CN105486797A - LC-Q-TOF/MS (liquid chromatography-quadrupole-time of flight/mass spectrometry) technology for detecting 544 kinds of pesticide residues in bud vegetables - Google Patents

Abstract

The present invention establishes a LC-Q-TOF/MS detection technology for 544 kinds of pesticide residues in sprout vegetables. LC-Q-TOF/MS in TOF/MS mode, respectively measure the retention time of each pesticide standard under the specified chromatographic mass spectrometry conditions, determine the ionization form and chemical formula of the compound under the ESI source, and obtain the parent ion of each compound Accurate mass numbers of the TOF/MS database. In the Q-TOF/MS mode, the fragment ion mass spectra of each pesticide standard were collected under 3-5 different collision energies, and the collected information was imported into the PCDL software to form a Q-TOF/MS database. By comparing the retention time, primary mass spectrometry and secondary mass spectrometry information in the sprout vegetable samples, it is determined whether the sample contains pesticide residues, and the secondary confirmation is carried out for the compounds with higher primary scores. If the secondary score is higher, that is Confirm the detection of relevant pesticide residues. The invention has the advantages of rapidity, high throughput, high precision, high reliability and the like, and can accurately screen the pesticides in sprout vegetables.

Description

LC-Q-TOF/MS detection technology for 544 kinds of pesticide residues in sprout vegetables

technical field

The invention relates to the fields of food hygiene and agricultural product safety detection, in particular to a method for detecting 544 kinds of pesticide residues in sprout vegetables.

Background technique

As early as 1976, the World Health Organization (WHO), the Food and Agriculture Organization (FAO) and the United Nations Environment Program (UNEP) jointly established the Global Environment Monitoring System/Food Project (Global Environment Monitoring System, GEMS/Food), aiming to grasp the status of food contamination in member countries , understand the intake of food pollutants, protect human health, and promote trade development. Now, all countries in the world have raised food safety to the strategic position of national security. Pesticide residue limit is one of the food safety standards and also the entry threshold for international trade. At the same time, the requirements for pesticide residues show a development trend of more and more varieties and stricter limits, that is, the threshold for pesticide residue limits established by international trade is getting higher and higher. Now the European Union has formulated 162,248 MRL standards for 839 pesticides, the United States has formulated 39,147 MRL standards for 351 pesticides, Japan has formulated more than 51,600 MRL standards for 579 pesticides, and my country has issued 3,650 MRL standards for 381 pesticides in 2014. MRL standard. At present, the uniform standard limit generally adopted in the world is 10 μg/kg. Therefore, both food safety and international trade call for high-throughput rapid pesticide residue detection technology, which undoubtedly provides opportunities and challenges for the majority of pesticide residue analysis workers. Among the current analytical techniques for pesticide residues, chromatography-mass spectrometry is the best analytical method to achieve high-throughput rapid detection of multiple residues.

At present, the analysis of pesticide residues is mainly based on gas chromatography, liquid chromatography, gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry. These detection techniques all first need pesticide standard control for qualitative. For example, for the detection of 100 kinds of pesticides, it is necessary to prepare corresponding 100 kinds of pesticide standard controls, and the pesticides other than these 100 kinds will be missed. In the actual work of pesticide and veterinary drug residue laboratories, most laboratories do not store hundreds of pesticide standard products. The reason is that pesticide standard products are not only expensive, but also valid for only 2 or 3 years, requiring repeated investment. There are only dozens of standard pesticides in general laboratories, and the types of pesticides that are routinely monitored are limited to these dozens, resulting in loopholes in food safety monitoring.

After years of painstaking research, the team of the present inventors has developed two kinds of accurate mass databases of 544 pesticides and a detection technology of 544 pesticide residues in sprout vegetables. More than 500 kinds of pesticide residues in vegetables can be quickly detected and detected at the same time, which meets the urgent need for high-throughput and rapid detection of pesticide residues in agricultural products.

