CN115267019B - Ultra-high performance liquid chromatography tandem mass spectrometry analysis method for cyhalodiamide in fruits - Google Patents
Ultra-high performance liquid chromatography tandem mass spectrometry analysis method for cyhalodiamide in fruits Download PDFInfo
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- 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 title claims abstract description 51
- 235000013399 edible fruits Nutrition 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000001195 ultra high performance liquid chromatography Methods 0.000 title claims abstract description 18
- 238000010846 tandem mass spectrometry analysis Methods 0.000 title claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 81
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000746 purification Methods 0.000 claims abstract description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 22
- 238000000605 extraction Methods 0.000 claims abstract description 22
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 20
- 239000003463 adsorbent Substances 0.000 claims abstract description 16
- 238000001514 detection method Methods 0.000 claims abstract description 16
- 238000004458 analytical method Methods 0.000 claims abstract description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000011780 sodium chloride Substances 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 238000004949 mass spectrometry Methods 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 19
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000004885 tandem mass spectrometry Methods 0.000 claims description 10
- 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 8
- 238000010828 elution Methods 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- 238000004811 liquid chromatography Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000005695 Ammonium acetate Substances 0.000 claims description 6
- 235000019257 ammonium acetate Nutrition 0.000 claims description 6
- 229940043376 ammonium acetate Drugs 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000012544 monitoring process Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 241001629511 Litchi Species 0.000 claims 2
- 238000010811 Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 27
- 238000011084 recovery Methods 0.000 abstract description 13
- 239000000049 pigment Substances 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 5
- 150000008442 polyphenolic compounds Chemical class 0.000 abstract description 4
- 235000013824 polyphenols Nutrition 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 3
- -1 C18 Substances 0.000 abstract description 2
- 238000010812 external standard method Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000002203 pretreatment Methods 0.000 abstract description 2
- 238000011002 quantification Methods 0.000 abstract description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 21
- 239000011159 matrix material Substances 0.000 description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- 239000012071 phase Substances 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000004044 response Effects 0.000 description 8
- 239000000575 pesticide Substances 0.000 description 7
- 239000012086 standard solution Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 5
- 244000183278 Nephelium litchi Species 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 239000012224 working solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 3
- 238000000622 liquid--liquid extraction Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000000447 pesticide residue Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005889 Cyantraniliprole Substances 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- 206010033799 Paralysis Diseases 0.000 description 2
- 230000001154 acute effect Effects 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- DVBUIBGJRQBEDP-UHFFFAOYSA-N cyantraniliprole Chemical compound CNC(=O)C1=CC(C#N)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl DVBUIBGJRQBEDP-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 210000000663 muscle cell Anatomy 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 241000426497 Chilo suppressalis Species 0.000 description 1
- 241000008892 Cnaphalocrocis patnalis Species 0.000 description 1
- 241000255967 Helicoverpa zea Species 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- 241000255777 Lepidoptera Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000500437 Plutella xylostella Species 0.000 description 1
- 241000700159 Rattus Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- XORXDJBDZJBCOC-UHFFFAOYSA-N azanium;acetonitrile;acetate Chemical compound [NH4+].CC#N.CC([O-])=O XORXDJBDZJBCOC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 201000011243 gastrointestinal stromal tumor Diseases 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000010829 isocratic elution Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical compound NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 102000042094 ryanodine receptor (TC 1.A.3.1) family Human genes 0.000 description 1
- 108091052345 ryanodine receptor (TC 1.A.3.1) family Proteins 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 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 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000048 toxicity data Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/28—Control of physical parameters of the fluid carrier
- G01N30/34—Control of physical parameters of the fluid carrier of fluid composition, e.g. gradient
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
- G01N30/724—Nebulising, aerosol formation or ionisation
- G01N30/726—Nebulising, aerosol formation or ionisation by electrical or glow discharge
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- G01N2030/042—Standards
- G01N2030/047—Standards external
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- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
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- G01N30/06—Preparation
- G01N2030/065—Preparation using different phases to separate parts of sample
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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Abstract
The invention discloses an ultra-high performance liquid chromatography tandem mass spectrometry analysis method for cyhalodiamide in fruits. Including pretreatment and chromatographic mass spectrometry. The invention adopts acetonitrile as an extractant, a mixture of anhydrous magnesium sulfate and sodium chloride as an extraction salt, n-hexane removes partial pigment, 4 dispersion adsorbents such as PSA, C18, multi-wall carbon nano-tubes and GCB are combined for purification to further remove impurities such as pigment, sugar, polyphenol and the like in fruits, and an external standard method is used for quantification. The pretreatment method has the advantages of simple and convenient operation, good purification effect, high recovery rate, good reproducibility, small organic solvent consumption and the like, has lower minimum detection concentration of the cyhalodiamide, and is suitable for the analysis and detection of the cyhalodiamide in fruits.
