CN104535704B - A kind of GC-NCI-MS assay method of four chlorantraniliprole residual quantities - Google Patents
A kind of GC-NCI-MS assay method of four chlorantraniliprole residual quantities Download PDFInfo
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- PSOVNZZNOMJUBI-UHFFFAOYSA-N chlorantraniliprole Chemical compound CNC(=O)C1=CC(Cl)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl PSOVNZZNOMJUBI-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000005886 Chlorantraniliprole Substances 0.000 title claims abstract description 32
- 238000003556 assay Methods 0.000 title claims abstract description 10
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
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- 238000001819 mass spectrum Methods 0.000 claims abstract description 6
- 239000000523 sample Substances 0.000 claims description 53
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- 239000000243 solution Substances 0.000 claims description 17
- 239000012086 standard solution Substances 0.000 claims description 17
- 239000012224 working solution Substances 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000004458 analytical method Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000284 extract Substances 0.000 claims description 8
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- 238000002098 selective ion monitoring Methods 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 239000012496 blank sample Substances 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 4
- NDAUXUAQIAJITI-UHFFFAOYSA-N albuterol Chemical compound CC(C)(C)NCC(O)C1=CC=C(O)C(CO)=C1 NDAUXUAQIAJITI-UHFFFAOYSA-N 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 229960002052 salbutamol Drugs 0.000 claims description 3
- 238000010828 elution Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 210000004185 liver Anatomy 0.000 claims description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 3
- 238000012113 quantitative test Methods 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 241000426497 Chilo suppressalis Species 0.000 description 2
- 102000019027 Ryanodine Receptor Calcium Release Channel Human genes 0.000 description 2
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- 241001480238 Steinernema Species 0.000 description 1
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Abstract
The invention discloses a kind of GC-NCI-MS assay method of four chlorantraniliprole residual quantities, the method is mainly used in the method measuring four chlorantraniliprole content residual in the complex matrices such as Cereals, animal derived food food agricultural product.Four chlorantraniliproles residual in sample are extracted, C with acetonitrile or containing the acetonitrile solution homogeneous of 1% acetic acid
18after/PSA Solid-Phase Extraction column purification is concentrated, Gas Chromatography-Negative chemical ionization source-mass spectrum (GC-NCI-MS) detects, and adopts and does not set up the typical curve corrected, quantified by external standard method containing the vehicle solution of agricultural chemicals to be measured.This method average recovery rate is 83.3% ~ 90.3%, average relative standard's deviation (RSD) is 3.5% ~ 6.9%, detection limit lower than 1.43 μ g/kg, have easy and simple to handle, quick, impurity elimination is effective, highly sensitive, characteristic is strong, reproducible, qualitative, quantitative advantage accurately." uniform limit " technical requirement of 0.01mg/kg residue limits can be met, for guarantee our people food security, export abroad trade sound development provide strong technical support.
Description
Technical field
The present invention relates to a kind of GC-NCI-MS assay method of four chlorantraniliprole residual quantities, be more particularly the method adopting Gas Chromatography-Negative chemical ionization source-mass spectrum (GC-NCI-MS) qualitative, quantitative to measure four chlorantraniliprole content residual in the animals and plants derived food of the complex matrices such as animal muscle and goods such as Cereals, pork, beef, mutton, chicken, belong to the determination techniques field of persticide residue.
Background technology
Bisamide insecticides is the pesticide product that the whole world is popular in recent years, the injurious insect control of the crops such as paddy rice, vegetables, cotton can be widely used in, there is the advantages such as low toxicity, Environmental security, high activity, comprise the kinds such as Rynaxypyr, cyanogen insect amide, fipronil bisamide, four chlorantraniliproles (SYP-9080) are the new products managed by the research and development of China National Chemicals Import(Sinochem) subordinate Shenyang Chemical Engineering Inst, Zhong Hua agrochemical company limited, the first bisamide insecticides with independent intellectual property right of China, has obtained the interim registration in National agricultural portion.