Contents of the invention

On the basis of evaluating the mass spectrometry behavior characteristics of more than 1,000 commonly used pesticides in the world, the present invention innovatively establishes TOF/MS and Q-TOF/MS accurate mass databases for 544 kinds of pesticides; LC-Q-TOF/MS technical method for detection and confirmation of 544 pesticides based on TOF/MS and Q-TOF/MS accurate mass databases, with compound mass spectrum information such as number, isotope distribution, and isotope abundance as the identification standard; Innovatively developed a high-throughput sample preparation technology for pesticide residues in sprout vegetables. Realized the rapid detection of more than 500 kinds of pesticides in sprout vegetables with only one sample preparation and one sample injection detection, and the Q-TOF/MS database confirmation of the detected pesticides was realized, which completely changed the The original qualitative mode using compound standards as a reference is a fast, high-throughput, accurate and reliable new technology for pesticide residue detection that does not require standard comparison.

One, the innovation of the present invention lies in:

1. Innovatively established an accurate mass database of 544 pesticides with an accurate mass of 0.0001m/z, including TOF/MS database and Q-TOF/MS database.

2. The TOF/MS database contains English names, chemical molecular formulas, retention times, accurate mass numbers, isotope distributions, isotope abundances, and full-scan mass spectrum information of precursor ions and fragment ions for 544 pesticides. The information is large, accurate and comprehensive.

3. The full-scan mass spectrogram information of each pesticide fragment ion in the Q-TOF/MS database is obtained by optimizing the full-scan mass spectrogram under eight different collision energies to obtain four fragment ions with rich ion information under different collision energies Full scan image.

4. Innovatively established an identification standard based on compound mass spectrum information such as high-resolution accurate mass number, isotope distribution, and isotope abundance. Based on TOF/MS and Q-TOF/MS accurate mass databases, 544 pesticides were detected and analyzed. The proven LC-Q-TOF/MS technology method has completely changed the original qualitative mode using compound standards as a reference. It is a fast, high-throughput, accurate and reliable pesticide residue detection method that does not require standard control. technology.

5. The residue detection technology method established in the present invention can provide the target compound by searching and comparing with the corresponding information of the compound in the TOF/MS database based on the retention time, accurate mass number, isotope distribution and isotope abundance of the target compound. The match score value for the compound. According to the score value of the target compound, the qualitative detection of pesticides is realized.

6. The residue detection technology and method established in the present invention can be based on the full-scan mass spectrogram information of the fragment ions of the target compound, and by searching and comparing with the full-scan mass spectrogram information of the compound fragment ions in the Q-TOF/MS database, the target compound can be given The matching degree score value can realize the qualitative confirmation of the target compound. Compared with the traditional detection qualitative confirmation method, due to the use of full-scan mass spectrogram information comparison, it has higher qualitative accuracy.

7. Developed a high-throughput sample preparation technology for pesticide residues in agricultural products that matches the residue detection technology. It realizes the rapid detection and confirmation of more than 500 pesticides in agricultural products with only one sample preparation and two sample injections.

8. LC-Q-TOF/MS main detection technical indicators: scanning range 50-1600m/z; measured accurate mass can reach 0.0001m/z; mass accuracy can be controlled within 10ppm of molecular mass; scanning speed is 50- The 1600m/z range is 4 times per second. LC-Q-TOF/MS main detection technology features: one-time sample preparation, 544 kinds of pesticide detection, qualitative and confirmation can be completed within 1 hour; more than 80% of the pesticide confirmation points reach more than 10; 544 kinds of pesticides detected at the same time Among the pesticides, the detection sensitivity of 327 pesticides is lower than the standard of 10 μg/kg, accounting for 64.1%, which basically meets the requirements of screening for MRL levels of pesticide residues in various countries.

Two, the technical scheme that the present invention adopts:

1. Establish an accurate mass database

1.1 Establishment of TOF/MS database

In TOF/MS mode, respectively measure the retention time of each pesticide standard under the specified chromatographic mass spectrometry conditions, determine the ionization form (+H, +NH ₄ , +Na) and chemical formula of the compound under the ESI source, and obtain each Accurate mass numbers, isotopic peak distributions and abundance ratios of parent ions of each compound. The name, retention time, molecular formula, accurate mass number, isotope peak distribution and abundance ratio of 544 pesticides were imported into the database CSV software file to form a TOF/MS database.

1.2 Establishment of Q-TOF/MS database

The parent ions of 544 pesticides in the TOF/MS database were sequentially input in the AgilentMassHunter data acquisition interface. In the Q-TOF/MS mode, the fragment ion full-scan mass spectra were collected for 544 pesticides under 8 collision energies respectively. Preferably, 3-5 full-scan mass spectrograms of fragment ions under different collision energies with rich ion information are imported into the database software file, and are associated with the corresponding pesticide information to form a Q-TOF/MS database.

