CN105548439A - GC-MS/MS (gas chromatography-tandem mass spectrometry) determining method of penthiopyrad residual quantity - Google Patents

GC-MS/MS (gas chromatography-tandem mass spectrometry) determining method of penthiopyrad residual quantity Download PDF

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CN105548439A
CN105548439A CN201610065642.9A CN201610065642A CN105548439A CN 105548439 A CN105548439 A CN 105548439A CN 201610065642 A CN201610065642 A CN 201610065642A CN 105548439 A CN105548439 A CN 105548439A
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pyrrole metsulfovax
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郭庆龙
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    • 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
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    • 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
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    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
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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
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample

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Abstract

The invention discloses a GC-MS/MS (gas chromatography-tandem mass spectrometry) determining method of penthiopyrad residual quantity. The method is a method mainly used for determining the residual penthiopyrad content in agricultural products of complicated matrix food such as cereal grains and animal derived food. Acetonitrile or an acetonitrile solution containing one-percent acetic acid is used for performing homogeneous extraction of the residual penthiopyrad in samples; after C<18>/PSA (primary secondary amine) solid phase extraction column purification and concentration, GC-MS/MS detection is performed; a corrected standard work curve is built by using a blank matrix solution not containing pesticide to be detected; an external reference method is used for quantification. The GC-MS/MS determining method has the advantages that the average recovery rate is 86.4 percent to 95.3 percent; the average RSD (relative standard deviation) is 5.0 percent to 8.7 percent; the detection limit is lower than 0.25mug/kg; the operation is simple, convenient and fast; the impurity removal effect is good; the sensitivity is high; the characteristic performance is high; the repeatability is good; the qualitative and quantitative analysis is accurate. The technical requirements of countries such as America, European Union and Japan on corresponding product safety detection can be met; powerful technical support is provided for guaranteeing the food safety of Chinese people and healthy development of export abroad trade.