Description
Technical Field
The invention belongs to the field of pesticide detection, and particularly relates to an ultra-high performance liquid chromatography-tandem mass spectrometry method for cyhalodiamide in fruits.
Background
The cyhalodiamide belongs to phthalic diamide pesticide, is a novel pesticide independently developed by Zhejiang chemical industry institute, and has the action mechanism that calcium ions in intracellular calcium libraries are released without limit by activating ryanodine receptors in insect muscle cells, so that the insect muscle cells are causedThe meat is paralyzed and paralyzed loosely, thus stopping feeding and finally leading to death. The cyhalodiamide is mainly applied to the control of lepidoptera pests such as chilo suppressalis, cotton bollworms, plutella xylostella, rice leaf rollers and the like on crops, and has the characteristics of high efficiency, broad insecticidal spectrum and the like. Acute oral LD of cyhalodiamide on rats 50 The value is more than 5000mg/kg, and the acute percutaneous LD 50 Values > 2000mg/kg; no irritation to rabbit skin and eyes; the results show that the cyhalodiamide has low toxicity to animals, but the toxicity data about the cyhalodiamide to fish, bees, silkworms and the like are temporarily absent. In recent years, food safety problems and ecological environment risks caused by excessive use of pesticides are increasingly focused, pesticide residues and food safety problems are also widely focused in the international society, and particularly, detection concentrations of chemical pesticides in fresh-eating-based foods such as fruits are increasingly low, so that more efficient and sensitive analysis methods are needed to rapidly determine the content of the chemical pesticides in the foods, and method support is provided for accurately evaluating the residual level of the pesticides in the fruits. The current analysis method of the cyhalodiamide has few reports, mainly relates to the content analysis of matrixes such as rice, environmental water, soil and the like, and has not been reported in fruits; the purification mode adopts a traditional chromatographic column and a simple PSA (pressure sensitive adhesive) dispersion adsorbent for purification, and lacks systematic comparison evaluation of extraction and purification parameters of the cyhalodiamide in different matrixes.
Disclosure of Invention
The invention aims to solve the technical problem of providing an ultra-high performance liquid chromatography tandem mass spectrometry method for detecting the cyhalodiamide in fruits, which can detect the cyhalodiamide in the fruits and meet the requirements of accuracy, precision and sensitivity in pesticide residue analysis.
The invention relates to an ultra-high performance liquid chromatography tandem mass spectrometry analysis method of cyhalodiamide in fruits, which comprises the following steps:
A. sample pretreatment
(1) Extraction of
Adding 10mL of acetonitrile into 5.0g of each fruit sample, mixing uniformly by vortex, adding 4g of anhydrous magnesium sulfate and 1g of sodium chloride, centrifuging after vortex, and collecting an extracting solution;
(2) Purification of
Adding 5mL of n-hexane into each 2mL of the extract, shaking, standing, discarding the upper layer purified solution, and adding 100mg of PSA and 100mg of C into the lower acetonitrile phase 18 Purifying in a centrifuge tube containing 10mg of multi-walled carbon nanotubes and 10mg of GCB mixed dispersion adsorbent, shaking, swirling, centrifuging, collecting supernatant, and filtering with an organic needle filter to obtain ultra-high performance liquid chromatography-tandem mass spectrometry;
B. the conditions of the ultra-high performance liquid chromatography tandem mass spectrometry are as follows:
the chromatographic conditions for liquid chromatography were as follows: the mobile phase is A: 2mmol/L aqueous ammonium acetate solution containing 0.1% formic acid, mobile phase B: acetonitrile; the gradient elution program adopted is 80% A (0.5 min), 0.5-2.0 min 40% A,40% A (1 min), 3.0-4.0 min 15% A,15% A (0.5 min), 4.5-6.5 min 80% A,80% A (1 min); the flow rate was set at 0.3mL/min; column temperature: sample injection amount is 2 mu L at 35 ℃;
mass spectrometry conditions: electrospray negative ion mode (ESI-); capillary voltage: 4KV; the flow rate of the atomized air is 3.0mL/min, the flow rates of the drying air and the heating air are 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 is as follows: multiple reactive ion monitoring mode (MRM), cyhalodiamide quantitative ion pair: 522.05 > 254.15, qualitative ion pair 522.05 > 214.1.