2. Establish a technical method for the detection and confirmation of 544 pesticides by LC-Q-TOF/MS based on compound information such as high-resolution accurate mass, isotope distribution, and isotope abundance. The technical steps include:

2.1 Sample preparation: The vegetable sprouts samples were extracted with 1% acetic acid acetonitrile, purified with Carbon/NH ₂ column, acetonitrile + toluene (3+1, v/v) to elute residual pesticides, concentrated, dissolved and filtered to prepare Sample liquid;

The sprout vegetables include mung bean sprouts, Chinese toon sprouts and grass heads;

2.2 Chromatography and mass spectrometry detection: Use liquid chromatography equipped with a reversed-phase chromatographic column (ZORBAXSB-C18, 2.1mm×100mm, 3.5μm) to separate the pesticides in the sample liquid to be tested, and LC-Q-TOF equipped with an electrospray ion source - MS detection;

2.3TOF/MS database qualitative detection method: Call the established TOF/MS database in AgilentMassHunter qualitative software, and search for the target compound qualitatively according to the TOF/MS database. The retention time deviation of the search parameters is limited to ±0.5min, and the accurate mass deviation is limited ±10ppm, select +H, +NH ₄ , +Na mode for the ionization form, and the software will base on the deviation between the measured value of each compound’s retention time, accurate mass and other elements and the theoretical value in the TOF/MS database, as well as the isotope distribution and The four parameters of isotope ratio, by scientifically setting the weight of each element in the calculation of matching score (the weight of accurate mass deviation is the highest), give the search matching score value, and search for compounds with higher matching score value, For suspected compounds, the accuracy of the method for qualitatively detecting pesticide residues in agricultural products based on the TOF/MS database is over 90%;

2.4Q-TOF/MS database qualitative confirmation method: In the TargetedMS/MS acquisition mode, input the precursor ion, retention time and optimal collision energy of the suspected compound, and detect the sample solution again, and compare the detected mass spectrum with the Q -The full-scan mass spectrum of the compound fragment ions in the TOF/MS database is matched under mirror image comparison conditions. According to whether the characteristic ion distribution is consistent with the spectral library, the accurate mass deviation of the secondary fragments and the ratio of fragment ions are given a score, and the matching A higher score indicates that the target compound was confirmed to be detected. The confirmation method uses full-scan mass spectrogram matching confirmation, so that more than 80% of the pesticide confirmation points can reach more than 10, which has higher qualitative accuracy than the standard requirement of 4 confirmation points.

Three, technical content of the present invention:

The invention provides two accurate mass databases of 544 kinds of pesticides and a detection technology for detecting 544 kinds of pesticide residues in sprout vegetables.

1. The two accurate mass databases provided by the present invention are TOF/MS database and Q-TOF/MS database.

1.1 The technical content of the TOF/MS database includes: chemical formulas, accurate mass numbers, retention times, and English names of pesticides for 544 pesticides. Examples of the technical content of the three compounds in the TOF/MS database are as follows:

1.2 The technical content of the Q-TOF/MS database includes: fragment ion information mass spectra of 544 pesticides under 4 collision energies. An example of the technical content of the Q-TOF/MS database is shown in Figure 1.

2. The present invention provides a technical method for LC-Q-TOF/MS detection and confirmation of 544 kinds of pesticides in sprout vegetables. The technical methods of detection and confirmation include the following:

2.1 Sample preparation

2.1.1 Take the edible part of the sprout vegetable sample, chop it up, mix it evenly, seal it, and mark it.

2.1.2 Weigh 10g of sprout vegetable samples (accurate to 0.01g), add 40mL of 1% acetic acid acetonitrile into an 80mL centrifuge tube, use a high-speed homogenizer at 13500r/min, homogenize and extract for 1min, add 1g of sodium chloride, 4g of anhydrous magnesium sulfate, shake for 5min, centrifuge at 4200r/min for 5min, take 20mL of the supernatant, concentrate it to about 1mL by rotary evaporation in a water bath at 40°C, and wait for purification.

