WO2019200946A1 - Base de données d'identification électronique de composés pesticides dans des produits agricoles comestibles basée sur gc-q-orbitrap et procédé de détection associé - Google Patents

Base de données d'identification électronique de composés pesticides dans des produits agricoles comestibles basée sur gc-q-orbitrap et procédé de détection associé Download PDF

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Publication number
WO2019200946A1
WO2019200946A1 PCT/CN2018/120999 CN2018120999W WO2019200946A1 WO 2019200946 A1 WO2019200946 A1 WO 2019200946A1 CN 2018120999 W CN2018120999 W CN 2018120999W WO 2019200946 A1 WO2019200946 A1 WO 2019200946A1
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pesticide
ion
orbitrap
mass
fragment
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PCT/CN2018/120999
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English (en)
Chinese (zh)
Inventor
庞国芳
范春林
吴兴强
韩奎国
常巧英
张紫娟
陈辉
白若镔
Original Assignee
中国检验检疫科学研究院
北京合众恒星检测科技有限公司
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Priority claimed from CN201810337240.9A external-priority patent/CN108760909A/zh
Application filed by 中国检验检疫科学研究院, 北京合众恒星检测科技有限公司 filed Critical 中国检验检疫科学研究院
Priority to US16/314,619 priority Critical patent/US11181512B2/en
Publication of WO2019200946A1 publication Critical patent/WO2019200946A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation

Definitions

  • the invention designs an electronic identity database and a detection method for pesticide compounds in edible agricultural products based on GC-Q-Orbitrap, and the invention can realize non-target, multi-index and rapid screening for more than 600 pesticide residues in various edible agricultural products.
  • 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 first need to be qualitatively compared to pesticide standards. For example, the detection of 100 pesticides requires the preparation of the corresponding 100 pesticide standard controls, and these 100 pesticides will be missed. In the actual work of pesticide residue laboratories, most laboratories do not stock hundreds of pesticide standards. The reason is that pesticide standards are not only expensive, but also valid for only 2 or 3 years, requiring repeated investment. There are only a few dozen standard pesticide standards in the laboratory, and the number of pesticides that are routinely monitored is limited to these dozens, which leads to food safety monitoring loopholes.
  • the invention solves the problem that the rapid detection of multiple pesticides at the same time can not be realized in the current pesticide residue screening technology method, and develops an electronic identity database and detection method of pesticide compounds based on GC-Q-Orbitrap for edible agricultural products, which realizes that no need Standard product control can quickly screen and detect more than 600 pesticide residues in agricultural products, which meets the urgent need for rapid detection of high-throughput pesticide residues in agricultural products.
  • An electronic identity database of pesticide compounds in edible agricultural products based on GC-Q-Orbitrap comprising a plurality of pesticide compound electronic identification cards, including pesticide compound information, retention time, mass spectrum, and fragment ion information, characteristics thereof Lie in:
  • the pesticide compound information includes a compound name, a compound molecular formula
  • the mass spectrum is a first-level full scan obtained by the GC-Q-Orbitrap instrument at the retention time;
  • the fragment ions are determined by selection in the mass spectrum, and the fragment ions include one base peak ion and a plurality of confirming ions, and the base peak ions are fragment ions having high signal intensity and large mass, the base peak The ion does not select the ion of the isotope peak;
  • the fragment ion information includes an ion abundance ratio and a theoretical accurate mass number
  • the ion abundance ratio is a signal intensity ratio of the fragment ion to the base peak ion;
  • the database is sorted by retention time in the electronic ID card.
  • the electronic identity database further includes an intelligent matching model, and the matching model adds an intelligent matching value P m to the electronic identity card, and the computing model is:
  • M b is the theoretical exact mass of the base peak ion
  • M i is the exact mass of the ith confirmed ion
  • W i is the weight
  • I i is the ion abundance ratio of the ith confirmed ion, confirming the order of the ions
  • the ion abundance ratio is from large to small
  • W b is the weight of the base peak ion
  • W q is the comprehensive weight of the confirmed ion
  • n is the number of fragment ions.
  • the selection of the fragment ions depends on the ion abundance and the ion mass number, wherein the ion abundance is the signal intensity of the ions in the mass spectrum, and the number of the fragment ions is five, and the principle of the fragment ion selection is :
  • , M i , M j are the exact masses of the two closest fragment ions, The arrangement of the ion fragments is in accordance with the ion abundance ratio from large to small.
  • M i is the exact mass of the i-th fragment ion element
  • n is the number of elements of the fragment ion
  • y i is the number of elements corresponding to the i-th fragment ion.
  • M' M 1 y' 1 +M 2 y' 2 +...+M n y' n
  • M 1 , M 2 , ..., M n is the exact mass of the fragment ion element
  • y' 1 , y' 2 , ... y' n are the number of corresponding elements of the preferred fragment ion element composition.
  • a retention index of the pesticide compound is calculated, and a retention time of the pesticide compound is determined by the retention index being close to a standard retention index of the pesticide compound;
  • the calculation method of the retention index R I is:
  • the retention time t R is the correction, and the z-z + 1, respectively pesticide compound (x) of the effluent before and after the n-paraffins of the number of carbon atoms, the t R (z) ⁇ t R (x) ⁇ t R (z+1), the number z of carbon atoms contained in normal paraffins in a general pesticide compound is greater than 4.
  • chromatographic mass spectrometry conditions are:
  • GC column is TG-5SILMS, 30m ⁇ 0.25mm (id) ⁇ 0.25 ⁇ m special column for mass spectrometry; temperature programming process: 40 ° C for 1 min, then programmed to 30 ° C / min to 130 ° C, then 5 ° C /min warmed to 250 ° C, and then heated to 300 ° C at 10 ° C / min, held for 5 min; carrier gas: helium, purity ⁇ 99.999%, flow rate 1.2mL / min; inlet type: PTV; injection volume: 1 ⁇ L ; injection method: temperature programmed injection, no split time 1.5min;
  • Mass spectrometry conditions EI source voltage: 70 eV; ion source temperature: 230 ° C; transmission line temperature: 280 ° C; solvent delay: 4 min.
  • Scanning mode Full MS; mass scanning range 50-600 m/z, resolution 60,000 FHWM (200 m/z); epoxy heptachlor was used to adjust retention time.
  • a method for detecting pesticide compounds in edible agricultural products based on GC-Q-Orbitrap comprising:
  • sample to be tested is extracted by homogenization of acetic acid acetonitrile, dehydrated, centrifuged, concentrated, and then purified by Carbon/NH2 column, and the residual pesticide is eluted by acetonitrile + toluene, and concentrated and filtered to prepare a sample solution to be tested;
