a SEM image of the 3-AN-9-NECA:PY=4:1+IL extraction head in this application; Figure 20 This is a SEM image of the 3-AN-9-NECA:PY=3:2+IL extraction head in this application; Figure 21 This is a SEM image of the 3-AN-9-NECA:PY=2:3+IL extraction head in this application; Figure 22 This is a SEM image of the 3-AN-9-NECA:PY=1:4+IL extraction head in this application; Figure 23 This is an adsorption peak area diagram of the optimized extraction head with the 3-AN-9-NECA to PY concentration ratio used in this application for the detection of geraniol. Figure 24 This is an adsorption force diagram of the extraction head with different ionic liquid concentrations in this application; Figure 25 This is an adsorption force diagram of the extraction head at different extraction temperatures in this application; Figure 26 This is the standard curve of geraniol in this application; Figure 27 This is the detection spectrum of the tea sample in this application; Figure 28 This is the chromatogram of the spiked tea sample in this application; Detailed Implementation The invention will now be further described with reference to the accompanying drawings.

[0019] I. Reagents and Main Instruments Main instruments and models: Gas chromatograph-mass spectrometer (Shimadzu GC-MS-QP2010), vacuum tube furnace (TF1200-80), electrochemical workstation (CHI600E), ultrasonic cleaner (KQ5200E), thermostatic magnetic stirrer (S10-3), scanning electron microscope (SEM), and injector (self-made in the laboratory).

[0020] 3-Amino-9-ethylcarb(3-AN-9-NECA)azole, pyrrole (PY), tetrabutylammonium perchlorate (99%), 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF6), geraniol (98%), sodium chloride (AR, Tianjin Fuyu Fine Chemical Co., Ltd.), anhydrous ethanol (analytical grade, Sinopharm Group), acetonitrile (premium chromatographic grade, Merck & Co., Ltd.), and water were all purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. All other reagents not mentioned in this experiment were of analytical grade.

[0021] II. GC-MS Operating Conditions A DB-1701 column was used for separation. The column oven temperature was 40 °C; the inlet temperature was 250 °C; the injection mode was splitless; the pressure was 92.3 kPa; the total flow rate was 50.0 mL / min; the column flow rate was 1.65 mL / min; the linear velocity was 46.3 cm / sec; and the purge flow rate was 3.0 mL / min. The column oven temperature program was set as follows: 40 °C for 3 min, increased to 90 °C at 5 °C / min and held for 3 min; then increased to 160 °C at 7 °C / min and held for 4 min; finally increased to 250 °C at 8 °C / min and held for 1 min. The ion source temperature was 230 °C; the interface temperature was 250 °C; the elution time was 5 min, the solvent delay was 3 min, and the retention time was 66 min. The retention time and qualitative and quantitative ions of Dodecanol are shown in the table below.

[0022] Table 2-1 Characteristic Selective Ions of Dodecanol

[0023] III. Coating Preparation (I) Preparation of stainless steel wire After measuring a 1.8 cm stainless steel wire with a ruler, smooth it with an iron ruler. Before using the smooth stainless steel wire, sonicate it for 5 minutes with nitric acid:water = 1:1 (HNO3:H2O = 1:1), then rinse it twice with deionized water, and then wash it twice with anhydrous ethanol. Let it air dry naturally.

[0024] (ii) Polymerization of SPME coating SPME coatings were prepared on an electrochemical workstation (CHI600E) using a single-cell three-electrode configuration. Electrochemical deposition was achieved via cyclic voltammetry (the three electrodes were: a 1.8 cm stainless steel wire as the working electrode, a platinum wire as the auxiliary electrode, and Ag / AgCl as the reference electrode; CV parameters were: Init E(V): 0, High E(V): 1.8, Scan Rate (V / s): 0.05, Sweep Segments: 100, Sensitivity (A / V): 1 × 10⁻⁶. -3 The assembled three-electrode system was immersed in the prepared solution. Under the set CV parameters, the electrochemical workstation (CHI600E) was started to prepare SPME heads for 3-amino-9-ethylcarbazole, 3-amino-9-ethylcarbazole-pyrrole, pyrrole, 3-AN-9-NECA-IL, 3-AN-9-NECA-PY-IL, and PY-IL. The total concentration of the dimonomer copolymer solution was 0.05 mol / L, with a concentration ratio of 3-amino-9-ethylcarbazole (3-AN-9-NECA) to pyrrole (PY) of 3:2, a tetrabutylammonium perchlorate concentration of 0.05 mol / L, an IL concentration of 8.0 μL / mL, and acetonitrile as the solvent.