2.1.3 Add about 2cm high anhydrous sodium sulfate to the Carbon/NH2 column. Rinse the SPE column with 4mL of acetonitrile + toluene (3+1, v/v) first, and discard the effluent. When the liquid level reaches the top of sodium sulfate, quickly transfer the concentrated sample solution to the purification column, and connect it with a new one. Heart bottle received. Then use 2 mL of acetonitrile + toluene (3+1, v/v) to wash the sample solution bottle three times each time, and transfer the washing solution into the SPE column. Connect a 50mL reservoir to the column, and then use 25mL of acetonitrile + toluene (3+1, v/v) to elute the pesticides, combine them in a heart bottle, and concentrate in a 40°C water bath to about 0.5mL.

2.1.4 Dry the concentrated solution under nitrogen, add 2mL of acetonitrile + 0.1% formic acid water (2+8, v/v) and mix well, filter through a 0.2μm filter membrane and constant volume to obtain the sample solution to be tested a .

2.2 LC-Q-TOF/MS detection

2.2.1 Liquid chromatography separation: the sample solution a to be tested is separated by a liquid chromatography system equipped with a reversed-phase chromatographic column (ZORBAXSB-C18, 2.1mm×100mm, 3.5μm); mobile phase A is 5mM ammonium acetate-0.1 % formic acid-water; mobile phase B is acetonitrile; liquid chromatography gradient elution program is: 0min: 1% B, 3min: 30% B, 6min: 40% B, 9min: 40% B, 15min: 60% B, 19min: 90%B, 23min: 90%B, 23.01min: 1%B, last run for 4min; flow rate: 0.4mL/min; column temperature: 40°C; injection volume: 10μL.

2.2.2 Mass spectrometry detection: Agilent6530LC-Q-TOF/MS in electrospray ionization positive ion mode (ESI+); capillary voltage: 4000V; drying gas temperature: 325°C; drying gas flow rate 10L/min, sheath flow rate 11L/min, The temperature of the sheath gas is 325°C; the atomizing gas pressure is 40psi, the cone voltage is 60V, and the fragmentation voltage is 140V. The mass-to-nucleus ratio range of the full scan is 50-1600m/z, and the internal standard reference solution is used to correct the mass accuracy of the instrument in real time. The mass spectrometry data was collected and processed by AgilentMassHunterWorkstationSoftware (version B.05.00).

2.3 TOF/MS database qualitative detection

Invoke the established TOF/MS database in the AgilentMassHunter qualitative software, set the retention time deviation of the search parameters to ±0.5min, the accurate mass deviation to ±10ppm, and select +H, +NH4, +Na mode for the ionization form; according to TOF/MS The database performs a qualitative search on the mass spectrometry data of the sample solution collected above, and calculates the search matching score value of each compound through software, and the compound with a search matching score value > 70 is a suspected compound.

2.4Q-TOF/MS database qualitative confirmation

In the Targeted MS/MS acquisition mode, input the precursor ion, retention time and optimal collision energy of the suspected compound to be detected, and detect the sample solution a again, and compare the detected mass spectrum with the compound fragment ion in the Q-TOF/MS database. Full-scan mass spectrum, matching confirmation under mirror image contrast conditions. If the matching score is greater than 70, the target compound is confirmed to be detected.

The beneficial effect that the present invention has compared with prior art is:

1. The present invention uses compound information such as high-resolution accurate mass, isotope distribution, and isotope abundance as identification standards, and establishes more than 500 pesticide detection and confirmation techniques, which completely change the original method of using compound standards as references. Qualitative mode is a fast, high-throughput, accurate and reliable new technology for pesticide residue detection that does not require standard control;

2. The present invention realizes the qualitative detection and confirmation of more than 500 kinds of pesticide residues on the premise of no need for comparison with standard substances, which can greatly save the cost of purchasing standard substances, and is also more environmentally friendly and safer;

3. The invention can complete the detection, characterization and confirmation of more than 500 kinds of pesticides within one hour. Compared with traditional detection methods, the work efficiency can be improved hundreds of times;

4. The present invention can extract and purify more than 500 kinds of pesticide residues in sprout vegetable samples at one time, and conduct one-time sampling detection. Compared with traditional detection methods, it can save detection costs and improve work efficiency hundreds of times;

5. Among the 544 kinds of pesticides detected by the present invention at the same time, there are 327 kinds of pesticides whose detection sensitivity is lower than 10 μg/kg, accounting for 64.1%, basically meeting the requirements of screening for MRL levels of pesticide residues in various countries;

6. On the premise that no comparison of pesticide standards is required, the present invention can identify and confirm the target compound based on the accurate mass database, so that more than 80% of the pesticide confirmation points can reach more than 10, and all pesticides meet the European Union's requirements for four confirmation points for compounds. requirements, the qualitative results are more accurate and reliable;

7. The pesticides in the sprout vegetable samples that can be tested in the present invention include one or more of the following substances: organophosphorus pesticides, carbamate pesticides, benzimidazole pesticides, sulfonylurea pesticides, nicotine Pesticides, pyrethroid pesticides and other types of pesticides and metabolites;

8. The detection technical indicators established by the present invention: the scanning range is 50-1600m/z; the measured accurate mass can reach 0.0001m/z; the mass accuracy can be controlled within 10ppm of the molecular mass; the scanning speed is in the range of 50-600m/z 4 times per second;

9. The accurate mass database of two kinds of 544 kinds of pesticides provided by the present invention and a detection technology for detecting 544 kinds of pesticide residues in sprout vegetables have been promoted and applied in 7 pesticide residue analysis laboratories. After 30 The detection and verification of more than 500 commercially available sprout vegetable samples in provinces and cities has obtained important residue detection data.

Description of drawings

Figure 1 Mung bean sprouts sample full-scan mode TOF score diagram;

Figure 2 Example diagram of the secondary collection method for suspected pesticides in mung bean sprout samples;

Fig. 3 Secondary Q-TOF/MS confirmation scores of pesticides detected in mung bean sprouts samples.

Figure 4 TOF score diagram of grass head sample in full scan mode;

Figure 5 is an example diagram of the secondary collection method for suspected pesticides in grass head samples;

Figure 6. Secondary Q-TOF/MS confirmation score chart of pesticides detected in grass head samples.

detailed description

Example 1

An implementation example of LC-Q-TOF/MS detection and confirmation technology for 544 pesticides (see Table 1) in sprout vegetables (taking mung bean sprouts as an example) includes the following steps:

1. Specific steps of sample pretreatment technology:

1.1 Take the edible part of the mung bean sprouts sample, chop it up, mix it evenly, seal it, and mark it;

1.2 Weigh 10g of mung bean sprouts sample (accurate to 0.01g), add 40mL of 1% acetic acid acetonitrile to an 80mL centrifuge tube, use a high-speed homogenizer at 13500r/min, extract the homogenate for 1min, add 1g of sodium chloride, 4g of anhydrous sulfuric acid Magnesium, shake for 5min, centrifuge at 4200r/min for 5min, take 20mL of the supernatant, concentrate it to about 1mL by rotary evaporation in a water bath at 40°C, and wait for purification.

1.3 Add about 2cm high anhydrous sodium sulfate to the Carbon/NH ₂ column. Rinse the SPE column with 4 mL of acetonitrile + toluene (3+1, v/v) first, and discard the effluent. When the liquid level reaches the top of sodium sulfate, quickly transfer the concentrated sample solution to the SPE column, and then connect a new Heart bottle received. Then use 2 mL of acetonitrile + toluene (3+1, v/v) to wash the sample solution bottle three times each time, and transfer the washing solution into the SPE column. Connect a 50mL liquid reservoir to the column, use 25mL acetonitrile + toluene (3+1, v/v) to elute pesticides and related chemicals, combine them in a heart bottle, and concentrate in a 40°C water bath to about 0.5mL.

1.4 Blow dry the concentrated solution under nitrogen, add 2 mL of acetonitrile + water (2+8, v/v) and mix evenly, filter through a 0.2 μm filter membrane and constant volume to obtain the sample solution to be tested.

2. LC-Q-TOF/MS operating conditions

Chromatographic conditions: liquid chromatography mobile phase A is 5mM ammonium acetate-0.1% formic acid-water; mobile phase B is acetonitrile; gradient elution program is: 0min: 1%B, 3min: 30%B, 6min: 40%B , 9min: 40%B, 15min: 60%B, 19min: 90%B, 23min: 90%B, 23.01min: 1%B, and then run for 4min; flow rate is 0.4mL/min; column temperature: 40℃; Sample volume: 10 μL.