Preferably, the column for liquid chromatography is: porosill 120SB-C18 column (75 mm. Times.2.1 mm, 2.7-. Mu.m) column.
Further preferred is:
A. sample pretreatment
(1) Extraction of
Weighing 5.0g of fruit sample, placing into a 50mL centrifuge tube, adding 10mL of acetonitrile, mixing by vortex for 5min, adding 4g of anhydrous magnesium sulfate and 1g of sodium chloride, centrifuging at 5000rpm for 5min after vortex, and collecting extract;
(2) Purification of
Transferring 2mL of the extract from the centrifuge tube, adding 5mL of n-hexane, shaking vigorously for 1min, standing for 5min, discarding the upper purified solution, adding 100mg of PSA and 100mg of C into the acetonitrile phase of the lower layer 18 10mg of multiwall carbon nanotubes and 10mg of GCBPurifying in a centrifuge tube mixed with a dispersion adsorbent, shaking vigorously, swirling for 10s, centrifuging at 10000r/min for 2min, collecting supernatant, and passing through a 0.22 μm organic needle filter for ultra-high performance liquid chromatography-tandem mass spectrometry;
B. the conditions of the ultra-high performance liquid chromatography tandem mass spectrometry are as follows:
the chromatographic conditions for liquid chromatography were as follows: the mobile phase is A: 2mmol/L aqueous ammonium acetate solution containing 0.1% formic acid, mobile phase B: acetonitrile. The gradient elution program adopted is 80% A (0.5 min), 0.5-2.0 min 40% A,40% A (1 min), 3.0-4.0 min 15% A,15% A (0.5 min), 4.5-6.5 min 80% A,80% A (1 min); the flow rate was set at 0.3mL/min; column temperature: sample injection amount is 2 mu L at 35 ℃;
mass spectrometry conditions: electrospray negative ion mode (ESI-); capillary voltage: 4KV; the flow rate of the atomized air is 3.0mL/min, the flow rates of the drying air and the heating air are 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 is as follows: multiple reactive ion monitoring mode (MRM), cyhalodiamide quantitative ion pair: 522.05 > 254.15, qualitative ion pair 522.05 > 214.1.
Compared with the prior art, the invention has the following advantages and effects
The invention establishes an analysis and detection method of cyhalodiamide in fruits, acetonitrile is used as an extracting agent, a mixture of anhydrous magnesium sulfate and sodium chloride is used as an extracting salt, n-hexane is used for removing partial pigment, and 4 dispersing adsorbents such as PSA, C18, multi-wall carbon nano tubes and GCB are used for combined purification to further remove impurities such as pigment, sugar and polyphenol in the fruits, and an external standard method is used for quantification. The pretreatment method has the advantages of simple and convenient operation, good purification effect, high recovery rate, good reproducibility, small organic solvent consumption and the like, has lower minimum detection concentration of the cyhalodiamide, and is suitable for the analysis and detection of the cyhalodiamide in fruits.
Drawings
FIG. 1 shows the purification effect of 9 different purification combinations on cyantraniliprole;
FIG. 2 is a graph showing the response effect of mass spectrum positive and negative ion modes on cyhalodiamide;
FIG. 3 shows the effect of different size columns on the separation of cyhalodiamide;
FIG. 4 is the response effect of mobile equal and gradient elution on cyhalodiamide;
FIG. 5 is a standard graph of cyhalodiamide;
FIG. 6 is a standard solution chromatogram of cyhalodiamide (10 μg/L);
FIG. 7 is a fruit sample addition chromatogram of cyhalodiamide (10 μg/kg).
