CN115876909A - Method for measuring pesticide content in flea beetle by ultra-high performance liquid chromatography tandem mass spectrometry - Google Patents
Method for measuring pesticide content in flea beetle by ultra-high performance liquid chromatography tandem mass spectrometry Download PDFInfo
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- CN115876909A CN115876909A CN202211079985.2A CN202211079985A CN115876909A CN 115876909 A CN115876909 A CN 115876909A CN 202211079985 A CN202211079985 A CN 202211079985A CN 115876909 A CN115876909 A CN 115876909A
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- flubendiamide
- chlorantraniliprole
- flea
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 241000738498 Epitrix pubescens Species 0.000 title claims description 31
- 239000000575 pesticide Substances 0.000 title abstract description 21
- 238000001195 ultra high performance liquid chromatography Methods 0.000 title abstract description 6
- 238000004885 tandem mass spectrometry Methods 0.000 title description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000005901 Flubendiamide Substances 0.000 claims abstract description 41
- ZGNITFSDLCMLGI-UHFFFAOYSA-N flubendiamide Chemical compound CC1=CC(C(F)(C(F)(F)F)C(F)(F)F)=CC=C1NC(=O)C1=CC=CC(I)=C1C(=O)NC(C)(C)CS(C)(=O)=O ZGNITFSDLCMLGI-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000005886 Chlorantraniliprole Substances 0.000 claims abstract description 36
- PSOVNZZNOMJUBI-UHFFFAOYSA-N chlorantraniliprole Chemical compound CNC(=O)C1=CC(Cl)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl PSOVNZZNOMJUBI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000605 extraction Methods 0.000 claims abstract description 33
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 241000902876 Alticini Species 0.000 claims abstract description 20
- 238000000746 purification Methods 0.000 claims abstract description 20
- 239000003463 adsorbent Substances 0.000 claims abstract description 17
- 238000001514 detection method Methods 0.000 claims abstract description 17
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000011780 sodium chloride Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000004458 analytical method Methods 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- AMWBKZHMFJEZRP-UHFFFAOYSA-N 3-fluorobenzene-1,2-dicarboxamide Chemical compound NC(=O)C1=CC=CC(F)=C1C(N)=O AMWBKZHMFJEZRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- CWFOCCVIPCEQCK-UHFFFAOYSA-N chlorfenapyr Chemical compound BrC1=C(C(F)(F)F)N(COCC)C(C=2C=CC(Cl)=CC=2)=C1C#N CWFOCCVIPCEQCK-UHFFFAOYSA-N 0.000 claims abstract 2
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- 238000011002 quantification Methods 0.000 claims description 11
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000010828 elution Methods 0.000 claims description 8
- 238000010811 Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry Methods 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
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- 238000000926 separation method Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002048 multi walled nanotube Substances 0.000 claims description 5
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004811 liquid chromatography Methods 0.000 claims description 4
- 238000004949 mass spectrometry Methods 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
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- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
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- 238000001035 drying Methods 0.000 claims description 3
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- 239000012488 sample solution Substances 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- RBGDLYUEXLWQBZ-UHFFFAOYSA-N 2-chlorobenzamide Chemical compound NC(=O)C1=CC=CC=C1Cl RBGDLYUEXLWQBZ-UHFFFAOYSA-N 0.000 claims description 2
- CTHMWRJVVKCPDA-UHFFFAOYSA-N 3-bromobenzene-1,2-dicarboxamide Chemical compound NC(=O)C1=CC=CC(Br)=C1C(N)=O CTHMWRJVVKCPDA-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- CFNHVUGPXZUTRR-UHFFFAOYSA-N n'-propylethane-1,2-diamine Chemical compound CCCNCCN CFNHVUGPXZUTRR-UHFFFAOYSA-N 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 claims 5