Description

A kind of GC-MS/MS assay method of pyrrole metsulfovax residual quantity
Technical field
The present invention relates to a kind of GC-MS/MS assay method of pyrrole metsulfovax residual quantity, be more particularly the method adopting gas chromatography tandem mass spectrum (GC-MS/MS) qualitative, quantitative to measure pyrrole metsulfovax 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
Pyrrole metsulfovax (Penthiopyrad) is the novel acid amide fungicides of Mitsui chemical company research and development, and English general penthiopyrad by name, test code number: MTF-753, commodity are called Afetofluapro.CAS accession number: 183675-82-3, chemical name is (RS)-N-[2-(1,3-dimethylbutyl)-3-thienyl]-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide, and chemical structural formula is:
Pyrrole metsulfovax has different fungicidal spectrums from existing carboxyl acylamide germifuge, except the same with existing carboxyl acylamide germifuge to basidiomycetes effectively except, it is also effective to sac fungus, imperfect fungi, existing recommended for preventing and treating gray mold to other germifuge tool resistances and powdery mildew.The normally used effective constituent dosage of this medicament is 100 ~ 200g/hm 2, it is widely used in numerous crops such as fruit tree, vegetables, lawn, control rust, sclerotiniose, gray mold, downy mildew, scab of apple and powdery mildew.Penthiopyrad in 2008 Japan obtain ratify first, for fruit tree, vegetables and ornamental plant, after again in November, 2011 Canada get permission registration.Trade mark is called Vertisan and Fontelis (be all its active component with penthiopyrad200g/L) and 3 products of Treoris (penthiopyrad100g/L+chlorothalonil (Bravo) 250g/L) are mainly used on fruit tree, vegetables and field crops, finds that pyrrole metsulfovax has very wide application prospect in practical application.
Along with the registration of pyrrole metsulfovax, popularization and use, formulated its maximum maximum permission quantity (MRL) in the food agricultural product such as veterinary antibiotics, Cereals and livestock products as European Union in China's main exit market, Canada and the country such as Australian, the MRL of Canadian regulation pyrrole metsulfovax in the animal derived foods such as fruits and vegetables, nut, Cereals and livestock products is 0.01 ~ 30mg/kg; The MRL of Australia's regulation pyrrole metsulfovax in the animal derived foods such as fruits and vegetables, nut, Cereals and livestock products is 0.01 ~ 5mg/kg; European Union specifies that the MRL of pyrrole metsulfovax in the animal derived foods such as fruits and vegetables, nut, Cereals and livestock products is 0.01 ~ 30mg/kg; If European Union, Japan and other countries regulation field use agricultural chemicals not register in this country, 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.
Present stage, less to the research of pyrrole metsulfovax determination of residual amount method, the detection method of report is mainly pyrrole metsulfovax method for detecting residue in vegetables and fruit, these detection methods all adopt Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) to measure the detection method of pyrrole metsulfovax residual quantity in vegetables and fruit, using LC-MS/MS to measure food Residual Pesticides in Farm Produce has fast, easy, sensitivity advantages of higher, but due to its price costly, a lot of testing agency, enterprise or scientific research institutions do not configure this instrument or configuration number of units is less, during due to different compounds employing LC-MS/MS detection, different mobile phases or chromatographic column need be used, such needs constantly change chromatographic column, mobile phase also expends the long time and balances system, this constrains the application of LC-MS/MS to a certain extent.Using gas chromatography tandem mass spectrum (GC-MS/MS) to analyze food Residual Pesticides in Farm Produce has fast, easy, highly sensitive, the advantages such as selectivity is strong, the multi-residue analysis of hundreds of kind agricultural chemicals can be realized, but have no the report of the GC-MS/MS detection method of pyrrole metsulfovax residual quantity in food agricultural product up to now, 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 pyrrole metsulfovax residual quantity in gas chromatography tandem mass spectrum (GC-MS/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-MS/MS assay method of pyrrole metsulfovax residual quantity, be mainly used in measuring pyrrole metsulfovax residual quantity 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-MS/MS assay method of pyrrole metsulfovax residual quantity, 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, get elution fractions be concentrated into dry after, dissolve constant volume with acetone/normal hexane mixed solvent that volume ratio is 1/1, after crossing film, treat that gas chromatography tandem mass spectrum (GC-MS/MS) detects.
(3) preparation of standard working solution
When same kind matrix blank sample not containing pyrrole metsulfovax 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 the pyrrole metsulfovax series standard working fluid of at least 3 concentration.
(4) gas chromatography tandem mass spectrometry (GC-MS/MS) measures
The standard working solution of each concentration gradient in step (3) is carried out GC-MS/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-MS/MS to measure, record the chromatographic peak area of pyrrole metsulfovax in sample liquid, substitute into standard working curve, obtain pyrrole metsulfovax content in sample liquid, then the Mass Calculation of sample representated by liquid obtains pyrrole metsulfovax residual quantity in sample per sample.If pyrrole metsulfovax residual quantity exceedes the range of linearity upper limit in upper machine solution, with constant volume solvent, upper machine solution concentration need be diluted within the range of linearity.
Step (1), if the sample of middle sample moisture content less, 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 1.2mL/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: 290 DEG C.
In step (4), Mass Spectrometry Conditions is: ionization pattern: electron impact ionization (EI, 70eV); Ion source temperature 280 DEG C; Collision gas: argon gas; Multiple-reaction monitoring scan mode MRM, monitoring parameter is:
