CN115267019A - 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
- Publication number
- CN115267019A CN115267019A CN202210770296.XA CN202210770296A CN115267019A CN 115267019 A CN115267019 A CN 115267019A CN 202210770296 A CN202210770296 A CN 202210770296A CN 115267019 A CN115267019 A CN 115267019A
- Authority
- CN
- China
- Prior art keywords
- cyhalodiamide
- liquid chromatography
- mass spectrometry
- performance liquid
- tandem mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 56
- 235000013399 edible fruits Nutrition 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000001195 ultra high performance liquid chromatography Methods 0.000 title claims abstract description 12
- 238000010846 tandem mass spectrometry analysis Methods 0.000 title claims abstract description 9
- 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 30
- 238000000746 purification Methods 0.000 claims abstract description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 20
- 238000000605 extraction Methods 0.000 claims abstract description 18
- 239000003463 adsorbent Substances 0.000 claims abstract description 16
- 238000001514 detection method Methods 0.000 claims abstract description 15
- 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
- 238000011002 quantification Methods 0.000 claims abstract description 9
- 150000002500 ions Chemical class 0.000 claims description 27
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- 238000010811 Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 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
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000004811 liquid chromatography Methods 0.000 claims description 7
- 238000001819 mass spectrum Methods 0.000 claims description 7
- 239000002904 solvent Substances 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
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000004587 chromatography analysis Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000012544 monitoring process Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 32
- 238000011084 recovery Methods 0.000 abstract description 12
- 239000000049 pigment Substances 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 7
- 238000004949 mass spectrometry Methods 0.000 abstract description 4
- 150000008442 polyphenolic compounds Chemical class 0.000 abstract description 4
- 235000013824 polyphenols Nutrition 0.000 abstract description 4
- 238000010812 external standard method Methods 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- -1 C18 Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 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
- 239000005889 Cyantraniliprole Substances 0.000 description 6
- 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 6
- 238000000926 separation method Methods 0.000 description 6
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 5
- 244000183278 Nephelium litchi Species 0.000 description 4
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003260 vortexing Methods 0.000 description 4
- 239000012224 working solution Substances 0.000 description 4
- 241000238631 Hexapoda Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000010829 isocratic elution 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
- 238000001228 spectrum Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 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
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 210000003205 muscle Anatomy 0.000 description 2
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 235000015742 Nephelium litchi Nutrition 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
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000003556 assay Methods 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
- 239000006229 carbon black Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 238000001914 filtration Methods 0.000 description 1
- 201000011243 gastrointestinal stromal tumor Diseases 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 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
- 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
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000000663 muscle cell Anatomy 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
- 230000010355 oscillation Effects 0.000 description 1
- 238000005192 partition Methods 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
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research 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
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 230000003595 spectral effect Effects 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
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000004885 tandem mass spectrometry Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000048 toxicity data Toxicity 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
- G01N30/62—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
-
- 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
- G01N2030/042—Standards
- G01N2030/047—Standards external
-
- 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
- G01N2030/062—Preparation extracting sample from raw material
-
- 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
- G01N2030/065—Preparation using different phases to separate parts of sample
-
- 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
- G01N2030/143—Preparation by elimination of some components selective absorption
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Dispersion Chemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses an ultra-high performance liquid chromatography tandem mass spectrometry analysis method of cyhalodiamide in fruits. Including pretreatment and chromatographic mass spectrometry. The invention adopts acetonitrile as an extracting agent, a mixture of anhydrous magnesium sulfate and sodium chloride as an extraction salt, n-hexane removes part of pigments, and 4 dispersed adsorbents such as PSA, C18, multi-walled carbon nanotubes and GCB are jointly purified to further remove impurities such as pigments, sugar, polyphenol and the like in fruits, and the method is used for quantification 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 the cyhalodiamide, and is suitable for analyzing and detecting 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 analysis method for cyhalodiamide in fruits.