[0025] (III) Fabrication of the injection device and aging of the SPME coating After the SPME coating polymerization was completed, the coating was removed and allowed to air dry naturally. Then, it was aged in a TF1200-80 vacuum tube furnace with a programmed temperature rise. Specifically, the temperature was increased from 50°C to 250°C at a rate of 10°C / min, held for 2 hours, and then decreased to 50°C at a rate of 10°C / min. After aging, the extraction head was attached to the self-made solid-phase microextraction handle with epoxy resin and curing agent.

[0026] IV. Solution Preparation Using anhydrous ethanol as the solvent, a geraniol stock solution with a concentration of 50 µg / mL was prepared for use. During the test, 20 µL, 40 µL, 80 µL, 120 µL, and 160 µL of the stock solution were respectively placed into extraction flasks containing 10 mL of saturated sodium chloride solvent to prepare extraction solutions with concentration gradients of 0.1 µg / mL, 0.2 µg / mL, 0.4 µg / mL, 0.6 µg / mL, and 0.8 µg / mL, and then sealed for use.

[0027] V. HS-SPME Operating Procedures Transfer 10.00 mL of saturated sodium chloride solution to a 15.00 mL extraction flask, place a magnetic stir bar inside, add geraniol solution, seal the flask with raw rubber tape, plug with a rubber stopper, and then seal with an aluminum cap. Maintain the temperature of the S10-3 thermostatic magnetic stirrer at 70℃ and the stirring speed at 600 r / min. Fix the extraction flask containing the solution in the S10-3, insert the syringe into the extraction flask, and push out the extraction head to expose it to the extraction flask. Perform headspace extraction for 30 min. After completion, pull the extraction head back into the protective sleeve and directly insert it into the GC-MS injection port for analysis and detection.

[0028] GC-MS technology combines the efficient separation method of gas chromatography with the precise detection method of mass spectrometry, enabling qualitative and quantitative analysis of samples. This application uses a DB-1701 column as the separation column and an electron impact ionization (EI) source as the mass separator for the MS.

[0029] VI. Product Property Characterization (I) Voltammetric behavior of extraction head preparation by electropolymerization SPME heads were prepared using CV, and CV patterns using acetonitrile as the medium were recorded (see [link]). Figures 1-6 The optimal potential for electropolymerization of the 3-AN-9-NECA extraction head is 1.2V-1.8V, within which the polymerized 3-AN-9-NECA coating is relatively stable. By comparing the extraction capabilities of different types of SPME coatings for analytes, the polymerized 3-AN-9-NECA-PY-IL coating was identified as the superior extraction coating. Specifically, as shown in the figure, the CV curve is closely related to the polymerization medium during SPME coating preparation. Figure 1 It is the CV plot of the monomer 3-AN-9-NECA, from Figure 1 It can be seen that it has two oxidation potentials, approximately 1.0 and 1.7, respectively. As the number of scans increases, its oxidation potential gradually decreases, and its conductivity gradually decreases. Figure 2 This is the CV diagram of pyrrole monomer. It can be seen from the diagram that pyrrole monomer has good electrical conductivity and its oxidation potential is around 0.8. Figures 3-6 The figure shows the CV curves of copolymerization of 3-AN-9-NECA and pyrrole at different concentrations. As can be seen from the figure, the conductivity of the two monomers after copolymerization is significantly enhanced. With the increase of the number of polymerization cycles and the growth of polymerization time, the peak current gradually increases and becomes more uniform and dense. This indicates that the two monomers after copolymerization have obvious advantages over single monomers or pyrrole monomers, resulting in better coating performance.

[0030] exist Figure 7As can be seen, after doping with IL (1-butyl-3-methylimidazolium hexafluorophosphate), the CV curve of the polymerized 3-AN-9-NECA-PY shows a significant increase in response current, with an oxidation peak appearing at around 0.9 V. As the number of scan cycles increases, the oxidation current gradually decreases, eventually showing a small oxidation peak at around 1.6 V. In subsequent experiments, the ratio of the two monomers and the concentration of IL were varied to optimize the overall performance of the coating.

[0031] (II) Microscopic characterization of different extraction heads 1. SEM characterization of 3-AN-9-NECA-PY type extraction head Figure 8 The figure shows the SEM characterization image of the polymerized coating using 3-amino-9-ethylcarbazole monomer. As shown, the polymerized 3-amino-9-ethylcarbazole monomer coating exhibits a cloud-like wrinkled structure. The coating is novel and orderly arranged, but the coating is relatively thin. Figure 9 Using pyrrole monomer as the monomer, the resulting coating exhibits a three-dimensional porous structure with a loose arrangement, resulting in good adsorption performance. Figure 10 The polymeric pyrrole coating is relatively thick and can adhere well to stainless steel wire, but the coating is also relatively loose and easily peels off. Figure 11 Therefore, a co-polypyrrole solution was used in a 3-AN-9-NECA solution to alter the structure of the two monomers, resulting in a denser and more stable coating.