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 pyrrole metsulfovax in conjunction with GC-MS/MS and quantitatively to detect, average recovery rate is 86.4% ~ 95.3%, average relative standard's deviation (RSD) is 5.0% ~ 8.7%, detection limit, lower than 0.25 μ g/kg, has easy and simple to handle, quick, accurate, highly sensitive and reproducible advantage.The U.S., European Union, Japan and other countries being met to the technical requirement of corresponding product safety detection, providing strong technical support for ensureing that our people's food security and export abroad trade develop in a healthy way.
Accompanying drawing explanation
Fig. 1 is the GC-MS/MS Selective ion mode chromatogram of the pyrrole metsulfovax mark liquid be added in blank pork matrix.
Fig. 2 is not containing the GC-MS/MS Selective ion mode chromatogram of the pork blank sample of pyrrole metsulfovax.
The pyrrole metsulfovax standard working curve that Fig. 3 is is substrate preparation with the pork blank sample not containing pyrrole metsulfovax.
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-5977C 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 98.0%, purchased from American Sigma company.
Embodiment 1: the detection of pyrrole metsulfovax residual quantity in wheat
(1) sample pre-treatments
Extract
Take 5g wheat samples (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, proceeds in post by said extracted solution, 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, be settled to 10mL with acetonitrile, get after 1mL scavenging solution nitrogen dries up, be settled to 1mL with acetone/normal hexane mixed solvent that volume ratio is 1/1, after crossing 0.22 μm of filter membrane, treat that GC-MS/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 acetone/normal hexane mixed solvent constant volume that volume ratio is 1/1; Wheat blank sample not containing pyrrole metsulfovax is pressed above-mentioned pre-treatment step process, get the blank extraction and cleaning liquid of 8mL, be concentrated into after doing, add acetone/normal hexane mixed solvent vortex dissolving that 8mL volume ratio is 1/1, be finally mixed with 1,2,5,10,20,50 μ g/L extraction standard working solutions with this solution.
(3) gas chromatography tandem mass spectrometry (GC-MS/MS) measures
The standard working solution of variable concentrations gradient is injected GC-MS/MS respectively, carries out the quantitative test of pyrrole metsulfovax 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 standard working curve; Under the same conditions sample extracting solution is injected GC-MS/MS to measure, record the chromatographic peak area of pyrrole metsulfovax in sample liquid, substitute into standard working curve, obtain pyrrole metsulfovax content in sample liquid, then the Mass Calculation of sample representated by liquid obtains pyrrole metsulfovax residual quantity 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 1.2mL/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: 290 DEG C.
Wherein, mass spectrometry parameters is:
Ionization pattern: electron impact ionization, i.e. EI pattern, energy 70eV.
Ion source temperature: 280 DEG C; Collision gas: argon gas.
Scan mode: multiple-reaction monitoring (SRM) scan pattern; MRM detected parameters is in table 1.
Table 1: the MRM detected parameters of embodiment 1
*for quota ion pair.
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 2.
The standard working curve of pyrrole metsulfovax in table 2 wheat bare substrate
Title Retention time (min) Regression equation Related coefficient
Pyrrole metsulfovax 19.52 Y＝15973X-857.96 0.9997
Recovery of standard addition and repeatability:
In the wheat not containing pyrrole metsulfovax, add the pyrrole metsulfovax 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 3.As can be seen from Table 3, in 3 mark-on levels, the average recovery rate of pyrrole metsulfovax is 86.4% ~ 92.5%, and average relative standard's deviation (RSD) is 5.0% ~ 8.7%, illustrates that the recovery of the inventive method is higher, reproducible.
The recovery of table 3 pyrrole metsulfovax and repeatability (n=6)
Detection limit:
The pyrrole metsulfovax extraction standard working solution of variable concentrations is injected GC-MS/MS, calculate detection limit with the cycles of concentration (cycles of concentration of wheat is 0.2 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 pyrrole metsulfovax is limited to 0.19 μ g/kg.
Embodiment 2: the detection of pyrrole metsulfovax residual quantity in pork
(1) sample pre-treatments
Extract
Take 5g pork 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, proceeds in post by said extracted solution, 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, be settled to 10mL with acetonitrile, get after 1mL scavenging solution nitrogen dries up, be settled to 1mL with acetone/normal hexane mixed solvent that volume ratio is 1/1, after crossing 0.22 μm of filter membrane, treat that GC-MS/MS measures.
(2) preparation of standard working solution
Acetone/normal hexane the mixed solvent being 1/1 by 1000 μ g/mL standard solution volume ratios is diluted to 10 μ g/mL standard intermediate liquids, pork blank sample not containing pyrrole metsulfovax is pressed above-mentioned pre-treatment step process, get the blank extraction and cleaning liquid of 8mL, be concentrated into after doing, add acetone/normal hexane mixed solvent vortex dissolving that 8mL volume ratio is 1/1, be finally mixed with 1,2,5,10,20,50 μ g/L extraction standard working solutions with this solution.
(3) gas chromatography tandem mass spectrometry (GC-MS/MS) measures
Operation steps, chromatogram are consistent with the mensuration of pyrrole metsulfovax in above-mentioned wheat samples with Mass Spectrometry Conditions.
Qualitative Identification: consistent with the mensuration of pyrrole metsulfovax in above-mentioned wheat samples.
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=17865X+3349.2, related coefficient is 0.9997.
Recovery of standard addition and repeatability:
The pyrrole metsulfovax standard solution of 10, a 20 and 200 μ g/kg3 concentration level is added in the pork not containing pyrrole metsulfovax, 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 4.As can be seen from Table 4, in 3 mark-on levels, the average recovery rate of pyrrole metsulfovax is 87.1% ~ 95.3%, and average relative standard's deviation (RSD) is 5.0% ~ 7.6%, illustrates that the recovery of the inventive method is high, reproducible.
The recovery of table 4 pyrrole metsulfovax and repeatability (n=6)
Detection limit:
The pyrrole metsulfovax extraction standard working solution of variable concentrations is injected GC-MS/MS, calculate detection limit with the cycles of concentration (cycles of concentration of pork is 0.2 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 pyrrole metsulfovax is limited to 0.25 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 (5)