Background
The cyhalodiamide belongs to a phthalic diamide pesticide, is a novel pesticide independently developed by Zhejiang chemical research institute company Limited, and has the action mechanism that calcium ions in an intracellular calcium reservoir are unlimitedly released by activating a ryanodine receptor in insect muscle cells, so that the insect muscle generates flabby paralysis and paralysis, the feeding is stopped, and finally the insect muscle dies. The cyhalodiamide is mainly applied to the prevention and control of lepidoptera pests such as chilo suppressalis, cotton bollworm, diamond back moth, rice leaf roller and the like on crops, and has the characteristics of high efficiency, wide insecticidal spectrum and the like. Acute oral LD of cyhalodiamide to rat50Value > 5000mg/kg, acute percutaneous LD50The value is more than 2000mg/kg; has no irritation to rabbit skin and eyes; the result shows that the cyhalodiamide has low toxicity to animals, but toxicity data about the cyhalodiamide on fish, bees, silkworms and the like are temporarily absent. In recent years, people pay more attention to food safety problems and ecological environment risks caused by overuse of pesticides, pesticide residues and food safety problems are also paid more attention to international society, and particularly, the detection concentration of chemical pesticides in fresh food-oriented foods such as fruits is lower, so that a more efficient and sensitive analysis method is needed for rapidly determining the content of the chemical pesticides in the fresh food-oriented foods, and a method support is provided for accurately evaluating the residue level of the pesticides in the fruits. The existing analysis methods related to the cyhalodiamide are few in reports, mainly relate to content analysis in matrixes such as rice, environmental water, soil and the like, and have no reports in fruits for a while; the purification mode adopts the traditional chromatographic column and the simple PSA dispersion adsorbent for purification, and lacks the extraction of the cyhalodiamide in different matrixes and the systematic comparative evaluation of the purification parameters.
Disclosure of Invention
The invention aims to solve the technical problem of providing an ultra-high performance liquid chromatography tandem mass spectrometry method for cyhalodiamide in fruits, which can detect cyhalodiamide in fruits and meet the requirements on accuracy, precision and sensitivity in pesticide residue analysis.
The ultra-high performance liquid chromatography tandem mass spectrometry analysis method of cyhalodiamide in fruits comprises the following steps:
A. sample pretreatment
(1) Extraction of
Adding 10mL of acetonitrile into 5.0g of each fruit sample, uniformly mixing by vortex, adding 4g of anhydrous magnesium sulfate and 1g of sodium chloride, centrifuging after vortex, and collecting an extracting solution;
(2) Purification
Adding 5mL n-hexane into 2mL extractive solution, shaking, standing, discarding the upper layer of purified solution, adding the lower layer of acetonitrile, 100mg PSA and 100mg C18Purifying in a centrifugal tube with 10mg of multi-walled carbon nanotube and 10mg of GCB mixed dispersion adsorbent, oscillating, whirling, centrifuging again, taking supernatant, passing through an organic needle type filter, and waiting for ultra performance liquid chromatography tandem mass spectrometry;
B. the conditions of the ultra 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 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 (1 min); the flow rate is set to be 0.3mL/min; column temperature: the sample size is 2 mu L at 35 ℃;
mass spectrum conditions: electrospray negative ion mode (ESI-); 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 reactive ion monitoring mode (MRM), cyhalodiamide quantification ion pair: 522.05 > 254.15, and the pair of qualitative ions 522.05 > 214.1.
Preferably, the column for liquid chromatography is: poroshell 120SB-C18 column (75 mm. Times.2.1 mm, 2.7-. Mu.m) chromatography column.
Further preferably:
A. sample pretreatment
(1) Extraction of
Weighing 5.0g of fruit sample, placing the fruit sample in 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 for 5min at 5000rpm after vortex, and collecting the extracting solution;
(2) Purification
Transferring 2mL of the extractive solution from 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 layer of acetonitrile, and adding 100mg of PSA and 100mg of C18Purifying in a centrifugal tube with 10mg of multi-walled carbon nano-tube and 10mg of GCB mixed dispersion adsorbent, violently oscillating, then whirling for 10s, centrifuging for 2min at 10000r/min, taking supernatant, passing through a 0.22 mu m organic needle type filter, and waiting for ultra performance liquid chromatography tandem mass spectrometry;
B. the conditions of the ultra 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: and (3) 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 (1 min); the flow rate is set to be 0.3mL/min; column temperature: the sample size is 2 mu L at 35 ℃;
mass spectrum conditions: electrospray negative ion mode (ESI-); 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 is as follows: multiple reactive ion monitoring mode (MRM), cyhalodiamide quantification ion pair: 522.05 > 254.15, and the pair of qualitative ions 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 extraction salt, n-hexane removes part of pigments, and 4 dispersed adsorbents such as PSA, C18, multi-walled carbon nanotubes and GCB are jointly purified to further remove impurities such as pigments, sugar and polyphenol in the fruits, and the quantification is carried out 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 consumption and the like, has low minimum detection concentration of the cyhalodiamide, and is suitable for the analysis and detection of the cyhalodiamide in fruits.