Detailed Description
The following examples are further illustrative of the invention and are not intended to be limiting thereof.
Example 1:
the invention relates to an ultra-high performance liquid chromatography tandem mass spectrometry analysis method of cyhalodiamide in fruits, which adopts the following main instruments and reagent information:
1. instrument:
ultra-high performance liquid chromatography tandem mass spectrometer (Shimadzu 8045), multitube vortex mixer (LICHEN vortex-2500 MT), centrifuge (GTR 22-1).
2. Reagent: acetonitrile (chromatographic purity, fisher company, USA), anhydrous magnesium sulfate (analytical purity, national drug group), sodium chloride (analytical purity, national drug group), ethylenediamine-N-propylsilane adsorbent (PSA, shanghai America), graphitized carbon black adsorbent (GCB, shanghai America), octadecyl bonded silica gel adsorbent (C) 18 Shanghai Annotation), multiwall carbon nanotubes (Nanjing Nanjiefeng nanomaterial technologies Co., ltd.), nano zirconia (Shanghai Ala Biotechnology Co., ltd.), florisil solid phase extraction columns (Agilent Co., ltd.), amino solid phase extraction columns (Agilent Co., ltd.), chlorofluorocyantraniliprole (99.5%) (CHEM SERVICE Co.).
3. Preparing a standard working solution: respectively accurately weighing 10mg of standard chlorofluorocyantraniliprole, dissolving with 10mL of chromatographic pure acetonitrile, preparing 1000mg/L stock solution, sealing and preserving in a refrigerator at 0-4 ℃ for 6 months.
Preparing a working solution: accurately transferring a proper amount of stock solution, and gradually diluting the stock solution into working solutions with different concentrations of 1, 5, 10, 20, 100 and 500 mug/L by using chromatographic pure acetonitrile, so as to prepare the solution at present.
4. Instrument working conditions:
chromatographic conditions: a Porosill 120SB-C18 column (75 mm. Times.2.1 mm, 2.7-. Mu.m) was used.
The chromatographic conditions of the liquid chromatography are as follows: the mobile phase is A: 2mmol/L ammonium acetate aqueous solution containing 0.1% formic acid by mass, mobile phase B: acetonitrile. The adopted gradient elution program comprises the volume fraction of 80% A (0.5 min), the volume fraction of 40% A (1 min), the volume fraction of 15% A (3.0-4.0 min), the volume fraction of 15% A (0.5 min), the volume fraction of 80% A (4.5-6.5 min) and the volume fraction of 80% A (1 min); the flow rate was set at 0.3mL/min; column temperature: the sample injection amount was 2. Mu.L at 35 ℃.
Mass spectrometry conditions:
electrospray negative ion mode (ESI-); capillary voltage: 4KV; the flow rate of the atomized air is 3.0mL/min, the flow rates of the drying air and the heating air are 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 is as follows: multiple reactive ion monitoring mode (MRM), cyhalodiamide quantitative ion pair: 522.05 > 254.15, qualitative ion pair 522.05 > 214.1.
5. Sample pretreatment
(1) Extraction of
Weighing 5.0g of fruit sample (to the accuracy of 0.01g, all fruit samples used in the embodiment are litchi whole fruits), placing into a 50mL centrifuge tube, adding 10mL acetonitrile, mixing uniformly for 5min by vortex (LICHEN Vorter-2500 MT), adding 4g of anhydrous magnesium sulfate and 1g of sodium chloride, centrifuging (GTR 22-1 type desk centrifuge) at 5000rpm after vortex (LICHEN Vorter-2500 MT) for 5min, and collecting the upper layer extract.
(2) Purification of
Transferring 2mL of the extract from the centrifuge tube, adding 5mL of n-hexane, shaking vigorously for 1min, standing for 5min, discarding the upper purified solution, adding 100mg of PSA and 100mg of C into the acetonitrile phase of the lower layer 18 Purifying in centrifuge tube containing 10mg of multiwall carbon nanotube and 10mg of GCB mixed dispersion adsorbent, shaking vigorously, swirling for 10s, centrifuging at 10000r/min for 2min, collecting supernatant, filtering with 0.22 μm organic needle filter, and standingAnd (4) performing ultra-high performance liquid chromatography tandem mass spectrometry, wherein the measuring method is shown in the step (4).
6. Experimental results
(1) Optimization of extraction steps
1) Optimization of extraction solvent
When the extraction solvent is selected, acetonitrile containing 0.1% formic acid and 2mmol/L ammonium acetate acetonitrile solution containing 0.1% formic acid can be used as the extraction solution of the invention, the extraction method (1) in the step 5 is used for extraction, the extraction efficiency of the 3 extraction solutions is slightly different, but the extraction rate is more than 90%, and the factors of saving cost, time and labor and the like are comprehensively considered, so that the acetonitrile homogenate extraction is selected as the extraction method of the cyhalodiamide in fruits.
2) Selection of extraction salts
Anhydrous magnesium sulfate is often used to remove moisture from the matrix and sodium chloride is added to separate the organic and aqueous phases. According to the invention, anhydrous magnesium sulfate and sodium chloride are selected to have a mass ratio of 4:1, so that good extraction efficiency can be obtained.
(2) Optimization of the purification conditions
In selecting the purification material, C is compared with 18 The purifying effect of the chlorofluorocyantraniliprole in the fruits is influenced by 8 purifying conditions such as PSA, GCB, multi-wall carbon nano tubes, nano zirconia, amino, florisil solid phase extraction columns, normal hexane liquid-liquid distribution and the like. 100 mug/kg of cyhalodiamide is adopted as the addition concentration, specifically 50 mug of the weighed blank fruit sample (5 g of litchi) is sucked from 10000 mug/L of cyhalodiamide standard solution, the mixture is fully mixed after being added, 10mL of acetonitrile is added after being placed for 2 hours, the mixture is uniformly mixed for 5 minutes by vortex, 4g of anhydrous magnesium sulfate and 1g of sodium chloride are added, the mixture is centrifuged for 5 minutes at 5000rpm after vortex, and 2mL of extract in a centrifuge tube is removed for purification.
C 18 The adsorbent has the function of removing nonpolar interferents such as fat, lipid and the like in the matrix; PSA can remove fatty acids, pigments, saccharides, etc. from the matrix; the GCB can remove impurities such as pigment; the multiwall carbon nanotube has larger specific surface area, and can effectively remove interference impurities such as pigment and the like; the nano zirconia has the performances of large specific surface area, large adsorption capacity and the like. According to the adsorption capacity and the property of the adsorbent, 50mg of C is respectively selected 18 Purifying by 50mg of PSA, 50mg of GCB, 5mg of multi-wall carbon nanotubes and 5mg of nano zirconia. Adding 2mL of the extract into a centrifuge tube respectively filled with the 5 dispersion adsorbents, purifying, shaking vigorously, swirling for 10s, centrifuging at 10000r/min for 2min, collecting supernatant, and filtering with 0.22 μm organic needle filter to obtain the final product.
The amino and florisil solid phase extraction columns were pre-rinsed with 5mL of acetonitrile/ethyl acetate (v/v=3/1) and acetone/n-hexane (v/v=1/9), respectively, and then the solid phase extraction columns were equilibrated with 5mL of ethyl acetate and n-hexane, respectively, when the solvent level reached the surface of the column adsorption layer, 2mL of the extract was immediately added, the eluate was received, and 10mL of acetonitrile/ethyl acetate (v/v=3/1) and acetone/n-hexane (v/v=1/9) were eluted, respectively, and dried at 50 ℃ on a nitrogen blower, dissolved with 2mL of methanol, and passed through a 0.22 μm organic needle filter, and subjected to ultra-high performance liquid chromatography tandem mass spectrometry.
And (3) placing 2mL of the extracting solution in a separating funnel, adding 5mL of n-hexane for extraction, standing after violent mixing, and after complete layering, passing the lower acetonitrile phase through a 0.22 mu m organic needle filter to perform ultra-high performance liquid chromatography tandem mass spectrometry (the chromatographic and mass spectrometry conditions are the same as the instrument working conditions in 4).
The results show that the recovery rate of the cyhalodiamide is over 90 percent after being purified by the 8 purifying conditions independently, and the recovery rate can meet the requirements.
TABLE 1 influence of different purification conditions on recovery
However, because different fruits contain different types and contents of impurities such as pigment, sugar and polyphenol, the single purifying material has poor purifying effect, larger matrix effect can be generated, the accuracy of quantitative results is influenced, and the mass spectrum is easy to pollute, so that the invention combines different purifying materials and explores the influence of the purifying materials on the matrix purifying effect and the recovery rate.
1.50mg of PSA, 50mg of C18 and 5mg of nano zirconia;
2.100mg of PSA, 100mg of C18 and 5mg of nano zirconia;
3.50mg of PSA, 50mg of C18, 5mg of multi-wall carbon nanotubes and 5mg of nano zirconia;
4.100mg of PSA, 100mg of C18, 5mg of multi-wall carbon nanotubes and 5mg of nano zirconia;
5.100mg PSA, 100mg C18, 5mg multiwall carbon nanotubes, 5mg GCB;
6.100mg PSA, 100mg C18, 5mg multiwall carbon nanotubes, 10mg GCB;
7.100mg PSA, 100mg C18, 10mg multiwall carbon nanotubes, 5mg GCB;
8.100mg PSA, 100mg C18, 10mg multi-walled carbon nanotubes, 10mg GCB;
9.5mL of n-hexane liquid was partitioned into 100mg of PSA, 100mg of C18, 10mg of multiwall carbon nanotubes, and 10mg of GCB;
the purification effect is shown in figure 1, liquid-liquid distribution is carried out by adopting normal hexane firstly, partial pigment is removed, and then 100mg of PSA and 100mg of C are used 18 The multi-wall carbon nano tube (10 mg) and the GCB dispersion adsorbent (10 mg) are combined for purification, so that most of impurities such as pigment, sugar, polyphenol and the like can be obviously removed, a good purification effect is achieved, and the recovery rate meets the analysis requirement (see Table 2). Taking the recovery rate, impurity removal effect and other factors into consideration comprehensively, selecting n-hexane for liquid-liquid distribution, and then using 100mg of PSA and 100mg of C 18 10mg of multi-walled carbon nanotubes and 10mg of GCB dispersed adsorbent were purified in combination to the optimal purification conditions.
TABLE 2 influence of different combinations of purification modes on recovery rate
(3) Matrix effect
Matrix Effects (ME) refer to the effect of components other than the analyte in a sample on the response value of the analyte. The matrix effect was calculated using the formula: ME (%) = [ (slope of matrix matching standard curve/slope of pure solvent standard curve) -1) ] ×100%, and 100mg/L of standard working solution of cyhalodiamide was diluted stepwise with the above-mentioned matrix-purified solution of blank fruit (without cyhalodiamide) after sample pretreatment in step 5 to prepare a matrix standard curve (determined by chromatography and mass spectrometry in step 4). The matrix effect is classified into 3 grades according to the ME absolute value, and is a weak matrix effect when the ME absolute value is in the range of 0-20%, a medium-strength matrix effect when the ME absolute value is in the range of 20-50%, and a strong matrix effect when the ME absolute value is above 50%. The solvent curve for cyhalodiamide is: y=8.01087e+0070 x+127881, r= 0.9988, the more complex substrate litchi samples were chosen as the substrate standard curve, y=7.63487e+0070 x+426383, r= 0.9991. Calculated according to the above formula, the matrix effect was-4.7%, with weak matrix effect. Thus, the experiment can be quantified using a solvent standard curve.
(4) Optimization of detection conditions
The invention examines the response influence of positive and negative ion scanning mode to the chlorofluorocyantraniliprole. The scanning modes of the instrument are respectively positive ion scanning and negative ion scanning, and 100 mug/L standard solution of the cyhalodiamide is subjected to sample injection analysis by an automatic sample injector, so that the formation and response conditions of characteristic ions of the cyhalodiamide are observed. The results show (fig. 2) that the response of cyhalodiamide is higher in the negative ion mode, and therefore, the negative ion scan mode was selected for this experiment.