1. a GC-MS/MS assay method for pyrrole metsulfovax residual quantity, 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, get elution fractions be concentrated into dry after, dissolve constant volume with acetone/normal hexane mixed solvent that volume ratio is 1/1, after crossing film, treat that gas chromatography tandem mass spectrum (GC-MS/MS) detects;
(3) preparation of standard working solution
Same kind matrix blank sample not containing pyrrole metsulfovax 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 the pyrrole metsulfovax series standard working fluid of at least 3 concentration;
(4) mensuration and result calculate
The standard working solution of each concentration gradient in step (3) is carried out GC-MS/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-MS/MS to measure, record the chromatographic peak area of pyrrole metsulfovax in sample liquid, substitute into extraction standard working curve, obtain pyrrole metsulfovax content in sample liquid, then the Mass Calculation of sample representated by liquid obtains pyrrole metsulfovax residual quantity in sample per sample; If pyrrole metsulfovax residual quantity exceedes the range of linearity upper limit in upper machine solution, with constant volume solvent, upper machine solution concentration need be diluted within the range of linearity.
2. the GC-MS/MS assay method of a kind of pyrrole metsulfovax residual quantity according to claim 1, is characterized in that, step (1), if the sample of middle sample moisture content less, must add suitable quantity of water and fully infiltrate before extraction.
3. the GC-MS/MS assay method of a kind of pyrrole metsulfovax residual quantity 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-MS/MS assay method of a kind of pyrrole metsulfovax residual quantity according to claim 1, it is characterized in that, step carries out C in (2) 18/ PSA Solid phase extraction, during acetonitrile, elution volume is 6 ~ 8mL.
5. the GC-MS/MS assay method of a kind of pyrrole metsulfovax residual quantity according to claim 1, it is characterized in that, in step (4), GC-MS/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 1.2mL/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: 290 DEG C; Ionization pattern: electron impact ionization (EI, 70eV); Ion source temperature 280 DEG C; Collision gas: argon gas; Multiple-reaction monitoring scan mode MRM, monitoring parameter is:
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CN113341016A (en) * 2021-06-08 2021-09-03 河南广电计量检测有限公司 Method for detecting residual bactericide in animal food

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CN113341016A (en) * 2021-06-08 2021-09-03 河南广电计量检测有限公司 Method for detecting residual bactericide in animal food

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Application publication date: 20160504