Drawings
FIG. 1 is a graph of the cleaning effect of 9 different cleaning combinations on cyhalodiamide;
FIG. 2 is a graph of the effect of mass spectrometry positive and negative ion modes on the response of chlorofluoro cyantraniliprole;
FIG. 3 is the effect of chromatographic columns of different specifications on the separation effect of cyhalodiamide;
FIG. 4 is a graph of the effect of mobile isocratic elution and gradient elution on the response of cyhalodiamide;
FIG. 5 is a standard graph of chlorofluorocarbon cyantraniliprole;
FIG. 6 is a standard solution chromatogram (10. Mu.g/L) of cyhalodiamide;
FIG. 7 is a fruit sample addition chromatogram (10. Mu.g/kg) of cyhalodiamide.
Detailed Description
The following examples are further illustrative of the present 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. the instrument comprises the following steps:
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 drugs), sodium chloride (analytically pure, national group of drugs), ethylenediamine-N-propylsilane adsorbent (PSA, shanghai 'an spectrum corporation), graphitized carbon black adsorbent (GCB, shanghai' an spectrum corporation)Si), octadecyl bonded silica gel adsorbent (C)18Shanghai' an spectral company), multiwalled carbon nanotubes (Nanjing Xifeng nanomaterial science and technology Co., ltd.), nano zirconia (Shanghai Aladdin Biotechnology Co., ltd.), flori silica solid phase extraction cartridge (Agilent Co., ltd.), amino solid phase extraction cartridge (Agilent Co., ltd.), chlorofluorocarbon cyantraniliprole (99.5%) (CHEM SERVICE Co., ltd.).
3. Preparing a standard working solution: 10mg of cyhalodiamide standard substance is respectively and accurately weighed, dissolved by 10mL of chromatographic pure acetonitrile to prepare 1000mg/L stock solution, and the stock solution is hermetically stored in a refrigerator at 0-4 ℃ with the storage life of 6 months.
Preparing a working solution: 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. The working conditions of the instrument are as follows:
chromatographic conditions are as follows: a Poroshell 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% by mass of formic acid, mobile phase B: and (3) acetonitrile. The gradient elution program employed was volume fraction 80% A (0.5 min), 0.5-2.0 min volume fraction 40A, volume fraction 40A (1 min), 3.0-4.0 min volume fraction 15% A, volume fraction 15% A (0.5 min), 4.5-6.5 min volume fraction 80% A,80% A (1 min); the flow rate is set to be 0.3mL/min; column temperature: the sample size was 2. Mu.L at 35 ℃.
Mass spectrum conditions:
electrospray negative ion mode (ESI-); 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 is as follows: multiple reactive ion monitoring mode (MRM), cyhalodiamide quantification ion pair: 522.05 > 254.15, and the pair of qualitative ions 522.05 > 214.1.
5. Sample pretreatment
(1) Extraction of
Weighing 5.0g of fruit sample (accurate to 0.01g, the fruit samples used in the embodiment are all whole fruits of litchi chinensis Sonn.), placing in a 50mL centrifuge tube, adding 10mL acetonitrile, vortexing (LICHEN vortex-2500 MT), mixing for 5min, adding 4g anhydrous magnesium sulfate, 1g sodium chloride, vortexing (LICHEN vortex-2500 MT), centrifuging at 5000rpm (GTR 22-1 desk top centrifuge) for 5min, and collecting the upper layer extractive solution.
(2) Purification
Transferring 2mL of the extractive solution from 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 layer of acetonitrile, and adding 100mg of PSA and 100mg of C18Purifying in a centrifugal tube with 10mg of multi-walled carbon nano-tube and 10mg of GCB mixed dispersion adsorbent, violently oscillating, vortexing for 10s, centrifuging for 2min at 10000r/min, taking supernatant, filtering through a 0.22 mu m organic needle filter, and performing ultra performance liquid chromatography tandem mass spectrometry, wherein the determination method is shown in step 4.