  • ⁇ T is the difference between the retention time of the unknown and the retention time of any pesticide compound in the database
  • P c is the intelligent matching value of the unknown, and the intelligent matching value of any pesticide compound in the P i database.
  • step 4 if ⁇ T ⁇ 0.15 and 10% ⁇ ⁇ P ⁇ 30%, it is judged whether or not the pesticide compound is included by the height of the mass spectrum peak and the degree of coincidence degree in the mass spectrum.
  • step 1) pretreatment of the sample
  • the invention establishes an electronic ID card under the corresponding GC-Q-Orbitrap detection condition according to each pesticide compound, and innovatively utilizes the unique retention index information of each pesticide to establish an electronic identification card to assist the pesticide compound. Confirmation has greatly increased the accuracy and reliability of electronic ID cards.
  • the invention establishes an electronic identification card information unique to each pesticide, and the electronic identification card includes pesticide compound information, retention time, mass spectrum, and fragment ion information, and is optimized for improving the accuracy and operability of the alignment.
  • the typical fragment ions are used as a basis for comparison, and the fragment ion information of the core alignment is determined by setting the base peak ions.
  • the invention's solution makes it unnecessary to prepare pesticide standard products in food pesticide detection, and replaces the pesticide physical standard with the electronic standard screening method as a reference traditional identification method to realize high-precision, high-efficiency and resource-saving non-target pesticide residue detection. A leap in the development of pesticide residue detection technology has been realized.
  • the invention has completed the extraction of electronic ID card information of more than 600 pesticide compounds, and established a corresponding electronic identity database, which uses the theoretical accurate mass to achieve an accuracy of 5 ppm, and more importantly, through a pair of edible agricultural products.
  • the GC-Q-Orbitrap test can simultaneously detect the residual information of multiple pesticides. After the comparison of the database, the pesticide can be quickly screened and confirmed. About 80% of the pesticide screening sensitivity is lower than the standard 10 micrograms/kg, greatly The false positive detection results are reduced, and the requirements for screening MRL levels of pesticide residues in various countries are better met.
  • the theoretical accurate mass as the accurate mass of the fragment ion detection, it can effectively avoid the problem of inaccurate and isotopic peaks of pesticide compounds, improve the accuracy of the whole detection, and reduce the inaccurate detection results caused by the interference of the detection equipment.
  • the theoretical estimation method adopted by the theoretical precision quality comprehensively utilizes the cracking mechanism of the molecular structure of the pesticide compound, and further improves the establishment accuracy of the electronic ID card and the database, and improves the accuracy of the detection.
  • This patent introduces the selection model of fragment ions, which can realize the automatic and rapid selection of fragment ions.
  • the intelligent matching value model by introducing the intelligent matching value model, the intelligent matching value of fast and automatic comparison is calculated for each compound, and the intelligent matching value takes into account the accurate quality.
  • the information on the abundance ratio of the number and the ion, and the influence of the ion abundance of the difference between the base peak ion and the different convincing ions, which highlights the difference, reveals the original human judgment based on the introduction of the intelligent matching value. Insufficient, able to achieve accurate brake matching, truly automated detection.
  • Figure 1 shows a GC-Q-Orbitrap pesticide compound electronic identity database model including an electronic identification card comprising a plurality of pesticide compounds including pesticide compound information, retention time, mass spectrum, fragment ion information, and smart match values.
  • the gas chromatographic column was TG-5SILMS, 30 m ⁇ 0.25 mm (i.d.) ⁇ 0.25 ⁇ m mass spectrometer dedicated column. Temperature programmed process: 40 ° C for 1 min, then programmed to 30 ° C / min to 130 ° C, then 5 ° C / min to 250 ° C, and then 10 ° C / min to 300 ° C, for 5 min; carrier gas: ⁇ Gas, purity ⁇ 99.999%, flow rate 1.2mL/min; inlet type: PTV; injection volume: 1 ⁇ L; injection mode: temperature-programmed injection, no split time 1.5min.
  • Mass spectrometry conditions EI source voltage: 70 eV; ion source temperature: 230 ° C; transmission line temperature: 280 ° C; solvent delay: 4 min.
  • Scanning method Full MS; mass scanning range 50-600 m/z, resolution 60,000 FHWM (200 m/z); epoxy heptachlor used to adjust retention time; data acquisition by TraceFinder (Version. 4.0).
  • the PTV mode was used to test the solvent standard in Full MS mode.
  • the molecular formula was C 14 H 9 Cl 5 O.
  • the total ion chromatogram of the Dicofol solvent standard is shown in Figure 2 at 19.19 min and 27.40 min. Two peaks appeared at the same time.
  • the mass spectrum at 19.19min (Fig. 3) and the mass spectrum at 27.40min (Fig. 4) showed that although the retention times of the two peaks were inconsistent, the ion species and ion abundance were very close and could not be inferred.
  • the ion composition and the exact mass are distinguished and identified, and for this purpose, the retention index is added to aid the judgment.
  • the retention index of the peak at 19.19min was calculated as 1995, and the retention index of the peak at 27.40min was 2476.
  • the retention index of Dicofol in the existing data was 2467.
  • the retention index was found to be closer to the original retention index at 27.40min.