- UPMXNNIRAGDFEH-UHFFFAOYSA-N 3,5-dibromo-4-hydroxybenzonitrile Chemical compound OC1=C(Br)C=C(C#N)C=C1Br UPMXNNIRAGDFEH-UHFFFAOYSA-N 0.000 claims 1
- 239000005489 Bromoxynil Substances 0.000 claims 1
- 239000002516 radical scavenger Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 16
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- 238000010846 tandem mass spectrometry analysis Methods 0.000 abstract 1
- 239000002917 insecticide Substances 0.000 description 9
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- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 3
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- 241000607479 Yersinia pestis Species 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- NNRSYETYEADPBW-UHFFFAOYSA-N cyhalodiamide Chemical compound CC1=CC(C(F)(C(F)(F)F)C(F)(F)F)=CC=C1NC(=O)C1=CC=CC(Cl)=C1C(=O)NC(C)(C)C#N NNRSYETYEADPBW-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
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- WCXDHFDTOYPNIE-RIYZIHGNSA-N (E)-acetamiprid Chemical compound N#C/N=C(\C)N(C)CC1=CC=C(Cl)N=C1 WCXDHFDTOYPNIE-RIYZIHGNSA-N 0.000 description 1
- PGOOBECODWQEAB-UHFFFAOYSA-N (E)-clothianidin Chemical compound [O-][N+](=O)\N=C(/NC)NCC1=CN=C(Cl)S1 PGOOBECODWQEAB-UHFFFAOYSA-N 0.000 description 1
- HOKKPVIRMVDYPB-UVTDQMKNSA-N (Z)-thiacloprid Chemical compound C1=NC(Cl)=CC=C1CN1C(=N/C#N)/SCC1 HOKKPVIRMVDYPB-UVTDQMKNSA-N 0.000 description 1
- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 description 1
- KGGHWIKBOIQEAJ-UHFFFAOYSA-N 2-fluorobenzamide Chemical compound NC(=O)C1=CC=CC=C1F KGGHWIKBOIQEAJ-UHFFFAOYSA-N 0.000 description 1
- 239000005875 Acetamiprid Substances 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 235000010149 Brassica rapa subsp chinensis Nutrition 0.000 description 1
- 235000000536 Brassica rapa subsp pekinensis Nutrition 0.000 description 1
- 241000499436 Brassica rapa subsp. pekinensis Species 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000005888 Clothianidin Substances 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 241000920340 Pion Species 0.000 description 1
- 102000019027 Ryanodine Receptor Calcium Release Channel Human genes 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000005839 Tebuconazole Substances 0.000 description 1
- 239000005940 Thiacloprid Substances 0.000 description 1
- 239000005941 Thiamethoxam Substances 0.000 description 1
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- 238000010829 isocratic elution Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
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- NWWZPOKUUAIXIW-FLIBITNWSA-N thiamethoxam Chemical compound [O-][N+](=O)\N=C/1N(C)COCN\1CC1=CN=C(Cl)S1 NWWZPOKUUAIXIW-FLIBITNWSA-N 0.000 description 1
- 238000003260 vortexing Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses an ultra-high performance liquid chromatography tandem mass spectrometry analysis method of chlorfenapyr fluorobenzene bisamide, flubendiamide and chlorantraniliprole in flea beetles. Acetonitrile is used as an extracting agent, a mixture of anhydrous magnesium sulfate and sodium chloride is used as extraction salt, PSA, C18 and nano-zirconia 3 dispersion adsorbents are used for jointly purifying impurities in flea beetles, and the impurities are quantified by using an external standard method. The method has the advantages of simple and convenient pretreatment operation, good purification effect, high recovery rate, good reproducibility, small organic solvent dosage and the like, has low minimum detection concentration of 3 pesticides, is suitable for the analysis and detection of the flubendiamide, the flubendiamide and the chlorantraniliprole in the flea beetles, and provides a basis for the accurate control of the flea beetles.
Description
Technical Field
The invention relates to the technical field of pesticide detection, and particularly relates to a method for determining residual amounts of flubendiamide, flubendiamide and chlorantraniliprole in flea beetles by using ultra performance liquid chromatography-tandem mass spectrometry.