6. Results of the experiment
(1) Optimization of extraction procedure
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 extracting solution of the invention, the extracting method (1) in the step 5 is used for extraction, the extraction efficiency of 3 extracting solutions is slightly different, but the extraction rate is more than 90%, and the acetonitrile homogenate is selected for extraction as the method for extracting the cyhalodiamide in the fruits by comprehensively considering the factors of saving cost, saving time, saving labor and the like.
2) Selection of extracted salts
Anhydrous magnesium sulfate is often used to remove water from the matrix and sodium chloride is added to separate the organic and aqueous phases. The invention selects the mass ratio of the anhydrous magnesium sulfate to the sodium chloride of 4:1, and can obtain better extraction efficiency.
(2) Optimization of purification conditions
In selecting the purification material, compare C18The purification effect of the cyhalodiamide in the fruits is influenced by 8 purification conditions such as PSA, GCB, multi-walled carbon nano tubes, nano zirconia, amino and Florisil solid-phase extraction columns, n-hexane liquid-liquid distribution and the like. Adopts 100 mu g/kg of cyhalonilTaking amine as an adding concentration, specifically, absorbing 50 mu L of chlorofluoro cyantraniliprole standard solution from 10000 mu g/L, adding weighed blank fruit samples (5 g of litchi), fully mixing after adding, placing for 2h, adding 10mL of acetonitrile, uniformly mixing for 5min by vortex, adding 4g of anhydrous magnesium sulfate and 1g of sodium chloride, centrifuging for 5min at 5000rpm after vortex, transferring 2mL of extracting solution in a centrifuge tube, and waiting for purification.
C18The adsorbent has the function of removing nonpolar interferents such as fat, lipid and the like in the matrix; PSA can remove fatty acid, pigment, saccharide, etc. from matrix; GCB can remove impurities such as pigment; the multi-walled carbon nano tube 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 characteristics of the adsorbent, 50mg of C is respectively selected1850mg of PSA, 50mg of GCB, 5mg of multi-walled carbon nanotubes and 5mg of nano-zirconia. Adding 2mL of the extract into centrifugal tubes respectively filled with the 5 dispersing adsorbents for purification, after vigorous oscillation, vortexing for 10s, then centrifuging for 2min at 10000r/min, taking supernatant, passing through a 0.22 mu m organic needle type filter, and waiting for ultra performance liquid chromatography tandem mass spectrometry.
The amino and Florisil solid phase extraction column is pre-leached by 5mL acetonitrile/ethyl acetate (v/v = 3/1), acetone/n-hexane (v/v = 1/9), 5mL ethyl acetate and n-hexane are used for balancing solid phase extraction of the small column, when the liquid level of the solvent reaches the surface of the adsorption layer of the small column, 2mL extracting solution is immediately added, eluent is received, 10mL acetonitrile/ethyl acetate (v/v = 3/1) and acetone/n-hexane (v/v = 1/9) are used for elution, the eluent is dried by blowing at 50 ℃ on a nitrogen blowing instrument, 2mL methanol is used for dissolution, and the eluent passes through a 0.22 mu m organic needle filter to be subjected to ultra performance liquid chromatography tandem mass spectrometry.
And (3) placing 2mL of extracting solution into a separating funnel, adding 5mL of n-hexane for extraction, violently mixing uniformly, standing, after complete layering, enabling the lower layer of acetonitrile to pass through a 0.22-micron organic needle type filter, and performing ultra performance liquid chromatography tandem mass spectrometry (the conditions of the chromatogram and the mass spectrum are the same as the working conditions of the instrument in the step 4).
The results show that the recovery rate of the cyhalodiamide is over 90 percent and the recovery rate can meet the requirements after the cyhalodiamide is purified by the 8 purification conditions alone.
TABLE 1 Effect of different purification conditions on recovery
However, different fruits contain different kinds and contents of impurities such as pigments, sugar, polyphenol and the like, so that a single purifying material is poor in purifying effect, a large matrix effect is generated, the accuracy of a quantitative result is influenced, and meanwhile, a mass spectrum is easily polluted.