Four chlorantraniliproles (SYP-9080) belong to ryanodine receptor activator insecticides, it is combined by ryanodine receptor in pest body, open calcium channel, make to be stored in intracellular calcium ion sustained release in sarcoplasm, calcium ion and sarcoplasm mesostroma protein combination, cause muscle contracts last.Insect bodies Symptoms is tic, food refusal, finally dead.Four chlorantraniliproles are low toxicity, broad spectrum pesticide, all have good activity to lepidoptera pest.Controlling object comprises rice leaf roller, striped rice borer, diamondback moth, beet armyworm, corn borer, sugarcane borer, steinernema, heart-eating worm etc.
Along with the registration of four chlorantraniliproles, popularization and use, about four chlorantraniliprole Residue Degradations dynamically and the research of the environmental behaviour such as final residue certainly will increase, simultaneously, if use agricultural chemicals not register in this country as European Union in China's main exit market, Japan and other countries regulation field, when not formulating corresponding residue limits standard, the food agricultural product being exported to its country comprise " uniform limit " that residue limits in the animal derived foods such as livestock meat all carries out 0.01mg/L.
Up to now, have no the report had about four chlorantraniliprole residues detection methods in food agricultural product both at home and abroad, the gaschromatographic mass spectrometry (GC-NCI-MS) in outfit negative chemical ionization source is analyzed food Residual Pesticides in Farm Produce tool and is had great advantage, Negative chemical ionization (NCI source) is called as mass spectrum " soft ionization source ", to the analysis thing containing electronegativity group, there is high selectivity and high sensitivity, because its characteristic is strong, when utilizing it to carry out retention analysis, matrix interference is little, can carry out qualitative and quantitative analysis very accurately to object.Existing various testing agency and enterprise have all purchased gas chromatograph-mass spectrometer (GCMS) (GC-MS), generally also be provided with Negative chemical ionization (NCI), now a lot of class agricultural chemicals is all containing electronegativity group, and organochlorine and pyrethroid pesticide molecule are mostly containing strong electronegative group such as-F ,-Cl ,-Br or-COO-, organophosphorus pesticide molecule is mostly containing the=electronegativity group such as S ,-OR ,-P ,-O-,-Cl or-P=O, and mostly containing-F group in the novel agrochemical developed in recent years, therefore, use GC-NCI-MS conveniently can realize the multi-residue analysis of Multiple Pesticides, compared with GC-NCI-MS, better antijamming capability can be obtained, lower sensitivity and better selectivity, four chlorantraniliproles belong to electronegativity compound, due to Cereals, the food agricultural product matrix more complicated such as animal derived food, the good sample-pretreating method of clean-up effect must be set up and instrumental conditions could meet testing requirement, therefore, the detection method setting up four chlorantraniliprole residual quantities in Gas Chromatography-Negative chemical ionization source-mass spectrum (GC-NCI-MS) qualitative and quantitative analysis Cereals and animal derived food is significant.
Summary of the invention
The object of this invention is to provide a kind of GC-NCI-MS assay method of four chlorantraniliprole residual quantities, be mainly used in measuring four chlorantraniliprole residual quantities in the complex matrices such as Cereals, animal derived food food agricultural product.
For realizing above object, the technical solution adopted in the present invention is: a kind of GC-NCI-MS assay method of four chlorantraniliprole residual quantities, comprises the steps:
(1) extract
Take mixing sample in tool plug centrifuge tube, after adding suitable quantity of water recovery, quantitatively add acetonitrile or extract containing the acetonitrile solution homogeneous of 1% acetic acid or oscillating ultrasonic, then adding the one in sodium chloride or sodium acetate and anhydrous magnesium sulfate, centrifugal after violent vortex 1min.
