Method for rapidly detecting acetamiprid, carbendazim and carbofuran in traditional Chinese medicine based on portable mass spectrometry technology

Abstract

The invention relates to the technical field of pesticide residue detection, in particular to a method for rapidly detecting acetamiprid, carbendazim and carbofuran in traditional Chinese medicine based on a portable mass spectrometry technology. The method specifically comprises the following steps: (1) extracting and purifying a sample to obtain a test solution; (2) diluting a pesticide into a mixed reference solution with a series of concentration gradients; (3) taking a sample without to-be-detected indexes, extracting and purifying to prepare blank matrix solutions, and respectively adding the blank matrix solutions into the mixed reference substance solutions with the series of concentration gradients to obtain blank matrix matching standard curve solutions; and (4) analyzing on a machine. According to the invention, a portable mass spectrum rapid screening method for residues of acetamiprid, carbendazim and carbofuran in traditional Chinese medicines is established by combining direct extraction with a hydrophilic-lipophilic balance material solid-phase extraction column purification method and combining with a small portable mass spectrum. The method has the advantages of rapidness, accuracy, sensitivity and the like, and has a good application prospect in the field of rapid detection of traditional Chinese medicine pesticide residues.

Description

Technical Field

[0001] The invention relates to the technical field of pesticide residue detection, and in particular to a rapid detection method for acetamiprid, carbendazim and carbofuran in traditional Chinese medicine based on portable mass spectrometry technology. Background Art

[0002] As an important part of traditional Chinese medicine culture, the quality and safety of Chinese medicinal materials have attracted worldwide attention. Pesticide pollution and residues in Chinese medicinal materials are one of the important factors affecting their quality and safety. In recent years, the abuse of pesticides in large-scale artificial cultivation has caused widespread pesticide residues in Chinese medicinal materials. At the same time, the harvesting, processing, storage, and transportation of Chinese medicinal materials will inevitably cause pesticide residue pollution, resulting in a high detection rate of pesticide residues in Chinese medicinal materials. Therefore, the development of fast and accurate pesticide residue detection technology in Chinese medicinal materials plays an important role in ensuring drug safety and strengthening full-chain industry supervision.

[0003] At present, the detection methods in the pesticide residue standards in traditional Chinese medicines include gas chromatography-tandem mass spectrometry and liquid chromatography-tandem mass spectrometry (LC-MS / MS). Most of the existing chromatography-tandem mass spectrometry methods rely on large mass spectrometry instruments, which have the advantages of high sensitivity and good repeatability, but the sample pretreatment is cumbersome, the analysis time is long, the instrument equipment is large, and the solvent consumption is large, which cannot meet the needs of rapid screening of pesticides. With the rapid development of mass spectrometry miniaturization and in-situ ionization technology, such as direct analysis in real time (DART), desorption electrospray ionization (DESI), and paper spray ionization (PSI), the expansion and application of portable mass spectrometry technology in the field of rapid detection has been greatly promoted.

[0004] The working principle of a small portable mass spectrometer is similar to that of a large mass spectrometer. It uses in-situ ionization and ion trap technology to ionize sample molecules, and uses electromagnetic fields to fragment them, separating product ions according to mass-to-charge ratios. Finally, the intensity of each ion is recorded by the detector, thereby achieving qualitative and quantitative analysis of sample components. Small mass spectrometers have rapid response capabilities and can quickly obtain data on site; their maintenance costs are relatively low and the operation is simple, so that non-professionals can use them after training. Small portable mass spectrometers are small in size, light in weight, low in power, and easy to carry. They can achieve on-site, rapid, and real-time analysis of pesticide residues in traditional Chinese medicines, and have very broad application prospects in real-world scenarios with on-site testing needs, such as medicinal material markets and planting bases.

[0005] In view of this, this study used acetamiprid, carbendazim and chlorpyrifos as detection indicators, and adopted portable mass spectrometry technology to explore its application in the rapid determination of pesticides in traditional Chinese medicines, so as to achieve rapid detection of acetamiprid, carbendazim and chlorpyrifos in traditional Chinese medicines, and provide a faster real-time analysis technology for the quality and safety supervision of traditional Chinese medicines. Summary of the invention

[0006] The purpose of the present invention is to provide a rapid detection method for acetamiprid, carbendazim and carbofuran in traditional Chinese medicine based on portable mass spectrometry technology. This study takes the widely used traditional Chinese medicines Panax notoginseng (root), honeysuckle (flower), and wolfberry (fruit) with high detection rates of pesticide residues as research objects, and takes the high detection rate pesticides acetamiprid, carbendazim and carbofuran as detection indicators. A sample pretreatment method of direct extraction combined with HLB solid phase extraction column purification is developed, which is used in conjunction with a small portable mass spectrometer to achieve high-sensitivity rapid screening of acetamiprid, carbendazim and carbofuran residues in traditional Chinese medicines.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] The present invention provides a method for rapid detection of acetamiprid, carbendazim and carbofuran in traditional Chinese medicine based on portable mass spectrometry technology, comprising the following steps:

[0009] (1) extracting and purifying the sample to obtain a test solution;

[0010] (2) diluting the pesticide into a series of mixed reference solutions with a concentration gradient;

[0011] (3) taking a sample that does not contain the index to be tested, extracting and purifying it to prepare a blank matrix solution, and adding it to the mixed reference solution of the series of concentration gradients to obtain a blank matrix matching standard curve solution;

[0012] (4) Adding the mixed reference solution and sample solution into an in-situ sampling ionization kit, inserting the kit into a mass spectrometer for analysis.

[0013] (5) Mass spectrometry conditions for analysis were as follows: ionization mode: positive ion mode; ion source voltage: 1.8-2.2 kV; scanning range: 50-1000 m / z; parent ion 190-230 m / z, daughter ion 120-170 m / z, collision induced dissociation voltage 1.4-1.6 V.

[0014] Preferably, the sample in step (1) is one or more of Panax notoginseng, honeysuckle or wolfberry; and the pesticide is one or more of acetamiprid, carbendazim or carbofuran.

[0015] Preferably, when the pesticide is acetamiprid, the mass spectrometry conditions are: ionization mode: positive ion mode; ion source voltage: 2 kV; scanning range: 50-1000 m / z; parent ion 223 m / z, daughter ion 126 m / z, collision induced dissociation voltage 1.5 V;

[0016] When the pesticide is carbendazim, the mass spectrometry conditions are: ionization mode: positive ion mode; ion source voltage: 2 kV; scanning range: 50-1000 m / z; parent ion 192 m / z, daughter ion 160 m / z, collision induced dissociation voltage 1.5 V;

[0017] When the pesticide is carbofuran, the mass spectrometry conditions are: ionization mode: positive ion mode; ion source voltage: 2kV; scanning range: 50-1000m / z; parent ion 222m / z, daughter ion 165m / z, collision induced dissociation voltage 1.5V.

[0018] Preferably, the extraction method in steps (1) and (3) is: mixing the crushed sample with acetonitrile to obtain a slurry, centrifuging to obtain a supernatant, concentrating under reduced pressure, and diluting to obtain a sample extract.

[0019] Preferably, the mass volume ratio of the sample to acetonitrile is 2 g:40-50 mL; the homogenization time is 2-4 min, and the rotation speed is 10000-14000 rpm; the centrifugation time is 4-6 min, and the rotation speed is 4000-6000 rpm.

[0020] Preferably, the purification method in step (1) is: purifying the sample extract through an HLB solid phase extraction column and collecting the purified liquid.

[0021] Preferably, the extract is diluted 4 to 5 times.

[0022] Preferably, the concentration of the blank matrix matching standard curve solution in step (3) is 0.025 to 8.0 μg / mL.

[0023] Preferably, when the pesticide is acetamiprid, the concentrations of the blank matrix matching standard curve solution are 0.2, 0.4, 0.8, 1.6, 4.0, and 8.0 μg / mL, respectively;

[0024] When the pesticide is carbendazim, the concentrations of the blank matrix matching standard curve solution are 0.025, 0.05, 0.1, 0.2, 0.5, and 1.0 μg / mL, respectively;

[0025] When the pesticide is carbofuran, the concentrations of the blank matrix matching standard curve solution are 0.05, 0.1, 0.2, 0.4, 1.0, and 2.0 μg / mL, respectively.

[0026] The in-situ ionization box used in the present invention adopts nanospray technology.

[0027] The portable mass spectrometry operation method provided by the present invention comprises the following steps: inserting the loaded nanospray reagent kit into a small portable mass spectrometry injection port, setting parameters of the small portable mass spectrometry, ionizing the sample for small portable mass spectrometry detection, drawing a standard curve and conducting quantitative analysis.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] (1) The present invention is based on direct extraction combined with HLB solid phase extraction column purification method, and is combined with a small portable mass spectrometer to establish a portable mass spectrometry rapid screening method for acetamiprid, carbendazim, and carbofuran residues in traditional Chinese medicine. Studies have shown that the detection limits of acetamiprid, carbendazim, and carbofuran are 0.3 mg / kg, 0.05 mg / kg, and 0.10 mg / kg, respectively, and the quantitative limits are 1 mg / kg, 0.125 mg / kg, and 0.25 mg / kg, respectively. The recovery rate is between 73% and 95%, and it has been verified by LC-MS / MS method.

[0030] (2) This method uses an in-situ ionization box without chromatographic separation, which greatly shortens the analysis time. According to the existing standard method, the mass spectrometry analysis time of acetamiprid, carbendazim, and carbofuran is about 20 minutes, while the in-situ ionization box combined with a portable mass spectrometer can complete the sample analysis within 2 minutes;

[0031] (3) The detection limits and quantification limits of acetamiprid in wolfberry and honeysuckle matrix, and carbendazim in Panax notoginseng matrix are lower than the maximum residue limits specified in the "GB2763-2021 National Food Safety Standard Maximum Residue Limits of Pesticides in Food" and the "Chinese Pharmacopoeia 2025 Edition Public Draft", indicating that the portable mass spectrometer has a certain sensitivity and qualitative ability, which can meet the needs of rapid screening of pesticide residues in traditional Chinese medicine;

[0032] (4) The screening method established in this study was used to screen 17 batches of positive samples of Lycium barbarum, Panax notoginseng and honeysuckle, and the test results were basically consistent with the results of LC-MS / MS. In summary, this method has the advantages of rapidity, sensitivity and accuracy, and has good application prospects in the field of rapid detection of pesticide residues in traditional Chinese medicine. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0034] Figure 1 The following are the secondary mass spectra of three pesticides: (a) acetamiprid, (b) carbendazim, and (c) carbofuran;

[0035] Figure 2 This is the collision energy optimization diagram of acetamiprid, carbendazim and chlorpyrifos. DETAILED DESCRIPTION

[0036] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0037] Example 1

[0038] 1.1 Instruments and reagents

[0039] Cell portable mass spectrometry analysis system (33.3 cm × 23.5 cm × 14.6 cm, mass ≤ 8.5 kg, power ≤ 85 W, Qingpu Technology (Suzhou) Co., Ltd.), equipped with PMS ClientPro mass spectrometry analysis software; LCMS-TQ8050 liquid chromatography tandem triple quadrupole mass spectrometer (Shimadzu Corporation); electronic analytical balance (Shanghai Yueping); high-speed centrifuge (ThermoScientific); automatic high-speed homogenizer (RayKol Group Co., Ltd.); Hei-VAPAdvantage rotary evaporator (Heidolph, Germany).

[0040] Carbofuran was purchased from Alta Technology Co., Ltd. with a purity greater than 98%; carbendazim and acetamiprid were purchased from Tanmo and Anpu Technology Co., Ltd., respectively; methanol and acetonitrile (chromatographically pure, Fisher, USA); Panax notoginseng, honeysuckle and wolfberry medicinal materials; HLB solid phase extraction column (CNW) was purchased from Shanghai Anpu Experimental Technology Co., Ltd.

[0041] 1.2 Experimental methods

[0042] 1.2.1 Preparation of pesticide mixed reference solution

[0043] Using acetonitrile as solvent, prepare 400μg / mL acetamiprid, 50μg / mL carbendazim, and 100μg / mL single reference substance solutions of three pesticides as mother solutions, and store them at 4℃ for later use. Take 1mL of each of the three pesticide single reference substance mother solutions, dilute to 10mL with acetonitrile, and prepare pesticide mixed reference substance stock solutions with concentrations of acetamiprid (40μg / mL), carbendazim (5μg / mL), and carbendazim (10μg / mL). Take the pesticide mixed reference substance stock solution and dilute it with acetonitrile to a series of pesticide mixed reference substance solutions with a concentration gradient.

[0044] 1.2.2 Preparation of blank matrix matching standard curve

[0045] Take 2g of sample without the index to be tested and treat it with the same preparation method as the test solution to prepare a blank matrix solution. Take 0.8mL of the blank matrix solution and add 0.2mL of the pesticide mixed reference solution with a series of concentration gradients to obtain the blank matrix matching standard curve solution. The concentrations of the blank matrix matching standard curve solutions of acetamiprid, carbendazim and carbofuran are shown in Table 1.

[0046] Table 1 Blank matrix matching standard curve solution concentration

[0047]

[0048]

[0049] 1.2.3 Preparation of test solution

[0050] Extraction: Take 2 g of the test sample powder (passed through No. 3 sieve), weigh accurately, add 45 mL of acetonitrile, homogenize for 3 minutes (speed not less than 12000 revolutions per minute), centrifuge (5000 revolutions per minute) for 5 minutes, separate the supernatant, concentrate under reduced pressure to about 3-5 mL, cool, dilute to 10 mL with acetonitrile, shake well, and obtain.

[0051] Purification: Take 4 mL of the sample extract prepared above, purify it through a hydrophilic-lipophilic balance material (HLB SPE) solid phase extraction column (200 mg, 6 mL), collect all the purified liquid, mix well, and obtain.

[0052] 1.2.4 Portable mass spectrometry

[0053] Take 0.8 mL of the test solution prepared above, add 0.2 mL of acetonitrile, mix well, and wait for determination.

[0054] 20 μL of blank matrix matching standard curve solution and the above solution were loaded into the nanospray kit respectively, and inserted into the instrument for detection.

[0055] The mass spectrometry analysis conditions were as follows: ionization mode: positive ion mode; ion source voltage: 2 kV; m / z scanning range: 50-1000. The mass spectrometry analysis parameters such as ionization mode, ion pair information and detection limit of the three pesticides are shown in Table 2, and the secondary mass spectra are shown in Figure 1 .

[0056] Table 2 Mass spectrometry analysis parameters

[0057]

[0058] 1.2.5 LC-MS / MS method validation

[0059] The verification method of pesticides refers to the draft of the determination method of pesticide residues in 2341 of the 2025 edition of the Chinese Pharmacopoeia. LC-MS / MS is used for determination, and the chromatographic and mass spectrometric conditions are briefly described as follows:

[0060] Liquid chromatography conditions: octadecylsilane bonded silica gel as filler (Agilent XDB-C18 column length 10 cm, inner diameter 1.8 mm, particle size 2.1 μm); 0.1% formic acid solution (containing 5 mmol / L ammonium formate) as mobile phase A, methanol-0.1% formic acid solution (containing 5 mmol / L ammonium formate) (95:5) as mobile phase B, gradient elution according to Table 3; flow rate 0.3 mL / min, column temperature 40°C.

[0061] Table 3 Mobile phase gradient

[0062]

[0063] Mass spectrometry conditions: Detection was performed by triple quadrupole tandem mass spectrometer; the ion source was electrospray ionization (ESI) source. Positive ion scanning mode. Monitoring mode was multiple reaction monitoring (MRM). The reference retention time, monitoring ion pairs, and collision voltage (CE) of each compound are shown in Table 4.

[0064] Table 4 Retention time, monitoring ion pairs and collision voltage (CE) of each pesticide

[0065]

[0066] The preparation of mixed reference solution is the same as in 1.2.1.

[0067] The preparation of matrix mixed control solution is the same as in 1.2.2.

[0068] The preparation of the test solution is the same as in 1.2.3.

[0069] Determination method: Accurately pipette 0.1 μL of matrix mixed control solution and solution to be determined under 1.2.4 respectively, inject into liquid chromatography-tandem mass spectrometer, and calculate according to external standard curve method to obtain the result.

[0070] 2 Results

[0071] 2.1 Optimization of detection methods

[0072] In this experiment, the collision energy optimization was performed by collecting collision-induced dissociation energy (cid_amp) traversal data, ranging from 0 to 2.5 V, with a step size of 0.5 V, and selecting the collision-induced dissociation energy with the strongest daughter ion intensity for each pesticide index as the optimal value for each index. Figure 2 It can be seen that the optimal collision-induced dissociation energy of acetamiprid, carbendazim and chlorpyrifos is 1.5V.

[0073] 2.2 Methodological Investigation Results

[0074] 2.2.1 Linear range and detection limit

[0075] Different concentrations of blank matrix matching standard curve solutions were prepared for sample analysis, and linear regression analysis was performed with mass concentration as the horizontal axis (x) and the quantitative ion mass spectrometry signal intensity as the vertical axis (y) to obtain the linear equations of each index pesticide (see Table 5). The pesticides had a good linear relationship within their respective linear ranges, and the correlation coefficients (r) were all greater than 0.99. The detection limit and quantification limit of the method were determined by 3 times and 10 times the signal-to-noise ratio, respectively. The detection limits of acetamiprid, carbendazim and carbofuran in wolfberry, Panax notoginseng and honeysuckle matrices were 0.3 mg / kg, 0.05 mg / kg and 0.10 mg / kg, respectively, and the quantification limits were 1 mg / kg, 0.125 mg / kg and 0.25 mg / kg, respectively.

[0076] The "GB2763-2021 National Food Safety Standard Maximum Residue Limits of Pesticides in Food" and the "Chinese Pharmacopoeia" 2025 Edition 0212 General Rules for the Inspection of Medicinal Materials and Decoctions stipulate that the maximum residue limit (Maximum Residue Level, MRL) of acetamiprid in wolfberry and honeysuckle is 2 mg / kg and 15 mg / kg respectively, the MRL of carbendazim in Panax notoginseng is 1 mg / kg, and the MRL of the banned pesticide chlorpyrifos in medicinal materials and decoctions (plant-based) is 0.02 mg / kg. The quantification limits of the acetamiprid and carbendazim determination methods established using portable mass spectrometry are lower than the MRL values ​​specified in GB2763-2021 and the draft public notice of the 2025 edition of the "Chinese Pharmacopoeia", indicating that the portable mass spectrometer has a certain sensitivity and qualitative capability and can meet the daily inspection needs of pesticide residues in traditional Chinese medicine; the quantification limit of the chlorpyrifos detection method established by portable mass spectrometry is still different from the limit specified in the pharmacopoeia standard, and can be used as a daily screening method for chlorpyrifos in traditional Chinese medicine.

[0077] 2.2.2 Recovery and reproducibility

[0078] A spike recovery test was conducted in the Chinese medicine samples that were determined to be free of the above three pesticides. Three parallel experiments were conducted at each concentration. The spike recovery of each pesticide and the relative standard deviation of 8 repeated measurements are shown in Table 5. The average recovery (n=3) of acetamiprid, carbendazim and carbofuran was between 73% and 95%, and the relative standard deviation of 8 repeated measurements was 10% to 34%. This shows that the pesticide residue rapid detection technology formed by the pretreatment method combined with the portable mass spectrometer has good sensitivity and accuracy, and is suitable for the rapid detection of pesticide residues such as acetamiprid, carbendazim and carbofuran in Chinese medicine varieties such as honeysuckle, wolfberry, and Panax notoginseng.

[0079] Table 5 Methodological investigation results of acetamiprid, carbendazim and carbofuran

[0080]

[0081] 2.3 Analysis of actual Chinese medicine samples and validation of LC-MS / MS standard methods

[0082] Using the method of the present invention, 5 batches of honeysuckle, 6 batches of wolfberry and 6 batches of positive samples of Panax notoginseng collected from the market were measured respectively, and compared with the standard LC-MS / MS method for pesticide residue determination, and the results are shown in Table 6. The portable mass spectrometry established in this description was used to analyze the residues of acetamiprid, carbendazim and carbofuran in 17 batches of samples, and the detected amounts were 1.760-3.537 mg / kg, 0.176-0.503 mg / kg and 0.378-1.146 mg / kg, respectively. At the same time, the standard method LC-MS / MS method was used for verification, and it was found that more than 70% of the data results of pesticide residues in traditional Chinese medicine determined by traditional large mass spectrometry were basically consistent with the portable mass spectrometry results, and the relative deviation between the two was less than 20%, and no false positive or false negative results appeared in the portable determination results, proving that it is suitable for the simultaneous rapid detection of multiple pesticide residues in complex matrices of traditional Chinese medicine.

[0083] Table 6 Comparison of the results of pesticide determination in traditional Chinese medicine samples

[0084]

[0085]

[0086] Note: “ / ” means that the indicator is not detected.

[0087] The method provided by the present invention has strong qualitative and semi-quantitative capabilities, and compared with traditional laboratory analysis methods, the present method adopts in-situ ionization mass spectrometry technology to greatly shorten the total analysis time, greatly reduce the amount of solvent used, and has the convenience of on-site operation, and has reached a level similar to that of traditional methods in terms of detection sensitivity. The method of the present invention can improve the detection speed, shorten the detection time, and is suitable for rapid screening of large quantities of medicinal materials, which is more in line with the development trend of modern analytical chemistry that is efficient and green. However, it is worth noting that portable mass spectrometry belongs to in-situ ionization method, which lacks the separation function of chromatography, so that the background interference caused by the matrix components during determination is large, which may affect the determination sensitivity and accuracy of the instrument, so the instrument sensitivity and anti-interference ability need to be further improved.

[0088] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A rapid detection method for acetamiprid, carbendazim and carbofuran in traditional Chinese medicine based on portable mass spectrometry technology, characterized in that: The steps include: (1) extracting and purifying the sample to obtain a test solution; (2) diluting the pesticide into a series of mixed reference solutions with a concentration gradient; (3) taking a sample that does not contain the index to be tested, extracting and purifying it to prepare a blank matrix solution, and adding it to the mixed reference solution of the series of concentration gradients to obtain a blank matrix matching standard curve solution; (4) adding the mixed reference solution and the sample solution into an in-situ sampling ionization spray kit, inserting the kit into a mass spectrometer for analysis; (5) Mass spectrometry conditions for analysis were as follows: ionization mode: positive ion mode; ion source voltage: 1.8-2.2 kV; scanning range: 50-1000 m / z; parent ion 190-230 m / z, daughter ion 120-170 m / z, collision induced dissociation voltage 1.4-1.6 V.

2. The detection method according to claim 1, characterized in that: The sample in step (1) is one or more of Panax notoginseng, honeysuckle or wolfberry; and the pesticide is one or more of acetamiprid, carbendazim or carbofuran.

3. The detection method according to claim 1, characterized in that: When the pesticide is acetamiprid, the mass spectrometry conditions are: ionization mode: positive ion mode; ion source voltage: 2 kV; scanning range: 50-1000 m / z; parent ion 223 m / z, daughter ion 126 m / z, collision induced dissociation voltage 1.5 V; When the pesticide is carbendazim, the mass spectrometry conditions are: ionization mode: positive ion mode; ion source voltage: 2 kV; scanning range: 50-1000 m / z; parent ion 192 m / z, daughter ion 160 m / z, collision induced dissociation voltage 1.5 V; When the pesticide is carbofuran, the mass spectrometry conditions are: ionization mode: positive ion mode; ion source voltage: 2kV; scanning range: 50-1000m / z; parent ion 222m / z, daughter ion 165m / z, collision induced dissociation voltage 1.5V.

4. The detection method according to claim 1, characterized in that: The extraction method in steps (1) and (3) is: mixing the crushed sample with acetonitrile to obtain a homogenous slurry, centrifuging to obtain a supernatant, concentrating under reduced pressure, and diluting to obtain a sample extract.

5. The detection method according to claim 4, characterized in that: The mass volume ratio of the sample to acetonitrile is 2 g:40-50 mL; the homogenization time is 2-4 min, and the rotation speed is 10000-14000 rpm; the centrifugation time is 4-6 min, and the rotation speed is 4000-6000 rpm.

6. The detection method according to claim 4, characterized in that: The purification method in step (1) is: purifying the sample extract through an HLB solid phase extraction column and collecting the purified liquid.

7. The detection method according to claim 4, characterized in that: The dilution multiple of the extract is 4 to 5 times.

8. The detection method according to claim 1, characterized in that: The concentration of the blank matrix matching standard curve solution in step (3) is 0.025-8.0 μg / mL.

9. The detection method according to claim 8, characterized in that: When the pesticide is acetamiprid, the concentrations of the blank matrix matching standard curve solution are 0.2, 0.4, 0.8, 1.6, 4.0, and 8.0 μg / mL, respectively; When the pesticide is carbendazim, the concentrations of the blank matrix matching standard curve solution are 0.025, 0.05, 0.1, 0.2, 0.5, and 1.0 μg / mL, respectively; When the pesticide is carbofuran, the concentrations of the blank matrix matching standard curve solution are 0.05, 0.1, 0.2, 0.4, 1.0, and 2.0 μg / mL, respectively.

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