1.50mg PSA, 50mg C18, 5mg nano zirconia;
2.100mg PSA, 100mg c18, 5mg nano zirconia;
3.50mg PSA, 50mg C18, 5mg multiwall carbon nanotubes, 5mg nanozirconia;
4.100mg PSA, 100mg c18, 5mg multiwall carbon nanotubes, 5mg 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 multiwall carbon nanotubes, 10mg gcb;
9.5mL of n-hexane liquid, 100mg of PSA, 100mg of C18, 10mg of multi-walled carbon nanotubes and 10mg of GCB;
the purification effect is shown (figure 1), liquid-liquid distribution is carried out by adopting n-hexane firstly, partial pigment is removed, and then 100mg of PSA and 100mg of C are used18The 10mg multi-walled carbon nanotube and the 10mg GCB dispersed adsorbent are purified together, most of impurities such as pigment, saccharide, polyphenol and the like can be obviously removed, a good purification effect is achieved, and the recovery rate also meets the analysis requirement (see table 2). Comprehensively considering the factors of recovery rate, impurity removal effect and the like, and selectingLiquid-liquid partition with n-hexane, and 100mg of PSA and 100mg of C1810mg of multi-walled carbon nanotube and 10mg of GCB dispersion adsorbent are jointly purified to be the optimal purification condition.
TABLE 2 Effect of different combinations of purification modes on recovery
(3) Matrix effect
Matrix Effect (ME) refers to the effect of components other than the analyte in the sample on the analyte response value. The matrix effect was calculated using the formula: ME (%) = [ (gradient of matrix matching standard curve/gradient of pure solvent standard curve) -1) ]. Times.100%, 100mg/L standard working solution of cyhalodiamide is diluted step by step with matrix purified solution (without cyhalodiamide) of blank fruit pretreated by the sample in the step 5, and a matrix standard curve is prepared (measured by chromatography and mass spectrometry in the step 4). The matrix effect is divided into 3 grades according to the ME absolute value, when the ME absolute value is in the range of 0-20%, the matrix effect is weak matrix effect, when the ME absolute value is in the range of 20% -50%, the matrix effect is medium-intensity matrix effect, and when the ME absolute value is above 50%, the matrix effect is strong matrix effect. The solvent curve for cyhalodiamide is: y =8.01087e, 007X +, 127881, r =0.9988, selecting a litchi sample with a more complex matrix as a matrix standard curve, Y =7.63487e, 007X +, 426383, r =0.9991. Calculated according to the above formula, the matrix effect is-4.7% and weak matrix effects are present. Therefore, the assay can be quantified using a solvent standard curve.
(4) Optimization of detection conditions
The invention inspects the response influence of the positive and negative ion scanning mode on the cyhalodiamide. The scanning modes of the instrument are respectively a positive ion scanning mode and a negative ion scanning mode, an automatic sample injector is adopted for sample injection analysis of a 100 mu g/L standard solution of the cyhalodiamide, and the formation and response conditions of characteristic ions of the cyhalodiamide are observed. The results show (figure 2) that the response of chlorofluorocarbon cyantraniliprole is high in the negative ion mode, and therefore the negative ion scan mode was chosen for this experiment.
The invention examines the separation, response and retention effects of three common liquid chromatographic columns of 50mm, 75mm, 100mm and the like on cyhalodiamide. Taking a standard solution of 100 mu g/L cyhalodiamide as a separation object, wherein the working conditions of the instrument are the same as those of the step 4, and only the chromatographic column is different, and the method specifically comprises the following steps: shimadzum-pack GIST-HP C18 (50 mm. Times.2.1mm, 3.0- μm), poroshell 120SB-C18 column (75 mm. Times.2.1mm, 2.7- μm) and Shizum-pack Velock SP-C18 (100 mm. Times.2.7mm, 3.0- μm) 3 types of chromatography columns were selected for analysis of 100 μ g/kg of added samples. The results show (FIG. 3) that when a Poroshell 120SB-C18 column (75 mm. Times.2.1 mm, 2.7-mum) is used, the separation effect of the cyhalodiamide is better, the baseline separation can be better realized, a good symmetrical peak pattern is obtained, and the accuracy of the quantitative result is ensured.
After the chromatographic column is determined, the separation effect of isocratic elution and gradient elution on the cyhalodiamide in the 100 mu g/kg added sample is examined, the working conditions of the instrument are shown in step 4, and only the elution conditions are changed. Wherein the adopted isocratic elution adopts the volume ratio of a mobile phase A (2 mmol/L ammonium acetate aqueous solution containing 0.1 percent formic acid) to a mobile phase B (acetonitrile) to be 65/35; the gradient elution procedure 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 (1 min). By contrast (figure 4), gradient elution significantly improved the response of cyhalodiamide, and finally the present invention determined to employ a gradient elution procedure.