(2) purify
Pipette certain volume sample extracting solution, be concentrated into about 1mL, through C
18/ PSA Solid-Phase Extraction column purification, acetonitrile, collects eluent, is concentrated into after doing, and dissolves constant volume, after crossing film, treat that Gas Chromatography-Negative chemical ionization source-mass spectrum (GC-NCI-MS) detects with acetone/normal hexane mixed solvent that volume ratio is 1/1.
(3) preparation of standard working solution
When same kind matrix blank sample not containing four chlorantraniliproles is processed by above-mentioned steps (1), (2), obtain sample extraction purification residue, add appropriate solvent and mixed standard solution, vortex mixes, and is mixed with four chlorantraniliprole series hybrid standard working fluids of at least 3 concentration.
(4) Gas Chromatography-Negative chemical ionization source-mass spectroscopy (GC-NCI-MS) measures
The standard working solution of each concentration gradient in step (3) is carried out GC-NCI-MS mensuration, with the chromatographic peak area of standard working solution, regretional analysis is carried out to its respective concentration, obtain standard working curve; Under the same conditions the sample liquid after purification in step (2) is injected GC-NCI-MS to measure, record the chromatographic peak area of four chlorantraniliproles in sample liquid, substitute into typical curve, obtain four chlorantraniliprole content in sample liquid, then the Mass Calculation of sample representated by liquid obtains four chlorantraniliprole residual quantities in sample per sample.
Step (1), if the sample of the middle moisture content less such as sample Cereals and animal's liver, must add suitable quantity of water and fully infiltrate before extraction.
Add sodium chloride when adopting acetonitrile to extract in step (1) to saltout, add sodium acetate when adopting the acetonitrile solution containing 1% acetic acid to extract and saltout.
Step carries out C in (2)
18/ PSA Solid phase extraction, during acetonitrile, elution volume is 6 ~ 8mL.
In step (4), GC conditions is: chromatographic column: HP-5MS capillary chromatographic column, column length 30m, internal diameter 0.25mm, thickness 0.25 μm; Injector temperature 250 DEG C; Carrier gas: He, not shunt mode sample introduction, sample size: 1 μ L; Constant current mode, flow velocity 1.0mL/min; Heating schedule: initial temperature 60 DEG C keeps 2min, rises to 200 DEG C, then rises to 220 DEG C with the speed of 2 DEG C per minute, then rise to 280 DEG C with the speed of 20 DEG C per minute with the speed of 20 DEG C per minute, keeps 10min; Transmission line temperature: 280 DEG C.
In step (4), Mass Spectrometry Conditions is: ion source temperature 150 DEG C; Quadrupole rod temperature 150 DEG C; Ionization pattern: negative chemical ionization, i.e. NCI pattern, energy 70eV; Scan mode: the ion of Salbutamol Selected Ion Monitoring (SIM) mode monitoring is: 332,334,336.
When measuring sample liquid and extraction standard working solution in step (4), if sample liquid Pesticides chromatographic peak retention time agricultural chemicals retention time corresponding to standard solution is consistent, and in the sample mass spectrogram after background correction, selected ion all occurs, and abundance of ions than with the abundance of ions of standard solution than consistent, then can judge to exist in sample liquid this agricultural chemicals; If above-mentioned two conditions can not meet simultaneously, then judge not containing this kind of agricultural chemicals.
Beneficial effect of the present invention is:
The present invention utilizes dispersive solid-phase extraction technology, establish sample-pretreating method that is easy, that also can effectively avoid sample mesostroma to disturb fast, this pre-treating method to be applied in Cereals, animal derived food the qualitative confirmation of four chlorantraniliproles in conjunction with GC-NCI-MS and quantitatively to detect, average recovery rate is 83.3% ~ 90.3%, average relative standard's deviation (RSD) is 3.5% ~ 6.9%, detection limit, lower than 1.43 μ g/kg, has easy and simple to handle, quick, accurate, highly sensitive and reproducible advantage." uniform limit " technical requirement of 0.01mg/kg residue limits can be met, for guarantee our people food security, export abroad trade sound development provide strong technical support.