Background
The brofenpyrad fluorobenzene bisamide, the fluorobenzene amide and the chlorantraniliprole belong to diamide insecticides (diamide insecticides), and the insecticides are pesticides with the largest market using amount after neonicotinoid insecticides in recent years. The action mechanism is that a large amount of intracellular calcium ions are released by activating a ryanodine receptor calcium channel, so that the insect muscle is contracted and paralyzed to die. The bisamide insecticide has the characteristics of broad spectrum, high efficiency, low toxicity and safety, and is widely concerned by domestic and foreign research institutions.
Flea beetles are important pests on cruciferous vegetables and can cause damage to vegetables in the whole growth process, especially adult damage to vegetable seedlings is serious, root systems are damaged by eating root barks, and plants in the later period gradually wilt and wither. Most of the pesticides registered on flea beetles in China at present are neonicotinoid insecticides such as acetamiprid, thiamethoxam, clothianidin and thiacloprid, and the neonicotinoid insecticides have high toxicity to non-target organisms such as bees and silkworms. The bromaci fluorobenzene diamide is an ideal medicament which is registered in China in 2020 and has a good control effect on yellow flea beetles on cabbage and Chinese cabbage. According to the report of related documents, the bisamide pesticide has good control effect on flea beetles and is widely popularized and applied. The method is characterized in that the residual quantity of the bisamide insecticide in the flea beetle is detected, and a pesticide control effect test is combined, so that the field dosage of the bisamide insecticide is determined, and the purpose of accurately controlling the flea beetle is achieved. The extraction and purification steps in the pesticide pretreatment process are important factors influencing the accuracy of a quantitative result, impurities need to be removed to the maximum extent under the condition of meeting the sensitivity, the pollution to instruments, particularly liquid chromatograph-mass spectrometer (LC-MS) can be avoided, and the accuracy and repeatability of the result are ensured.
Disclosure of Invention
In order to solve at least one technical problem, the invention aims to provide a method for detecting the flubendiamide, the flubendiamide and the chlorantraniliprole in the flea beetle, which meets the requirements of accuracy, precision and sensitivity in production.
In order to achieve the purpose, the invention adopts the following technical scheme:
an ultra-performance liquid chromatography tandem mass spectrometry analysis method of bromantraniliprole, flubendiamide and chlorantraniliprole in flea beetles comprises the following steps:
s1, extraction: homogenizing a flea beetle sample, mixing the homogenized flea beetle sample with an extraction solvent and extraction salt, performing oscillation extraction to obtain an extracting solution, and taking a supernatant I;
s2, purification: mixing the supernatant I obtained in the step S1 with a purifying agent for purification, collecting a supernatant II, and filtering to obtain a sample solution to be measured;
s3, ultra-high liquid chromatography-mass spectrometry measurement: and separating the residues of the brobendiamide, the flubendiamide and the chlorantraniliprole in the sample liquid to be detected by adopting a liquid chromatography separation column, and detecting by mass spectrometry to obtain the residual contents of the brobendiamide, the flubendiamide and the chlorantraniliprole in the flea beetle.
Further, the assay of the present invention may replace flea beetles with other chewing mouthpart pests of the order coleoptera.
Preferably, as a preferred embodiment, in step S1, before adding the extraction solvent, an appropriate amount of water is added, and the ratio of the mass of the flea beetle sample to the volume of water is 1.
Preferably, in step S1, the extraction solvent is one or more of acetonitrile, acetonitrile containing 0.5% formic acid, and acetonitrile containing 0.5% acetic acid.
Preferably, as a preferred embodiment, the extraction solvent in step S1 is acetonitrile.
Preferably, in step S1, the ratio of the mass of the flea beetle sample to the volume of the extraction solvent is 1.
Preferably, as a preferred embodiment, the extraction salt in step S1 is a mixture of anhydrous magnesium sulfate and sodium chloride; among them, the mass ratio of anhydrous magnesium sulfate to sodium chloride is preferably 1. For example, when a 1. + -. 0.05g sample of flea beetle is analysed, a mixture of 0.5g anhydrous magnesium sulphate and 2g sodium chloride may be added to remove the water.