(5) Methodology investigation
Quantitative determination is carried out by adopting an external standard method, the concentration of the cyhalodiamide is taken as a horizontal coordinate, the peak area of the quantitative ion is taken as a vertical coordinate, a quasi-solution curve is drawn (the working condition of the instrument refers to the step 4), the figure is shown in figure 5, and the regression equation is y =8.01087e +007x +127881 (R =8.01087e + +127881)2= 0.9989). The detection limit of the ultra-high performance liquid chromatography tandem mass spectrometer to the cyhalodiamide is 0.1 mu g/kg, and the quantification limit is 1 mu g/kg.
Taking a blank fruit sample (the matrix purifying solution of the litchi after the sample pretreatment in the step 5, which does not contain cyhalodiamide), respectively setting the 3-level concentration of the cyhalodiamide for addition, such as 10 mug/kg, 100 mug/kg and 500 mug/kg, and performing an addition recovery test, wherein the 10 mug/kg addition concentration is to absorb 50 mug/L from 1000 mug/L of standard solution to add the weighed blank fruit sample, the 100 mug/kg addition concentration is to absorb 50 mug/L from 10000 mug/L of standard solution to add the weighed blank fruit sample, the 500 mug/kg addition concentration is to absorb 25 mug/L from 10000 mug/L of standard solution to add the weighed blank fruit sample, fully mixing after the addition, carrying out the extraction and purification steps after standing for 2h (see the step 5), setting 5 times of addition concentration per level for repetition, and then carrying out chromatography and mass spectrometry (see the step 4). As shown in Table 3, when the concentrations of chlorofluorocarbon cyantraniliprole added to fruits were 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% (FIG. 6, FIG. 7).
TABLE 3 recovery and standard deviation for different addition concentrations
The invention establishes an analysis and detection method of cyhalodiamide in fruits. The cyhalodiamide of the invention presents a good linear relation in the concentration range of 1-500 mug/L, the average recovery rate of the cyhalodiamide added in fruits is 89.3-101.3%, the Relative Standard Deviation (RSD) is 3.01-8.50%, and the method quantification limit is 1 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 present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (3)
1. An ultra-high performance liquid chromatography tandem mass spectrometry analysis method of cyhalodiamide in fruits is characterized by comprising the following steps:
A. sample pretreatment
(1) Extraction of
Adding 10mL of acetonitrile into 5.0g of each fruit sample, uniformly mixing by vortex, adding 4g of anhydrous magnesium sulfate and 1g of sodium chloride, centrifuging after vortex, and collecting an extracting solution;
(2) Purification
Adding 5mL n-hexane into 2mL extractive solution, shaking, standing, discarding the upper layer of purified solution, adding the lower layer of acetonitrile, 100mg PSA and 100mg C18Purifying in a centrifugal tube with 10mg of multi-walled carbon nanotube and 10mg of GCB mixed dispersion adsorbent, oscillating, whirling, centrifuging again, taking supernatant, passing through an organic needle type filter, and waiting for ultra performance liquid chromatography tandem mass spectrometry;
B. the conditions of the ultra 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 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 (1 min); the flow rate is set to be 0.3mL/min; column temperature: the sample size is 2 mu L at 35 ℃;
mass spectrum conditions: electrospray negative ion mode (ESI-); 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 is as follows: multiple reactive ion monitoring mode (MRM), cyhalodiamide quantification ion pair: 522.05 > 254.15, and the pair of qualitative ions 522.05 > 214.1.
2. The ultra-high performance liquid chromatography tandem mass spectrometry analysis method of cyhalodiamide in fruits according to claim 1, characterized in that the columns of the liquid chromatography are: poroshell 120SB-C18 column (75 mm. Times.2.1 mm,2.7- μm) chromatography column.