Accompanying drawing explanation
The GC-NCI-MS Selective ion mode chromatogram of Fig. 1 to be concentration be four chlorantraniliprole mark liquid of 100ng/mL.
Fig. 2 is not containing the GC-NCI-MS Selective ion mode chromatogram of the rice blank sample of four chlorantraniliproles.
Fig. 3 is the GC-NCI-MS Selective ion mode chromatogram of four chlorantraniliproles be added in blank rice matrix.
The four chlorantraniliprole standard working curves that Fig. 4 is is substrate preparation with the rice blank sample not containing four chlorantraniliproles.
Embodiment
Now with following embodiment, the present invention is described, but is not limit the scope of the invention.
The instrument used in embodiment and reagent
T18Basic homogenizer (IKA, Germany); CR21G III hydro-extractor (Hitachi, Japan); MS3 basic model vortex mixer (IKA, Germany); TurboVapLV type sample automatic concentration instrument (Caliper, USA); 7890N gas chromatography-5975C mass spectrometer (Agilent, USA); C
18/ PSA solid-phase extraction column (6mL, 500mg/500mg) is purchased from Tianjin Bonaaijieer Technology Co., Ltd.
Reagent: acetonitrile, acetone, normal hexane (HPLC level, Merke, Germany); Acetic acid (HPLC level, CNW, Germany); Anhydrous magnesium sulfate, sodium chloride and sodium acetate are pure for analyzing, all purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
Standard substance: purity 95.5%, purchased from Zhong Hua agrochemical company limited.
Embodiment 1: the detection of four chlorantraniliprole residual quantities in rice
(1) sample pre-treatments
Extract
Take 5g rice sample through fully mixing in 50mL centrifuge tube, add the mixing of 5mL water, place 30min, accurately add 20mL acetonitrile, homogeneous extracts 2min, adds 3g anhydrous magnesium sulfate and 2g sodium chloride, after vortex 1min, and the centrifugal 5min of 7000r/min.After centrifugal, get 8mL acetonitrile extract in 40 DEG C revolve steaming or nitrogen blow to about 1mL, to be clean.
Purification
With 5mL acetonitrile prewashing C
18/ PSA solid-phase extraction column, when liquid level arrives the top of adsorbent, said extracted solution is proceeded in post, with 2mL acetonitrile wash test tube, and cleansing solution is moved in SPE post, when solution reaches adsorbent top, add on 4mL acetonitrile to pillar and carry out wash-out, eluent all receives in quantitative test tube, nitrogen dry up rear volume ratio be 1/1 acetone/normal hexane mixed solvent be settled to 1mL, after crossing 0.22 μm of filter membrane, treat that GC-NCI-MS measures.
(2) preparation of standard working solution
Accurately take 25 ± 0.1mg standard items in 25mL volumetric flask, dissolve with acetonitrile, constant volume obtains 1000.0 μ g/mL standard reserving solutions; Pipette 1.0mL standard reserving solution and be placed in 100mL volumetric flask, obtain 10.0 μ g/mL standard intermediate liquids with the acetone/normal hexane mixed solvent constant volume by volume ratio being 1/1; 10 μ g/mL standard solution dilutions are made into 5,2,1,0.5,0.2,0.1 μ g/mL standard solution.Rice blank sample not containing spiral shell worm ethyl ester is pressed above-mentioned pre-treatment step process, obtain sample extraction purification residue, acetone/normal hexane mixed solvent and the above-mentioned mixed standard solution of 100 μ L that 900 μ L volume ratios are 1/1 is added in this residue, vortex mixes, and is made into 10,20,50,100,200,500 μ g/L extraction standard working solutions.