[0032] Figures 12-18 SEM images of the 3AN-9-NECA-PY coatings at different concentration ratios are shown. When the concentration ratio of 3-AN-9-NECA to PY is 4:1, the two polymers are clearly seen to adhere orderly to the surface of the stainless steel wire, forming a relatively dense extraction coating (e.g., ...). Figure 12 The coating adhering to the surface of the stainless steel wire becomes significantly thicker than the coating of polymerized 3-AN-9-ethylcarbazole (e.g. Figure 13 Changing the concentration ratio of 3-AN-9-NECA to PY to 3:2 resulted in a cauliflower-like coating with a denser structure (e.g., ...). Figure 14-15 This structure provides favorable conditions for the adsorption of other molecules. Compared with the scanning electron microscope images of 3-AN-9-NECA monomer or PY monomer, this composite coating is more compact and has a larger usable surface area, which is beneficial for extraction. When the concentration ratio is 2:3, the cauliflower-like structure of polypyrrole in the porous network structure of the coating is more obvious (e.g., Figure 16 When the concentration ratio is 1:4, the coating exhibits a more polypyrrole structure (e.g., Figure 17 The coating is thicker but noticeably looser and easier to peel off (e.g.) Figure 18 ).

[0033] In a solution with a 3-AN-9-NECA to PY concentration ratio of 4:1, the addition of IL (1-butyl-3-methylimidazolium hexafluorophosphate) significantly altered the original cloud-like, wrinkled structure of the polymerized 3-AN-9-NECA, resulting in a more compact coating. This indicates that IL was effectively doped into the polymer coating. Figure 19 When IL was added to a polymerization solution with a 3:2 concentration ratio of 3-AN-9-NECA to PY, the gap between the coating layers decreased. Figure 20 In a solution with a 3-AN-9-NECA to PY concentration ratio of 2:3, the addition of IL significantly altered its structure, resulting in a smaller particle size. Figure 21 When IL was added to a solution with a 3-AN-9-NECA to PY concentration ratio of 2:3, the IL effectively adhered to the coating, exhibiting a needle-like structure. Figure 22 ).

[0034] (III) Condition Optimization 1. Effect of monomer concentration ratio Under otherwise unchanged conditions, this application prepared polymeric 3-AN-9-NCA-PY coatings with different concentration ratios. Maintaining a total concentration of 0.05 mol / L, the concentrations of 3-AN-9-NECA and PY monomers were varied to prepare four coatings with 3-AN-9-NECA:PY concentrations of 4:1, 3:2, 2:3, and 1:4, respectively, for the detection of geraniol. Figure 23 It can be seen that when the concentration ratio is 3:2, the adsorption force of the extraction head is the highest and the structure is stable.

[0035] 2. Effects of IL concentration With other conditions remaining unchanged, when 3-AN-9-NECA-PY is used and the concentration ratio is 3:2, the resulting extraction head can be adjusted by adding different concentrations of IL, with 1-butyl-3-methylimidazolium hexafluorophosphate being selected as the IL.

[0036] This experiment investigated the effects of four concentration gradients of ionic liquid (2 μL / mL, 4 μL / mL, 6 μL / mL, and 8 μL / mL) on the extraction head. Figure 24 It can be seen that the adsorption capacity of the SPME head increases with the increase of the amount of ionic liquid added. When the concentration of ionic liquid rises to 8 μL / mL, the adsorption capacity of the extraction head tends to stabilize. Therefore, it can be concluded that IL liquid can significantly increase the adsorption capacity of the extraction head to a certain extent.

[0037] 3. Extraction temperature Under otherwise constant conditions, temperature has a dual effect on the extraction process in HS-SPME. Increased temperature increases the diffusion coefficient of the analyte, facilitating its escape from the complex matrix and entry into the headspace phase, thus shortening the equilibrium time. However, absorption and adsorption are exothermic processes; under equilibrium conditions, increased temperature reduces the partition coefficient of the analyte between the coating and the sample, decreasing sensitivity. This experiment investigated the effect of extraction temperature on the adsorption capacity of the extraction head during headspace extraction. The changes in adsorption capacity at five temperatures (40°C, 50°C, 60°C, 70°C, and 80°C) were studied. When the temperature stabilized at 70°C, the adsorption capacity of the extraction head reached its maximum value, and when the temperature exceeded 70°C, the adsorption capacity gradually decreased with increasing temperature (see...). Figure 25 Therefore, the optimal extraction temperature for headspace extraction is 70ºC.

[0038] The extraction head used here is the best-performing polymerized 3-AN-9-NECA-PY-1-butyl-3-methylimidazolium hexafluorophosphate extraction head.

[0039] VII. Linearity and Sample Detection Analysis 1. Linear Analysis Different volumes of geraniol stock solution of the same concentration (50 μg / mL) were added to 20 mL headspace extraction flasks, along with 10 mL of saturated sodium chloride solution. Under optimized experimental conditions, the analyte was extracted from low to high concentration using the extraction head with the best extraction effect, followed by GC-MS analysis. A standard curve was plotted with the solution concentration on the x-axis and the corresponding peak area on the y-axis. Figure 26 As can be seen, the response peak area increases with increasing concentration and exhibits a good linear relationship. This method has good sensitivity and detection limit for the detection of geraniol.

[0040] The extraction head used here is the polymeric 3-AN-9-NECA-PY-1-butyl-3-methylimidazolium hexafluorophosphate extraction head, which has the best performance.

[0041] 2. Actual sample testing and analysis To evaluate the practicality of this method, this experiment applied it to the detection and analysis of geraniol in tea. The sample pretreatment method was as follows: 2.00 g of tea leaves and 3.60 g of sodium chloride were accurately weighed and added to a 20 mL headspace extraction flask. 10 mL of boiling distilled water was added at a tea-to-water ratio of 1:5 (mass-volume ratio, g / mL). A magnetic stir bar was added, and the flask was sealed with Teflon tape, then plugged with a rubber stopper and sealed with an aluminum cap. The extraction flask was placed in a 70 ℃ constant temperature water bath for 15 min to equilibrate. After sealing, the flask was analyzed under optimized conditions. Figure 27This is the chromatogram for the detection of tea samples. Simultaneously, to evaluate the above detection method, the samples were spiked and recovered, such as... Figure 28 Geraniol recoveries ranged from 87.6% to 101.7%, as shown in Table 2. This indicates that this method can be used for the detection of actual samples.

[0042] The extraction head used here is the polymeric 3-AN-9-NECA-PY-1-butyl-3-methylimidazolium hexafluorophosphate extraction head, which has the best performance.

[0043] Table 2. Analytical parameters of geraniol for 9-amino-ethylcarbazole-pyrrole SPME coating.

[0044] The above descriptions are merely some embodiments of the present invention. It should be noted that those skilled in the art can make other modifications and improvements without departing from the inventive concept of the present invention, and these all fall within the protection scope of the present invention.

Claims

1. An extraction head for detecting geraniol, characterized in that, The extraction head is a composite material of polymerized 3-amino-9-ethylcarbazole-pyrrole-IL, wherein IL is 1-butyl-3-methylimidazolium hexafluorophosphate.

2. The extraction head according to claim 1, characterized in that, The method for preparing the extraction head includes: A comonomer of 3-amino-9-ethylcarbazole and pyrrole was prepared, with IL being 1-butyl-3-methylimidazolium hexafluorophosphate and the solvent being a mixed solution of acetonitrile; The electrode system was inserted into the mixed solution, and a composite extraction head was prepared by cyclic voltammetry.

3. The extraction head according to claim 2, characterized in that, The concentration ratio of 3-amino-9-ethylcarbazole to pyrrole is 3:

2.

4. The extraction head according to claim 2, characterized in that, The concentration of the ionic liquid IL is 8 μL / mL.

5. The extraction head according to claim 2, characterized in that, The electrode system consists of: Ag / AgCl as the reference electrode; platinum wire as the auxiliary electrode; and stainless steel wire as the working electrode.

6. A method for detecting geraniol compounds, characterized in that, Includes the following steps: Geraniol compounds were extracted using the composite extraction head-up extraction method described in claims 1-5; Gas chromatography-mass spectrometry was constructed, and the extraction head was used to detect geraniol compounds.

7. The detection method according to claim 6, characterized in that, The head-of-head extraction of geraniol compounds using the composite extraction method includes the following steps: Prepare geraniol standard solution; Prepare geraniol working solution; Perform the HS-SPME operation; upon completion, Perform GC-MS operation.

8. The detection method according to claim 7, characterized in that, The HS-SPME operation includes the following steps: A saturated sodium chloride solution and a phenol-geraniol standard solution were added to the extraction flask to form the first mixture. The first mixture was heated and stirred in a water bath; Insert the injection device into the headspace extraction vial and expose the extraction head of the injection device above the extraction vial for headspace extraction.

9. The detection method according to claim 8, characterized in that, The GC-MS operation includes the following steps: After the HS-SPME operation steps are completed, Retract the extraction head into the protective sleeve, quickly insert it into the GC-MS injection port, analyze it, and then perform GC-MS separation and detection.

10. The detection method according to claim 8, characterized in that, The extraction temperature is 40 ℃-80 ℃.

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