Preferably, as a preferred embodiment, the sample is dewatered by adding the extraction salt, and the dewatering time is 1-5min, preferably 1min.
Preferably, as a preferred embodiment, the condition of the shaking extraction in step S1 is that the extract is centrifuged at 5000 to 10000r/min, 5 to 10min and 0 to 5 ℃.
Preferably, in the step S2, the purifying agent is selected from octadecyl bonded silica gel adsorbent (C) 18 ) One or more of graphitized carbon black adsorbent (GCB), N-propyl ethylenediamine adsorbent (PSA), multi-walled carbon nano-tube and nano-zirconia. As a most preferred embodiment, PSA, C is used 18 And the nano zirconia dispersion adsorbent is used for combined purification, and the mass ratio of the 3 adsorbents is preferably 20. For example, when analyzing 1. + -. 0.05g of flea beetle sample, 1mL of n-hexane may be added to distribute the solution, and then 100mg of PSA and 100mg of C may be added 18 And 5mg of nano-zirconia as a purifying agent.
Preferably, in step S2, the supernatant I is mixed with the purifying agent and then vortexed to purify the mixture, and then the mixture is centrifuged at 5000 to 10000r/min for 5 to 10min at 0 to 5 ℃ to obtain the supernatant II, and the supernatant II is filtered through a 0.22 μm filter membrane.
Preferably, in the step S3, the liquid chromatography uses a Shim-pack Velox SP-C18 column, and the specific specification may be 100mm × 3.0mm,2.7- μm.
Preferably, as a preferred embodiment, the chromatographic conditions in step S3 are as follows:
the mobile phase is A: 0.1% formic acid in 2mmol/L ammonium acetate in water, mobile phase B: acetonitrile;
the gradient elution program employed was 80% A (0.5 min), 0.5-2.0min 40% A,40% A (1 min), 3.0-4.0min 15% A,15% A (0.5 min), 4.5-6.5min 80% A,80% A (3.5 min); the flow rate is set to be 0.3mL/min; column temperature: the sample size was 2. Mu.L at 35 ℃.
Preferably, as a preferred embodiment, the mass spectrum conditions in step S3 are as follows:
electrospray positive and negative ion mode; capillary voltage: 4KV; the flow rate of the atomizing gas is 3.0mL/min, the flow rates of the drying gas and the heating gas are both 10.0mL/min, the interface temperature is 300 ℃, the desolventizing temperature is 526 ℃, and the heating block temperature is 400 ℃; the detection mode is as follows: multiple reaction ion monitoring mode (MRM), brobendiamide quantification ion pair: 664.95 & gt 644.9, 664.95 & gt 256, 664.95 & gt, 624.95; flubendiamide quantitative ion-pair: 681.0 > 254.25, and 681.0 > 271.95; chlorantraniliprole quantitative ion pair: 484.0 > 285.9, and 484.0 > 453.35.
Compared with the prior art, the invention has the beneficial effects that:
the invention establishes an analytical detection method for the brobendiamide, the flubendiamide and the chlorantraniliprole in the flea beetles, adopts acetonitrile as an extracting agent, a mixture of anhydrous magnesium sulfate and sodium chloride as extraction salt, and 3 kinds of dispersion adsorbents such as PSA, C18 and nano zirconia to jointly purify and remove impurities in the flea beetles, and uses an external standard method for quantification. The method has the advantages of simple and convenient pretreatment operation, good purification effect, high recovery rate, good reproducibility, small using amount of organic solvent and the like, has low minimum detection concentration of 3 pesticides, is suitable for the analysis and detection of the flubendiamide, the flubendiamide and the chlorantraniliprole in the flea beetle, and provides a basis for the accurate control of the flea beetle.