(3) Gas Chromatography-Negative chemical ionization source-mass spectroscopy (GC-NCI-MS) measures
The standard working solution of variable concentrations gradient is injected GC-NCI-MS respectively, carries out the quantitative test of four chlorantraniliprole content with external standard method, namely with the chromatographic peak area of standard working solution, regretional analysis is carried out to its respective concentration, obtain typical curve; Under the same conditions sample extracting solution is injected GC-NCI-MS to measure, record the chromatographic peak area of four chlorantraniliproles in sample liquid, substitute into typical curve, obtain four chlorantraniliprole content in sample liquid, then the Mass Calculation of sample representated by liquid obtains four chlorantraniliprole residual quantities in sample per sample.
Wherein chromatographic condition is:
Chromatographic column: HP-5MS capillary chromatographic column, column length 30m, internal diameter 0.25mm, thickness 0.25 μm.
Injector temperature: 250.0 DEG C, sample introduction pattern: Splitless injecting samples, sample size: 1 μ L.
Carrier gas: He, constant current mode, flow velocity 1.0mL/min.
Stove case heating schedule: initial temperature 60 DEG C keeps 2min, rises to 200 DEG C, then rises to 220 DEG C with the speed of 2 DEG C per minute, then rise to 280 DEG C with the speed of 20 DEG C per minute with the speed of 20 DEG C per minute, keeps 10min.
Transmission line temperature: 280 DEG C.
Wherein, mass spectrometry parameters is:
Ionization pattern: negative chemical ionization, i.e. NCI pattern, energy 70eV.
Ion source temperature: 150 DEG C; Quadrupole rod temperature 150 DEG C.
Scan mode: Salbutamol Selected Ion Monitoring (SIM) pattern; The ion of SIM monitoring is: 332,334,336;
Quota ion is 334;
Qualitative Identification: at identical conditions, if sample liquid Pesticides chromatographic peak retention time agricultural chemicals retention time corresponding to standard solution is consistent, and in the sample mass spectrogram after background correction, selected ion all occurs, and abundance of ions than with the abundance of ions of standard solution than consistent, then can judge to exist in sample liquid this agricultural chemicals; If above-mentioned two conditions can not meet simultaneously, then judge not containing this kind of agricultural chemicals.
With the chromatographic peak area of standard working solution, regretional analysis is carried out to its respective concentration, obtain standard working curve as table 1.
The typical curve of four chlorantraniliproles in table 1 rice bare substrate
| Title | Retention time (min) | Regression equation | Related coefficient |
| Four chlorantraniliprole SYP-9080 | 25.62 | Y＝27.156X-104.59 | 0.9998 |
Recovery of standard addition and repeatability:
In the rice not containing four chlorantraniliproles, add four chlorantraniliprole standard solution of 10, a 20 and 200 μ g/kg3 concentration level, add after 30min until agricultural chemicals and carry out the determination of residual amount by above-mentioned treatment step.Mensuration concentration and agricultural chemicals theory are added concentration compare, obtain agricultural chemicals TIANZHU XINGNAO Capsul, each Pitch-based sphere replicate determination 6 times, obtain its relative standard deviation, measurement result is in table 2.As can be seen from Table 2, in 3 mark-on levels, the average recovery rate of four chlorantraniliproles is 83.3% ~ 89.9%, and average relative standard's deviation (RSD) is 4.0% ~ 5.3%, illustrates that the recovery of the inventive method is higher, reproducible.
The recovery of table 2 four chlorantraniliprole and repeatability (n=6)
Detection limit:
Four chlorantraniliprole extraction standard working solutions of variable concentrations are injected GC-NCI-MS, calculate detection limit with the cycles of concentration (cycles of concentration of rice is 2.0 times) of 3 times of signal to noise ratio (S/N ratio)s of least concentration extraction standard solution chromatographic peak and sample handling processes, detecting of four chlorantraniliproles is limited to 0.92 μ g/kg.