  • the peak is regular, so the peak time of Dicofol is determined to be 27.40 min. It is inferred at 27.40 that the five actual measured primary fragments are 138.99464, 140.99152, 215.02583, 251.00265 and 249.99475, respectively, so that the theoretical values of the five primary fragments can be determined by combining structural information and molecular formula, respectively.
  • Dicofol's ion-accurate mass and its fragment mass are imported into the software to build an accurate mass database, and the confirmed first-order mass spectrum is also imported into the spectral library.
  • the above retention time information and primary mass spectrometry information constitute Dicofol's electronic identity card.
  • the invention creates a large number of experimental verification work, and completes the establishment of more than 600 kinds of commonly used pesticide electronic identity databases in the world, and realizes the replacement of pesticide physical standards by electronic standards.
  • the method optimizes and determines the GC-Q-Orbitrap screening parameters and conditions of pesticide residues, and achieves automatic comparison of test results with the pesticide electronic identity database. This process achieves high speed (40 minutes), high throughput (more than 600 types), high precision (0.00001m/z), high reliability (above 6 confirmation points), high information and automation. At the same time, a sample preparation was realized.
  • the GC-Q-Orbitrap detection technology was used to simultaneously screen more than 600 kinds of pesticides, and the multi-indicators, non-targets and rapid screening of pesticide residues in edible agricultural products were realized; the discovery ability and method efficiency of the technology were significantly improved.
  • Table 1 gives an example of five representative pesticide electronic IDs in the GC-Q-Orbitrap Accurate Mass Database and five representative pesticide mass spectra in the GC-Q-Orbitrap High Resolution Library.
  • Table 2 gives a list of more than 600 pesticides in the GC-Q-Orbitrap electronic identity database.
  • Figure 6 shows the method for electronic detection of pesticides according to the present invention.
  • the sample is prepared once, and the GC-Q-Orbitrap technique can screen more than 600 kinds of pesticides; the standard product is eliminated for reference, and the electronic standard is used for qualitative identification.
  • the replacement of physical standards with electronic ID cards has also led to a leap-forward development from targeted detection to non-targeted screening. It saves resources, reduces pollution, improves analysis speed, and fully meets the requirements of green development, environmental friendliness, and clean and efficient.
  • a 50 mL reservoir was attached to the column, and the pesticide and related chemicals were eluted with 25 mL of acetonitrile + toluene (3+1, v/v), combined in a chicken heart bottle, and concentrated in a 40 ° C water bath to about 0.5 mL.
  • the gas chromatographic column was TG-5SILMS, 30 m ⁇ 0.25 mm (i.d.) ⁇ 0.25 ⁇ m mass spectrometer dedicated column. Temperature programmed process: 40 ° C for 1 min, then programmed to 30 ° C / min to 130 ° C, then 5 ° C / min to 250 ° C, and then 10 ° C / min to 300 ° C, for 5 min; carrier gas: ⁇ Gas, purity ⁇ 99.999%, flow rate 1.2mL/min; inlet type: PTV; injection volume: 1 ⁇ L; injection mode: temperature-programmed injection, no split time 1.5min.
  • Mass spectrometry conditions EI source voltage: 70 eV; ion source temperature: 230 ° C; transmission line temperature: 280 ° C; solvent delay: 4 min.
  • Scanning method Full MS; mass scanning range 50-600 m/z, resolution 60,000 FHWM (200 m/z); epoxy heptachlor used to adjust retention time; mass spectrometry detection results collection and processing by TraceFinder (Version. 4.0); Obtain the chromatogram and mass spectrum of the cabbage under the specified chromatographic mass spectrometry, extract all the retention time in the chromatogram and its corresponding accurate mass, and establish the electronic ID of the pesticide in the cabbage corresponding to all retention time.
  • the sample solution was measured in the full scan mode, and the screening results were compared with the GC-Q-Orbitrap electronic identity database to obtain the pesticide detection.
  • the electronic ID card of the pesticide in the cabbage is sequentially compared with the electronic ID of each pesticide compound in the electronic identity database. If ( ⁇ T ⁇ 0.15 and ⁇ P ⁇ 10%), the pesticide compound is recorded if ( ⁇ T ⁇ 0.15 and 10% ⁇ ⁇ P ⁇ 30%), determine whether the pesticide compound is included by the height and coincidence degree of the mass spectrum peak in the mass spectrum, otherwise the electronic ID of the pesticide entering the next cabbage is compared; the detection is completed, and the display is completed. Information on pesticide compounds contained in the cabbage sample solution.
  • Example 1 The sample pretreatment step, the GC-Q-Orbitrap operating conditions, and the pesticide residue screening process in the sample are all referred to in Example 1.
  • GC-Q-Orbitrap screening results in tomato samples from a provincial capital 16 samples of commercially available tomato samples from a provincial capital were collected, and more than 600 pesticide residues were screened using GC-Q-Orbitrap technology. GC-Q-Orbitrap technique was detected. There are 16 kinds of pesticide residues, totaling 45 frequency, involving 15 samples. The specific results are shown in Table 4.
  • Example 1 The sample pretreatment step, the GC-Q-Orbitrap operating conditions, and the pesticide residue screening process in the sample are all referred to in Example 1.
  • GC-Q-Orbitrap screening results in grape samples from a provincial capital 16 samples of grape samples from a provincial capital were collected, and more than 600 pesticide residues were screened using GC-Q-Orbitrap technology. GC-Q-Orbitrap technique was detected. There were 21 pesticide residues, totaling 73 frequency, involving 16 samples. The specific results are shown in Table 5.