Mass spectrometry conditions: capillary voltage of Agilent6530LC-Q-TOF/MS mass spectrometer: 4000V; drying gas temperature: 325°C; drying gas flow rate of 10L/min, sheath flow rate of 11L/min, sheath flow gas temperature of 325°C; atomization gas pressure 40psi, cone voltage 60V, fragmentation voltage 140V. The mass-to-nucleus ratio range of the full scan is 50-1600m/z, and the internal standard reference solution is used to correct the mass accuracy of the instrument in real time. The mass spectrometry results were collected and processed by AgilentMassHunterWorkstationSoftware (version B.05.00).

3 Detection of pesticide residues in sprout vegetables (take mung bean sprouts as an example)

3.1 Measure the sample solution in full-scan mode, compare the detection results with the TOF database, and obtain the first-level TOF score, as shown in Figure 1.

3.2 For compounds whose scores meet the requirements, establish a secondary acquisition method in the software, see Figure 2 for details.

3.3 In MS/MS mode, re-run the sample solution to obtain the full scan data of the sample fragment ions, compare it with the fragment ion information in the MS/MS library, and obtain the secondary QTOF score, as shown in Figure 3.

4 LC-Q-TOF/MS detection results of mung bean sprouts in a provincial capital city

Collected 8 samples of mung bean sprouts sold in a provincial capital city, and applied LC-Q-TOF/MS technology to detect 544 kinds of pesticide residues. LC-Q-TOF/MS technology detected 16 kinds of pesticide residues, a total of 27 frequencies, involving samples 8, the specific results are shown in Table 2.

Table 1544 Pesticide LC-Q-TOF/MS Detection Parameters

Table 2 LC-Q-TOF/MS detection results of mung bean sprouts samples in a certain area

Example 2

Implementation example of LC-Q-TOF/MS detection and confirmation technology for 544 kinds of pesticides (see Table 1) in sprout vegetables (Taking Caotou as an example).

The sample pretreatment steps and LC-Q-TOF/MS operating conditions refer to the processing conditions in Example 1.

Measure the sample solution in full-scan mode, compare the detection results with the TOF database, and obtain the first-level TOF score, as shown in Figure 4; for the compounds whose scores meet the requirements, establish a second-level acquisition method in the software, as shown in Figure 4. 5. In MS/MS mode, re-run the sample solution to obtain the full scan data of the sample fragment ions, compare it with the fragment ion information in the MS/MS library, and obtain the secondary QTOF score, as shown in Figure 6.

LC-Q-TOF/MS detection results in the grass head samples of a provincial capital city: 1 grass head sample sold in a provincial capital city was collected, and 544 kinds of pesticide residues were detected by LC-Q-TOF/MS technology. LC-Q -TOF/MS technology detected 2 kinds of pesticide residues, a total of 2 frequencies, involving 1 sample, the specific results are shown in Table 3.

Table 3 Detection results of LC-Q-TOF/MS in Caotou samples in a certain area

Claims (10)

1. A detection method for detecting 544 kinds of pesticide residues in sprout vegetables, characterized in that: by establishing a TOF/MS database and a Q-TOF/MS database of 544 kinds of pesticides, the chromatographic mass spectrum information of the target compound Matching the information retrieval of the TOF/MS database and the Q-TOF/MS database, it realizes the qualitative detection and confirmation of more than 500 pesticides in agricultural products without the need for standard substances; the 544 pesticides described are listed in Table 1 Pesticides numbered 1-544. 2. a TOF/MS database as claimed in claim 1, is characterized in that: construct database by following method: under TOF/MS mode, measure respectively the retention time of every kind of pesticide standard substance under specified chromatographic mass spectrometry conditions, Determine the ionization form of the compound under the ESI source, select +H, +NH ₄ , +Na, and the chemical formula to obtain the accurate mass number, isotope peak distribution and abundance ratio of the parent ion of each compound, and the names of 544 pesticides , retention time, molecular formula, accurate mass number, isotope peak distribution and abundance ratio information are imported into the database CSV file to form a TOF/MS database. 3. A Q-TOF/MS database as claimed in claim 1, characterized in that: build the database by the following method: input the data of 544 kinds of pesticides in the TOF/MS database as described in claim 2 successively in the data acquisition interface For parent ions, in Q-TOF/MS mode, 544 pesticides were collected under 8 collision energies for fragment ion full-scan mass spectrometry, and 3-5 fragment ions with rich ion information under different collision energies were selected. The scanned mass spectrum is imported into the database software file, and is associated with the corresponding pesticide information to build a Q-TOF/MS database. 4. The detection method according to claim 1, characterized in that: the detection of pesticide residues does not require a pesticide standard as a control. 5. The detection method according to claim 1, characterized in that the method comprises the following procedures: (a) Sample preparation: The vegetable sprouts were extracted by homogenate with acetonitrile, dehydrated, centrifuged, and concentrated, then purified by Carbon/NH ₂ column, and residual pesticides were eluted with acetonitrile + toluene, and then prepared after concentration and filtration. Sample solution to be tested a; (b) Chromatography and mass spectrometry detection: using liquid chromatography equipped with a reversed-phase chromatographic column, under specific chromatographic conditions, to separate the pesticides in the sample liquid a to be tested; using LC-Q-TOF/MS equipped with an electrospray ion source -MS, under specific mass spectrometry conditions, detect pesticides; (c) TOF/MS database screening: call the established TOF/MS database as claimed in claim 2 in the qualitative software, and perform qualitative retrieval of the target compound in the mass spectrometry detection results according to the TOF/MS database, and search parameter retention time deviation It is limited to ±0.5min, the accurate mass deviation is limited to ±10ppm, and the ionization form is selected as +H, +NH ₄ , +Na mode. According to the deviation between the measured value of each element of each compound and the theoretical value in the TOF/MS database, The search matching score value is displayed, and the compound with a search matching score value > 70 is a suspected compound; (d) Q-TOF/MS database confirmation: In the TargetedMS/MS acquisition mode, input the parent ion, retention time and optimal collision energy of the suspected compound to be detected again, and compare the detection spectrum with The spectrogram in the Q-TOF/MS database according to claim 3 is matched and confirmed under mirror image comparison conditions, and its matching score value is >70, which means that the target compound is confirmed to be detected. 6. The detection method according to claim 5, characterized in that: in step (a), the sprout vegetables include mung bean sprouts, Chinese toon sprouts and grass head. 7. detection method according to claim 5, is characterized in that: in step (a), described Carbon/NH Column purification step is as follows: add anhydrous _{sodium sulfate} in Carbon/NH column, first use acetonitrile Rinse the SPE column with a mixture of + toluene, and discard the effluent. When the liquid level reaches the top of sodium sulfate, quickly transfer the concentrated sample solution to the purification column, and then connect it to a new heart bottle to receive it; then wash with the mixture of acetonitrile + toluene The sample bottle was washed three times, and the washing solution was transferred to the SPE column; then the pesticide was eluted with a mixture of acetonitrile and toluene, and the eluent was combined into a chicken heart bottle. 8. The detection method according to claim 5, characterized in that: in step (a), said sample liquid a to be tested after being concentrated and filtered refers to the eluent obtained in claim 7. Rotate and concentrate in a water bath at 40°C, dry the concentrated solution under nitrogen, add acetonitrile + formic acid water, mix well, filter through a filter membrane, and then constant volume to obtain the sample solution a to be tested. 9. detection method according to claim 5, is characterized in that: in step (b), described specific chromatographic condition refers to: the ammonium acetate-0.1% formic acid-water that liquid chromatography mobile phase A is 5mM; Phase B is acetonitrile; the gradient elution program is: 0min: 1% B, 3min: 30% B, 6min: 40% B, 9min: 40% B, 15min: 60% B, 19min: 90% B, 23min: 90 %B, 23.01min: 1%B, last run for 4min; flow rate: 0.4mL/min; column temperature: 40°C; injection volume: 10μL. 10. The detection method according to claim 5, characterized in that: in step (b), the specific mass spectrometry conditions refer to: capillary voltage of Agilent6530LC-Q-TOF/MS mass spectrometer: 4000V; drying gas temperature: 325°C; drying gas flow rate 10L/min, sheath flow rate 11L/min, sheath gas temperature 325°C; atomizing gas pressure 40psi, cone voltage 60V, fragmentation voltage 140V, full-scan mass-to-core ratio range 50-1600m /z, and the internal standard reference solution was used to calibrate the mass accuracy of the instrument in real time, and the mass spectrometry results were collected and processed through AgilentMassHunterWorkstationSoftware.