Embodiment 2: the detection of four chlorantraniliprole residual quantities in pork
(1) sample pre-treatments
Extract
Take 5g pork sample (grinding to form flour) through fully mixing in 50mL centrifuge tube, after adding 20mL water recovery 30min, accurately add the acetonitrile solution of 20mL containing 1% acetic acid, mechanical shaking extraction 20min, ultrasonic extraction 5min, add 3g anhydrous magnesium sulfate and 2g sodium acetate, after vortex 1min, the centrifugal 5min of 7000r/min.After centrifugal, get 8mL acetonitrile extract and revolve steaming or nitrogen blows near dry in 40 DEG C, after adding 1mL acetonitrile vortex, to be clean.
Purification
With 5mL acetonitrile prewashing C
18/ PSA solid-phase extraction column, when liquid level arrives the top of adsorbent, said extracted solution is proceeded in post, with 2mL acetonitrile wash test tube, and cleansing solution is moved in SPE post, when solution reaches adsorbent top, add on 4mL acetonitrile to pillar and carry out wash-out, eluent all receives in quantitative test tube, nitrogen dry up rear volume ratio be 1/1 acetone/normal hexane mixed solvent be settled to 1mL, after crossing 0.22 μm of filter membrane, treat that GC-NCI-MS measures.
(2) preparation of standard working solution
By 100ng/mL standard solution volume ratio be 1/1 acetone/normal hexane mixed solvent be diluted to 10ng/mL standard intermediate liquid, by 10 μ g/mL standard solution dilution be made into 5,2,1,0.5,0.2,0.1 μ g/mL standard solution.Pork blank sample not containing four chlorantraniliproles is pressed above-mentioned pre-treatment step process, obtain sample extraction purification residue, acetone/normal hexane mixed solvent and the above-mentioned mixed standard solution of 100 μ L that 900 μ L volume ratios are 1/1 is added in this residue, vortex mixes, and is made into 10,20,50,100,200,500 μ g/L extraction standard working solutions.
(3) Gas Chromatography-Negative chemical ionization source-mass spectroscopy (GC-NCI-MS) measures
Operation steps, chromatogram are consistent with the mensuration of four chlorantraniliproles in above-mentioned pork sample with Mass Spectrometry Conditions.
Qualitative Identification: consistent with the mensuration of four chlorantraniliproles in above-mentioned pork sample.
Linear relationship:
Carry out regretional analysis with the chromatographic peak area of standard working solution to its respective concentration, obtaining standard working curve is Y=76.117X-973.98, and related coefficient is 0.9991.
Recovery of standard addition and repeatability:
Four chlorantraniliprole standard solution of 10, a 20 and 200 μ g/kg3 concentration level are added in the pork not containing four chlorantraniliproles, add after 30min until agricultural chemicals and carry out the determination of residual amount by above-mentioned treatment step, mensuration concentration and agricultural chemicals theory are added concentration compare, obtain agricultural chemicals TIANZHU XINGNAO Capsul, each Pitch-based sphere replicate determination 6 times, obtain its relative standard deviation, measurement result is in table 3.As can be seen from Table 3, in 3 mark-on levels, the average recovery rate of four chlorantraniliproles is 86.9% ~ 90.3%, and average relative standard's deviation (RSD) is 3.5% ~ 6.9%, illustrates that the recovery of the inventive method is high, reproducible.
The recovery of table 3 four chlorantraniliprole and repeatability (n=6)
Detection limit:
Four chlorantraniliprole extraction standard working solutions of variable concentrations are injected GC-NCI-MS, calculate detection limit with the cycles of concentration (cycles of concentration of pork is 2.0 times) of 3 times of signal to noise ratio (S/N ratio)s of least concentration extraction standard solution chromatographic peak and sample handling processes, detecting of four chlorantraniliproles is limited to 1.43 μ g/kg.
Above embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various modification that the common engineering in this area is made technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.