3. The ultra-high performance liquid chromatography tandem mass spectrometry analysis method of cyhalodiamide in fruits according to claim 1 or 2, characterized by comprising the steps of:
A. sample pretreatment
(1) Extraction of
Weighing 5.0g of a fruit sample, placing the fruit sample in 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 for 5min at 5000rpm after vortex, and collecting an extracting solution;
(2) Purification
Transferring 2mL of the extractive solution into a centrifuge tube, adding 5mL of n-hexane, shaking vigorously for 1min, standing for 5min, discarding the upper layer of purified solution, adding the lower layer of acetonitrile into a solvent containing 100mg of PSA and 100mg of C18Purifying in a centrifugal tube with 10mg of multi-walled carbon nano-tube and 10mg of GCB mixed dispersion adsorbent, violently oscillating, then whirling for 10s, centrifuging for 2min at 10000r/min, taking supernatant, passing through a 0.22 mu m organic needle type filter, and waiting for ultra performance liquid chromatography tandem mass spectrometry;
B. the conditions of the ultra 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: and (3) 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 (1 min); the flow rate is set to be 0.3mL/min; column temperature: the sample size is 2 mu L at 35 ℃;
mass spectrum conditions: electrospray negative ion mode (ESI-); 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 is as follows: multi-reactive ion monitoring mode (MRM), cyhalodiamide quantification ion-pair: 522.05 > 254.15, and the pair of qualitative ions 522.05 > 214.1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210770296.XA CN115267019B (en) | 2022-06-30 | 2022-06-30 | Ultra-high performance liquid chromatography tandem mass spectrometry analysis method for cyhalodiamide in fruits |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210770296.XA CN115267019B (en) | 2022-06-30 | 2022-06-30 | Ultra-high performance liquid chromatography tandem mass spectrometry analysis method for cyhalodiamide in fruits |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115267019A true CN115267019A (en) | 2022-11-01 |
| CN115267019B CN115267019B (en) | 2024-03-22 |
Family
ID=83764181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210770296.XA Active CN115267019B (en) | 2022-06-30 | 2022-06-30 | Ultra-high performance liquid chromatography tandem mass spectrometry analysis method for cyhalodiamide in fruits |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115267019B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104502482A (en) * | 2014-12-30 | 2015-04-08 | 郭庆龙 | Detecting method for residual quantity of flubendiamide in fruits and vegetables |
| CN107607656A (en) * | 2017-08-07 | 2018-01-19 | 浙江省农业科学院 | The detection method of bromine cyanogen insect amide and metabolin J9Z38 in the flesh of fish |
| CN108732293A (en) * | 2018-05-28 | 2018-11-02 | 广东省农业科学院植物保护研究所 | The high performance liquid chromatography tandem mass spectrum analysis method of indenes piperazine benfluralin and its metabolin |
| CN108760963A (en) * | 2018-05-28 | 2018-11-06 | 广东省农业科学院植物保护研究所 | The high performance liquid chromatography tandem mass spectrum analysis method of pyraclostrobin and its metabolin |
| CN111999419A (en) * | 2020-09-28 | 2020-11-27 | 广东省农业科学院植物保护研究所 | Method for determining content of chlorofluoroether bacteria azole by high performance liquid chromatography-tandem mass spectrometry |
| WO2022120752A1 (en) * | 2020-12-10 | 2022-06-16 | 中国科学院深圳先进技术研究院 | Method for quantitative analysis of free amino acids in biological sample by liquid chromatography-tandem mass spectrometry |
-
2022
- 2022-06-30 CN CN202210770296.XA patent/CN115267019B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104502482A (en) * | 2014-12-30 | 2015-04-08 | 郭庆龙 | Detecting method for residual quantity of flubendiamide in fruits and vegetables |
| CN107607656A (en) * | 2017-08-07 | 2018-01-19 | 浙江省农业科学院 | The detection method of bromine cyanogen insect amide and metabolin J9Z38 in the flesh of fish |
| CN108732293A (en) * | 2018-05-28 | 2018-11-02 | 广东省农业科学院植物保护研究所 | The high performance liquid chromatography tandem mass spectrum analysis method of indenes piperazine benfluralin and its metabolin |
| CN108760963A (en) * | 2018-05-28 | 2018-11-06 | 广东省农业科学院植物保护研究所 | The high performance liquid chromatography tandem mass spectrum analysis method of pyraclostrobin and its metabolin |