Drawings
Figure 1 shows the effect of different adsorbents on the recovery of 3 pesticides;
FIG. 2 shows the effect of the response of different columns to 4 pesticides, 2a 50nm column, 2b 75nm column, and 2c 100nm column;
figure 3 shows the effect of mobile phase isocratic and gradient elution on the response of 3 pesticides, 3a isocratic and 3b gradient elution;
FIG. 4 shows a standard graph of 3 pesticides, 4a is bromobenzenediamide, 4b is flubendiamide, and 4c is chlorantraniliprole;
FIG. 5 shows standard solution chromatograms (10. Mu.g/L) for 3 pesticides;
FIG. 6 shows a sample addition chromatogram (50. Mu.g/kg) for 3 pesticides;
FIG. 7 is a sample chromatogram.
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be described in further detail with reference to specific embodiments. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and therefore the scope of the present invention is not limited by the specific embodiments disclosed below.
1. Method for detecting bromantraniliprole, flubendiamide and chlorantraniliprole in flea beetles
1. Instrument for measuring the position of a moving object
An ultra-high performance liquid chromatography tandem mass spectrometer (Shimadzu 8045), a multi-tube vortex mixer (LICHEN vortex-2500 MT) and a centrifuge (GTR 22-1).
2. Reagent
Acetonitrile (chromatographically pure, fisher corporation, usa), anhydrous magnesium sulfate (analytically pure, national group of medicine), sodium chloride (analytically pure, national group of medicine), ethylenediamine-N-propylsilane adsorbent (PSA, shanghai ' an spectrum corporation), graphitized carbon black adsorbent (GCB, shanghai ' an spectrum corporation), octadecyl bonded silica gel adsorbent (C18, shanghai ' an spectrum corporation), multiwalled carbon nanotube (nanjing pion nano materials science and technology limited), nano zirconia (shanghai alatin biotechnology limited), cyclic bromofenomide (96.3%, dr ehrentorfer), bromofenoxanilide (99.67%, basf corporation), fluorobenzeneamide (96.6%, dr ehrentorr), chlorobenzamide (97.5%, dr ehrentorfer).
3. Preparing a standard working solution:
respectively and accurately weighing 10mg of standard substances of the bromantraniliprole, the flubendiamide and the chlorantraniliprole, dissolving the standard substances with 10mL of chromatographically pure acetonitrile to prepare 1000mg/L stock solution, and hermetically storing the stock solution in a refrigerator at 0-4 ℃ for 6 months.
Accurately transferring appropriate amount of stock solution, diluting with chromatographic pure acetonitrile to obtain working solutions of different concentrations of 1, 5, 10, 20, 100, 500 μ g/L, and preparing at present.
4. Working conditions of the apparatus
4.1 chromatographic conditions
The chromatographic conditions of the liquid chromatography are as follows: the mobile phase is A: 0.1% formic acid in 2mmol/L ammonium acetate in water, mobile phase B: and (3) acetonitrile. The gradient elution procedure employed is 80% A (0.5 min), 0.5-2.0min 40% A,40% A (1 min), 3.0-4.0min 15% A,15% A (0.5 min), 4.5-6.5min 80% A,80% A (3.5 min); the flow rate is set to be 0.3mL/min; column temperature: the sample size was 2. Mu.L at 35 ℃.
4.2 Mass Spectrometry conditions
Electrospray positive and negative ion mode; capillary voltage: 4KV; the flow rate of the atomized gas is 3.0mL/min, the flow rates of the drying gas and the heating gas are both 10.0mL/min, the interface temperature is 300 ℃, the desolventizing temperature is 526 ℃, and the temperature of the heating block is 400 ℃; the detection mode comprises the following steps: multiple reaction ion monitoring mode (MRM), brobendiamide quantification ion pair: 664.95 & gt 644.9, 664.95 & gt 256, 664.95 & gt, 624.95; flubendiamide quantitative ion-pair: 681.0 > 254.25, and 681.0 > 271.95; chlorantraniliprole quantitative ion pair: 484.0 > 285.9, and 484.0 > 453.35.
5. Sample pretreatment
5.1 extraction
Weighing 1.0g (accurate to 0.01 g) of ground flea beetle sample, placing the weighed sample in a 10mL centrifuge tube, firstly adding 2mL of water to wet the sample, then adding 5mL of acetonitrile, whirling (LICHEN vortex-2500 MT) for uniformly mixing for 5min, adding 0.5g of anhydrous magnesium sulfate, 2g of sodium chloride, whirling (LICHEN vortex-2500 MT) and then centrifuging at 5000rpm and 2 ℃ (GTR 22-1 type desk centrifuge) for 10min.
5.2 purification
Transferring 2mL of the extract in the centrifuge tube, adding into the centrifuge tube filled with 100g of PSA and 100g of C18 mixed dispersion adsorbent, purifying, oscillating vigorously, vortexing for 10s, centrifuging at 10000r/min for 2min, collecting supernatant, passing through 0.22 μm organic needle filter, and determining.
5.3 design of the experiment
5.3.1 optimization of extraction procedure
5.3.1.1 optimization of extraction solvent
In selecting the extraction solvent, acetonitrile containing 0.5% formic acid, and acetonitrile containing 0.5% acetic acid can be used as the extraction solution of the present invention, and the extraction rates of 3 extraction solutions are 95%, 85%, and 87%, respectively. Therefore, acetonitrile homogenate extraction was chosen as the extraction solvent for bromobenzobisamide, flubendiamide and chlorantraniliprole in flea beetles.
5.3.1.2 selection of extraction salts
Anhydrous sodium sulfate was used to remove water from the matrix and sodium chloride was added to allow the organic and aqueous phases to separate. The substrate of the invention is flea beetles, the water content is relatively low, so the use amount of anhydrous magnesium sulfate needs to be reduced, and if the use amount is too large, the volume of acetonitrile is reduced. Therefore, the invention selects the mass ratio of the anhydrous magnesium sulfate to the sodium chloride as 1.
5.3.2 selection of purification conditions
When the purification materials are selected, the influence of 5 purification materials such as C18, PSA, GCB, multi-walled carbon nanotubes, nano-zirconia and the like on the purification effect of the flubendiamide, the flubendiamide and the chlorantraniliprole in the flea beetles is compared. As shown in FIG. 1, after the above 5 purification materials are purified alone, the multi-walled carbon nanotubes and GCB can cause serious adsorption, resulting in low recovery rate. C 18 PSA and nano zirconia can all obtain better recovery rate, thus the recovery rate for C 18 PSA and nano zirconia (shown in table 1), and the recovery rates are shown in table 2, in consideration of the influence on the recovery rates of the 3 types of pesticides.
TABLE 1 different combinations
| 1 | 50mg PSA, 50mg C18, |
| 2 | 100mg PSA and 100mg C18, 5mg nanozirconia |
| 3 | 100mg PSA and 100mg C18, 5mg nanozirconia |
The purification effect shows that the recovery rate of the target pesticides in the purification methods 1 and 2,3 is over 80 percent, and the recovery rate also meets the analysis requirement (see table 1). Factors such as recovery rate, impurity removal effect, interference conditions near the peak and the like are comprehensively considered, and 100mg PSA, 100mg C18 and 5mg nano-zirconia are selected to be jointly purified to be the optimal purification condition.
TABLE 2 Effect of different purification modes on recovery
5.3.3 optimization of assay conditions
The invention examines the separation, response and retention effects of three common liquid chromatographic columns of 50mm, 75mm, 100mm and the like on cyhalodiamide, when a Shim-pack Velox SP-C18 (100 mm multiplied by 3.0mm, 2.7-mum) chromatographic column is used, the separation effect of 3 target pesticides is better, baseline separation can be better realized, good symmetrical peak patterns are obtained, meanwhile, the response is higher, and the accuracy of a quantitative result is ensured.
After the chromatographic column is determined, the separation effect of isocratic elution and gradient elution on the brobendiamide, the flubendiamide and the chlorantraniliprole in the sample is considered, the response of the gradient elution can be obviously improved by 3 pesticides, and the gradient elution is finally determined. The gradient elution procedure employed is 80% A (0.5 min), 0.5-2.0min 40% A,40% A (1 min), 3.0-4.0min 15% A,15% A (0.5 min), 4.5-6.5min 80% A,80% A (3.5 min); the flow rate was set to 0.3mL/min.
5.3.4 methodology examination
And (3) quantifying by adopting an external standard method, and drawing a standard solution curve by taking the concentrations of the brobendiamide, the flubendiamide and the chlorantraniliprole as abscissa and the area of the quantified ion peak as ordinate, as shown in figure 5. The regression equation is:
bromobenzobisamide y =1.28276e +006x +19657.2 (r = 0.9949);
fluorobenzene diamide y =2.20934e 007x +440157 (r = 0.9928);
chlorantraniliprole y =2.62739e +007x-92034.1 (r = 0.9999).
The detection limit of the ultra-high performance liquid chromatography tandem mass spectrometer to the cyclic bromodiamide is 1 mug/kg, and the quantification limit is 5 mug/kg; the detection limit of the cyhalodiamide is 0.1 mu g/kg, and the quantification limit is 1 mu g/kg; the limit of detection of the tebuconazole is 1 mug/kg, and the limit of quantification is 5 mug/kg; the detection limit of the tetrachloro-worm amide is 1 mug/kg, and the quantification limit is 5 mug/kg. The detection limit of the ultra-high performance liquid chromatography tandem mass spectrometer on the brotrochan fluorobenzene diamide is 1 mu g/kg, and the quantification limit is 3 mu g/kg; the detection limit of the flubendiamide is 1 mu g/kg, and the quantification limit is 3 mu g/kg; the detection limit of chlorantraniliprole is 0.1 mug/kg, and the quantification limit is 0.3 mug/kg.
A blank flea beetle sample is taken, 3 adding concentrations of 10 mug/kg, 100 mug/kg, 500 mug/kg and the like are respectively set, an adding recovery rate test is carried out, and 5 times of adding concentrations are set for each adding concentration. As shown in Table 2, when the concentrations of the bromofenoxaprop-bendiamide, the flubendiamide and the chlorantraniliprole added to the flea beetle are 10 mug/kg, 100 mug/kg and 500 mug/kg, the average recovery rate is 85.4-96.9%, and the relative standard deviation is 5.58-8.39%.
TABLE 3 recovery and standard deviation for different addition concentrations
The invention establishes a method for detecting the brotrochar difluoride, the flubendiamide and the chlorantraniliprole in flea beetles. The concentration range of the flubendiamide, the flubendiamide and the chlorantraniliprole of the invention is in good linear relation within 1-500 mug/L, the average recovery rate of 3 pesticides added into the flea beetle is 85.4-96.9%, the relative standard deviation is 5.58-8.39%, and the quantitative limit of the method is 0.3-3 mug/kg. The method has the characteristics of simple and rapid operation, good sample reproducibility and strong applicability, and all technical indexes can meet the requirements of pesticide residue detection and analysis.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. An ultra-performance liquid chromatography tandem mass spectrometry analysis method for chlorfenapyr fluorobenzene bisamide, flubendiamide and chlorantraniliprole in flea beetles is characterized by comprising the following steps:
s1, extraction: homogenizing a flea beetle sample, mixing the homogenized flea beetle sample with an extraction solvent and extraction salt, performing oscillation extraction to obtain an extracting solution, and taking supernate I;
s2, purification: mixing the supernatant I obtained in the step S1 with a purifying agent for purification, collecting a supernatant II, and filtering to obtain a sample solution to be detected;
s3, ultra-high liquid chromatography-mass spectrometry measurement: and separating the residues of the bromantraniliprole, the flubendiamide and the chlorantraniliprole in the sample solution to be detected by adopting a liquid chromatography separation column, and detecting by mass spectrometry to obtain the residual contents of the bromantraniliprole, the flubendiamide and the chlorantraniliprole in the flea beetles.
2. The method for performing ultra performance liquid chromatography-tandem mass spectrometry on bromobenzodiamide, flubendiamide and chlorantraniliprole in flea beetle according to claim 1, wherein in step S1, before the extraction solvent is added, a proper amount of water is added, and the volume ratio of the mass of the flea beetle sample to the water is 1.
3. The method for performing ultra performance liquid chromatography-tandem mass spectrometry on bromobenzodiamide, flubendiamide and chlorantraniliprole in flea beetle according to claim 1, wherein in the step S1, the extraction solvent is one or more of acetonitrile, acetonitrile containing 0.5% of formic acid and acetonitrile containing 0.5% of acetic acid.
4. The HPLC-MS/MS of brobendiamide, flubendiamide, and chlorantraniliprole in flea beetle according to claim 3, wherein the extraction solvent used in step S1 is acetonitrile.
5. The method for performing ultra performance liquid chromatography-tandem mass spectrometry on the browbreaker bromoxynil bisamide, the flubendiamide and the chlorantraniliprole in the flea beetle according to claim 1, wherein in the step S1, the volume ratio of the mass of the flea beetle sample to the extraction solvent is 1.
6. The HPLC-MS/MS of brobendiamide, flubendiamide, and chlorantraniliprole in flea-beetle according to claim 1, wherein the extraction salt in step S1 is a mixture of anhydrous magnesium sulfate and sodium chloride; among them, the mass ratio of anhydrous magnesium sulfate to sodium chloride is preferably 1.
7. The HPLC-MS/MS of brobendiamide, flubendiamide, and chlorantraniliprole in flea beetle according to claim 1, wherein the scavenger is selected from octadecyl linkage in step S2Silica gel adsorbent (C) 18 ) One or more of graphitized carbon black adsorbent (GCB), N-propyl ethylenediamine adsorbent (PSA), multi-walled carbon nanotube and nano zirconia.
8. The HPLC-MS/MS method for detecting bromobenzenediamide, flubendiamide and chlorobenzamide in flea-beetle according to claim 7, wherein PSA and C are used 18 And the nano zirconia dispersion adsorbent is used for combined purification, and the mass ratio of the 3 adsorbents is preferably 20.
9. The HPLC-MS/MS method for analyzing bromoantraniliprole, flubendiamide and chlorantraniliprole in flea beetle according to claim 1, wherein in step S2, the supernatant I is mixed with the purifying agent, then vortexed to realize purification, and then centrifuged at 5000-10000 r/min for 5-10 min at 0-5 ℃ to obtain the supernatant II, and the supernatant II is filtered with a 0.22 μm filter membrane.
10. The method for performing ultra performance liquid chromatography-tandem mass spectrometry on bromobenzodiamide, flubendiamide and chlorantraniliprole in flea beetle according to claim 1, wherein the chromatographic conditions in the step S3 are as follows: the mobile phase is A: 0.1% formic acid in 2mmol/L ammonium acetate in water, mobile phase B: acetonitrile;
the gradient elution procedure employed is 80% A (0.5 min), 0.5-2.0min 40% A,40% A (1 min), 3.0-4.0min 15% A,15% A (0.5 min), 4.5-6.5min 80% A,80% A (3.5 min); the flow rate is set to be 0.3mL/min; column temperature: the sample size is 2 mu L at 35 ℃; the mass spectrometry conditions were as follows: electrospray positive and negative ion mode; capillary voltage: 4KV; the flow rate of the atomizing gas is 3.0mL/min, the flow rates of the drying gas and the heating gas are both 10.0mL/min, the interface temperature is 300 ℃, the desolventizing temperature is 526 ℃, and the heating block temperature is 400 ℃; the detection mode comprises the following steps: multiple reaction ion monitoring mode (MRM), brobendiamide quantification ion pair: 664.95 & gt 644.9, and 664.95 & gt 256, 664.95 >, 624.95; flubendiamide quantitative ion pair: 681.0 > 254.25, and 681.0 > 271.95; chlorantraniliprole quantitative ion pair: 484.0 > 285.9, qualitative ion pair 484.0 > 453.35.
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