Claims (4)
1. a GC-NCI-MS assay method for four chlorantraniliprole residual quantities, is characterized in that, said method comprising the steps of:
(1) extract
Take mixing sample in tool plug centrifuge tube, after adding suitable quantity of water, add acetonitrile or after extracting containing the acetonitrile solution homogeneous of 1% acetic acid or oscillating ultrasonic, add the one in sodium chloride or sodium acetate and anhydrous magnesium sulfate, centrifugal after violent vortex 1min;
(2) purify
Pipette certain volume sample extracting solution, be concentrated into about 1mL, through C
18/ PSA Solid-Phase Extraction column purification, acetonitrile, collects eluent, is concentrated into after doing, and dissolves constant volume, after crossing film, treat that Gas Chromatography-Negative chemical ionization source-mass spectrum (GC-NCI-MS) detects with acetone/normal hexane mixed solvent that volume ratio is 1/1;
(3) preparation of standard working solution
Same kind matrix blank sample not containing four chlorantraniliproles is processed by above-mentioned steps (1), (2), obtain sample extraction purification residue, add appropriate solvent and standard solution, vortex mixes, and is mixed with four chlorantraniliprole series standard working fluids of at least 3 concentration;
(4) mensuration and result calculate
GC-NCI-MS analysis condition is: chromatographic column: HP-5MS capillary chromatographic column, column length 30m, internal diameter 0.25mm, thickness 0.25 μm; Injector temperature 250.0 DEG C; Carrier gas: He, not shunt mode sample introduction, sample size: 1 μ L; Constant current mode, flow velocity 1.0mL/min; Heating schedule: initial temperature 60 DEG C keeps 2min, rises to 200 DEG C, then rises to 220 DEG C with the speed of 2 DEG C per minute, then rise to 280 DEG C with the speed of 20 DEG C per minute with the speed of 20 DEG C per minute, keeps 10min; Transmission line temperature: 280 DEG C; Ionization pattern: negative chemical ionization, i.e. NCI pattern, energy 70eV; Ion source temperature 150 DEG C; Scan mode: Salbutamol Selected Ion Monitoring (SIM) pattern, the ion of monitoring is: 332,334,336;
The standard working solution of each concentration gradient in step (3) is carried out GC-NCI-MS mensuration, with the chromatographic peak area of standard working solution, regretional analysis is carried out to its respective concentration, obtain extraction standard working curve; Under the same conditions the sample liquid after purification in step (2) is injected GC-NCI-MS to measure, record the chromatographic peak area of four chlorantraniliproles in sample liquid, substitute into extraction standard working curve, obtain four chlorantraniliprole content in sample liquid, then the Mass Calculation of sample representated by liquid obtains four chlorantraniliprole residual quantities in sample per sample.
2. the GC-NCI-MS assay method of a kind of four chlorantraniliprole residual quantities according to claim 1, is characterized in that, step (1), if middle sample Cereals and animal's liver sample, must add suitable quantity of water and fully infiltrate before extraction.
3. the GC-NCI-MS assay method of a kind of four chlorantraniliprole residual quantities according to claim 1, it is characterized in that, sodium chloride need be added when adopting acetonitrile to extract in step (1) to saltout, sodium acetate need be added when adopting the acetonitrile solution containing 1% acetic acid to extract and saltout.
4. the GC-NCI-MS assay method of a kind of four chlorantraniliprole residual quantities according to claim 1, it is characterized in that, step carries out C in (2)
18/ PSA Solid-Phase Extraction column purification, during acetonitrile, elution volume is 6 ~ 8mL.
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| Development and Validation of a Method for the Determination of 159 Pesticide Residues in Tobacco by Gas Chromatography-Tandem Mass Spectrometry;Xiaoshui Chen et al;《Journal of Agricultural and Food Chemistry》;20130606;第61卷(第24期);第5749页左栏第2段至第5750页右栏第2段，第5755页右栏第2段至第5756页左栏第1段，第5751页"样品前处理优化"小节 * |
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