The invention examines the separation, response and retention effects of three common liquid chromatographic columns of 50mm, 75mm and 100mm on the cyhalodiamide. The standard solution of 100 mug/L chlorofluorocyantraniliprole is used as a separation object, and the working conditions of the instrument are the same as those of the step 4, except that the chromatographic column is different, specifically: a100. Mu.g/kg addition sample was analyzed by selecting 3 types of Shimadzu Shim-pack GIST-HP C18 (50 mm. Times.2.1 mm, 3.0-. Mu.m), porosiell 120SB-C18 column (75 mm. Times.2.1 mm, 2.7-. Mu.m) and Shimadzu Shim-pack Velox SP-C18 (100 mm. Times.2.7 mm, 3.0-. Mu.m) columns. The results show (FIG. 3) that when a poroshall 120SB-C18 column (75 mm. Times.2.1 mm,2.7- μm) is used, the separation effect of the cyhalodiamide is better, the baseline separation can be better realized, the good symmetrical peak type is obtained, and the accuracy of the quantitative result is ensured.
After the chromatographic column is determined, the invention examines the separation effect of isocratic elution and gradient elution on the cyantraniliprole in 100 mug/kg added sample, the working condition of the instrument is referred to as step 4, and only the elution condition is changed. Wherein, the volume ratio of mobile phase A (2 mmol/L ammonium acetate aqueous solution containing 0.1% formic acid) to mobile phase B (acetonitrile) is 65/35; the gradient elution procedure was 80% A (0.5 min), 0.5-2.0 min 40% A,40% A (1 min), 3.0-4.0 min 15% A,15% A (0.5 min), 4.5-6.5 min 80% A,80% A (1 min). Comparison shows (figure 4) that gradient elution can significantly improve the response of the chlorofluorocyantraniliprole, and finally the invention determines to use a gradient elution procedure.
(5) Methodology investigation
By adopting external standard quantitative analysis, the concentration of the chlorofluorocyantraniliprole is taken as an abscissa, the quantitative ion peak area is taken as an ordinate, a quasi-solution curve is drawn (the working condition of the instrument is referred to as step 4), and as shown in fig. 5, the regression equation is y=8.01087e+0070+127881 (R 2 =0.9989). The detection limit of the ultra-high performance liquid chromatography tandem mass spectrometer on the cyhalodiamide is 0.1 mug/kg, and the quantitative limit is 1 mug/kg.
Taking blank fruit samples (the matrix purification solution of litchi after the pretreatment of the sample in the step 5 does not contain chlorofluorocyantraniliprole), respectively setting the concentration of 3 grades of added chlorofluorocyantraniliprole such as 10 mug/kg, 100 mug/kg and 500 mug/kg, and carrying out an addition recovery rate test, wherein the addition concentration of 10 mug/kg is specifically that 50 mug of the weighed blank fruit samples are sucked from 1000 mug/L standard solution, the addition concentration of 100 mug/kg is specifically that 50 mug of the weighed blank fruit samples are sucked from 10000 mug/L standard solution, the addition concentration of 500 mug/kg is specifically that 25 mug of the weighed blank fruit samples are sucked from 10000 mug/L standard solution, fully mixing after the addition, carrying out an extraction and purification step (see step 5) after 2 hours, setting 5 repetitions of each grade of addition concentration, and carrying out chromatography and mass spectrum (see step 4). As is clear from Table 3, when the concentration of cyhalodiamide added to fruits was 10. Mu.g/kg, 100. Mu.g/kg and 500. Mu.g/kg, the average recovery rate was 89.3% to 101.3% and the relative standard deviation was 3.01% to 8.50% (FIGS. 6 and 7).
TABLE 3 recovery and standard deviation for different additive concentrations
The invention establishes an analysis and detection method of the cyhalodiamide in fruits. The cyhalodiamide shows good linear relation in the concentration range of 1-500 mug/L, the average recovery rate of the cyhalodiamide added into fruits is 89.3-101.3%, the Relative Standard Deviation (RSD) is 3.01-8.50%, and the quantitative limit of the method is 1 mug/kg. The method has the characteristics of simple and rapid operation, good sample reproducibility and strong applicability, and various technical indexes can meet the detection and analysis requirements of pesticide residues.
The foregoing is a preferred embodiment of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the present invention should be made in the equivalent manner and are included in the scope of the present invention.
Claims (3)
1. The ultra-high performance liquid chromatography tandem mass spectrometry analysis method for the cyhalodiamide in the fruits is characterized by comprising the following steps of
The method comprises the following steps:
A. sample pretreatment
(1) Extraction of
Adding 10mL of acetonitrile into 5.0g of each fruit sample, mixing uniformly by vortex, adding 4g of anhydrous magnesium sulfate and 1g of sodium chloride, centrifuging after vortex,
collecting an extracting solution, wherein the fruit is litchi;
(2) Purification of
Adding 5mL of n-hexane into each 2mL of the extract, shaking, standing, discarding the upper layer of purified solution, adding the lower acetonitrile phase into a centrifuge tube filled with 100mg of PSA, 100mg of C18, 10mg of multi-walled carbon nanotube and 10mg of GCB mixed dispersion adsorbent, purifying, and oscillating
After vortex, re-centrifuging, taking supernatant, and passing through an organic needle filter to be subjected to ultra-high performance liquid chromatography tandem mass spectrometry;
B. the conditions of the ultra-high performance liquid chromatography tandem mass spectrometry are as follows:
the chromatographic conditions for liquid chromatography were as follows: the mobile phase is A: 2mmol/L ammonium acetate aqueous solution containing 0.1% formic acid, flow
Phase B: acetonitrile; the gradient elution procedure used was 80% A0.5 min, 0.5-2.0 min 40% A,40% A1 min, 3.0-4.0 min 15% A,15% A0.5 min), 4.5-6.5 min 80% A,80% A1 min; the flow rate was set at 0.3mL/min;
column temperature: sample injection amount is 2 mu L at 35 ℃;
mass spectrometry conditions: electrospray negative ion mode ESI-; capillary voltage: 4KV; atomizing air flow rate is 3.0mL/min, and drying
The air flow rate and the heating air flow rate are 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 reactive ion monitoring mode (MRM), cyhalodiamide quantitative ion pair: 522.05 > 254.15, qualitative ion pair 522.05 > 214.1.
2. The method for ultra performance liquid chromatography tandem mass spectrometry analysis of cyhalodiamide in fruit according to claim 1, wherein the column of liquid chromatography is: porosill 120SB-C18 column 75 mm. Times.2.1 mm,2.7- μm column.
3. Ultra performance liquid chromatography tandem mass spectrometry analysis method for cyhalodiamide in fruits according to claim 1 or 2
A method, comprising the steps of:
A. sample pretreatment
(1) Extraction of
Weighing 5.0g of a fruit sample, placing the fruit sample into a 50mL centrifuge tube, adding 10mL of acetonitrile, uniformly mixing for 5min by vortex, adding 4g of anhydrous magnesium sulfate and 1g of sodium chloride, centrifuging at 5000rpm for 5min after vortex, and collecting an extracting solution, wherein the fruit is litchi;
(2) Purification of
Transferring 2mL of the extracting solution in the centrifuge tube, adding 5mL of n-hexane, shaking vigorously for 1min, standing for 5min, discarding the upper layer of purified solution,
adding the lower acetonitrile phase into a centrifuge tube filled with 100mg of PSA, 100mg of C18, 10mg of multiwall carbon nanotubes and 10mg of GCB mixed dispersion adsorbent for purification, shaking vigorously, swirling for 10s, centrifuging at 10000r/min for 2min, taking supernatant, and passing through a 0.22 mu m organic needle filter for ultra-high performance liquid chromatography tandem mass spectrometry;
B. the conditions of the ultra-high performance liquid chromatography tandem mass spectrometry are as follows:
the chromatographic conditions for liquid chromatography were as follows: the mobile phase is A: 2mmol/L ammonium acetate aqueous solution containing 0.1% formic acid, flow
Phase B: acetonitrile; the gradient elution procedure used was 80% A0.5 min, 0.5-2.0 min 40% A,40% A1 min, 3.0-4.0 min 15% A,15% A0.5 min, 4.5-6.5 min 80% A,80% A1 min; the flow rate was set at 0.3mL/min;
column temperature: sample injection amount is 2 mu L at 35 ℃;
mass spectrometry conditions: electrospray negative ion mode ESI-; capillary voltage: 4KV; the flow rate of the atomized air is 3.0mL/min, the flow rates of the drying air and the heating air are 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 is as follows: multiple reactive ion monitoring mode (MRM), cyhalodiamide quantitative ion pair: 522.05 > 254.15, qualitative ion pair 522.05 > 214.1.
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