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Abstract

L'invention concerne une base de données d'identification électronique de composés pesticides dans des produits agricoles comestibles basée sur GC-Q-Orbitrap et un procédé de détection associé ; cette base de données d'identification électronique repose sur la collecte d'informations de carte d'identité électronique d'une pluralité de composés pesticides et le tri en fonction des temps de rétention sur la carte d'identité électronique, ladite carte d'identité électronique comprenant des informations du composé pesticide, un temps de rétention, un spectrographe de masse, des informations d'ions fragments et une valeur de concordance intelligente ; le procédé de détection comprend une étape de prétraitement d'échantillon, la définition de conditions opératoires GC-Q-Orbitrap et un processus de criblage de résidus de pesticides dans l'échantillon, la définition de conditions opératoires GC-Q-Orbitrap comprenant la définition d'une condition chromatographique appropriée et d'une condition de spectrométrie de masse appropriée, et un processus de criblage de pesticides consistant à utiliser préalablement le temps de rétention pour rechercher un composé pesticide dans la base de données d'identification électronique et à extraire des informations de carte d'identité électronique correspondantes en cas de concordance, puis à comparer une valeur de concordance intelligente, et à enregistrer et afficher un résultat si la valeur de concordance intelligente est inférieure à un seuil, le criblage étant alors terminé.
PCT/CN2018/120999 2018-04-16 2018-12-14 Base de données d'identification électronique de composés pesticides dans des produits agricoles comestibles basée sur gc-q-orbitrap et procédé de détection associé WO2019200946A1 (fr)

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US16/314,619 US11181512B2 (en) 2018-04-16 2018-12-14 Electronic ID database and detection method for pesticide compounds in edible Agro-products based on GC-Q-Orbitrap

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CN201810337240.9A CN108760909A (zh) 2017-04-17 2018-04-16 一种食用农产品农药残留非靶标、多指标、快速侦测的电子化方法
CN201810337240.9 2018-04-16
CN201811376107.0A CN109557197B (zh) 2017-04-17 2018-11-19 基于GC-Q-Orbitrap的食用农产品中农药化合物电子身份数据库的建立方法及检测方法
CN201811376107.0 2018-11-19

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CN108760909A (zh) * 2017-04-17 2018-11-06 中国检验检疫科学研究院 一种食用农产品农药残留非靶标、多指标、快速侦测的电子化方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112924590A (zh) * 2021-01-29 2021-06-08 浙江大学 采用gc/lc-qtof的土壤农药非靶向快速筛查方法

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