| CN111999419A (en) * | 2020-09-28 | 2020-11-27 | 广东省农业科学院植物保护研究所 | Method for determining content of chlorofluoroether bacteria azole by high performance liquid chromatography-tandem mass spectrometry |
| WO2022120752A1 (en) * | 2020-12-10 | 2022-06-16 | 中国科学院深圳先进技术研究院 | Method for quantitative analysis of free amino acids in biological sample by liquid chromatography-tandem mass spectrometry |
Non-Patent Citations (1)
| Title |
|---|
| 孙程鹏 等: "Sin-QuEChERS结合超高效液相色谱串联质谱法同时检测果蔬中5种双酰胺类杀虫剂", 食品安全质量检测学报, vol. 11, no. 6, pages 1 - 3 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115267019B (en) | 2024-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Du et al. | Simultaneous determination of cypermethrin and permethrin in pear juice by ultrasound-assisted dispersive liquid-liquid microextraction combined with gas chromatography | |
| CN103399096B (en) | Method for detecting content of malachite green and metabolin thereof in sediment of aquaculture environment | |
| CN106568873B (en) | The quantitative detecting method of Rynaxypyr residual quantity in a kind of soil | |
| CN102213700B (en) | Method for measuring content of pyrethroid pesticides in mainstream smoke of cigarettes | |
| Wang et al. | Multi-walled carbon nanotube as a solid phase extraction adsorbent for analysis of indole-3-butyric acid and 1-naphthylacetic acid in plant samples | |
| CN110780009B (en) | Method for simultaneously detecting 7 amide pesticide residues in fruits and vegetables by ultra-high performance liquid chromatography-tandem mass spectrometry | |
| CN106442781B (en) | The ultra performance liquid chromatography Mass Spectrometry detection method of Hostathion in a kind of Sediments | |
| CN115060839B (en) | Method for determining biscarfentrazone-ethyl metabolite based on liquid chromatography mass spectrometry | |
| Dikmen et al. | A novel and rapid extraction protocol for sensitive and accurate determination of prochloraz in orange juice samples: Vortex‐assisted spraying‐based fine droplet formation liquid‐phase microextraction before gas chromatography–mass spectrometry | |
| An et al. | Simultaneous determination of broflanilide and its metabolites in five typical Chinese soils by a modified quick, easy, cheap, effective, rugged, and safe method with ultra high performance liquid chromatography and tandem mass spectrometry | |
| CN109001311A (en) | The Liquid Chromatography-Tandem Mass Spectrometry detection method of interior exogenous female hormone in a kind of aquatic products | |
| CN111679008A (en) | GC-MS-MS method for simultaneously detecting volatile and semi-volatile acids, alcohols and phenols in tobacco leaves and cut tobacco | |
| CN106645493B (en) | A kind of method of Quizalotop-ethyl and its metabolite residue in detection of complex matrix | |
| ZHOU et al. | QuEChERS extraction for high performance liquid chromatographic determination of pyrazosulfuron-ethyl in soils | |
| CN115267019A (en) | Ultra-high performance liquid chromatography tandem mass spectrometry analysis method for cyhalodiamide in fruits | |
| Dong et al. | Determination of pyrethroid pesticide residues in vegetables by solvent sublation followed by high-performance liquid chromatography | |
| CN109100448B (en) | Method for detecting residual quantity of dipterex in tobacco | |
| CN115406994B (en) | Method for measuring pesticide content of spodoptera frugiperda by ultra-high performance liquid chromatography-tandem mass spectrometry | |
| CN113960236A (en) | Method for determining geosmin and dimethyl isoborneol in fish body based on rapid pretreatment technology | |
| CN113533608A (en) | Low-cost method suitable for rapidly detecting aflatoxin in large-batch edible oil samples | |
| Ferrari et al. | Neonicotinoids: An overview of the newest sample preparation procedures of environmental, biological and food matrices | |
| CN115876909A (en) | Method for measuring pesticide content in flea beetle by ultra-high performance liquid chromatography tandem mass spectrometry | |
| CN111650325A (en) | Method for detecting soil organochlorine pesticide | |
| CN111239295A (en) | Method for detecting amine with increased yield by combining dispersed solid-phase extraction with liquid chromatography tandem mass spectrometry | |
| Huelsmann et al. | Exploring polypyrrole as extraction phase for disposable pipette extraction method for multiclass organic micro-pollutant determination in river and tap water using gas chromatography-mass spectrometry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |