CN104502507A - GC-NCI-MS determination method for determining residual amount of chlorantraniliprole - Google Patents
GC-NCI-MS determination method for determining residual amount of chlorantraniliprole Download PDFInfo
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Abstract
The invention discloses a GC-NCI-MS determination method for determining residual amount of chlorantraniliprole, which is mainly used for determining content of residual chlorantraniliprole in complex matrix food agricultural products such as cereal grains and animal derived foods. The GC-NCI-MS determination method comprises the following steps: extracting the residual chlorantraniliprole in a sample by adopting acetonitrile or acetonitrile solution containing 1% of acetic acid in a homogenizing manner; purifying and concentrating by adopting a C18/PSA solid phase extraction column, performing gas chromatography-negative chemical ionization-mass spectrum (GC-NCI-MS) detection, establishing a correcting standard curve by adopting a blank matrix solution which does not contain pesticides, and quantifying by adopting an external standard method. With the adoption of the GC-NCI-MS determination method, the average recovery rate is 86.8%-96.9%, the average relative standard deviation (RSD) is 4.0-9.7%, the detection limit is 1.41 microg/kg; the GC-NCI-MS determination method has the advantages of simplicity and convenience in operation, rapidness, good impurity removal effect, high sensitivity, strong characteristic feather, good repeatability, and accuracy in qualitative and quantitative effect; the 0.01mg/kg residual limit for corresponding food safety detection by countries including America, Japan, European Union and Canada, namely, the technical requirement of uniform limit, is met, and therefore, powerful technical support is provided for guaranteeing food safety of Chinese people and healthy development of export trade.
Description
Technical field
The present invention relates to a kind of GC-NCI-MS assay method of Rynaxypyr residual quantity, be more particularly the method adopting Gas Chromatography-Negative chemical ionization source-mass spectrum (GC-NCI-MS) qualitative, quantitative to measure Rynaxypyr 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
Rynaxypyr (Chlorantraniliprole), trade name health is wide, it is the novel O-formammidotiazol-benzamide pesticide of E.I.Du Pont Company's exploitation, Rynaxypyr high-efficiency broad spectrum, good control effects is all had to lepidopterous Noctuidae, Pyralidae, Carposinidae, tortricid, miller section, diamond-back moth section, Gelechidae, Gracilariidae etc., coleoptera Culculionidae can also be controlled, Chrysomelidae; Diptera Agromyzidae; The multiple non-lepidoptera pest such as Bemisia tabaci.Chemical name is: [4-chloro-2-methyl-6-[(methyl-carbamoyl) benzene]-1-(3-chloropyridine-2-base)-1H-pyrazoles-5-formamide, English language Chemical name is called the bromo-N-of 3-
3-Bromo-N-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide。CAS accession number is 500008-45-7, and molecular weight is 483.15, and structural formula is:
The a lot of country of Rynaxypyr obtains registration, has achieved all certificates of agriculture chemical registration sales applications in China, can large scale application.Chemical constitution due to Rynaxypyr has the brand-new desinsection principle that other any pesticides do not possess, efficiently can activate insect ryania (muscle) acceptor, calcium ion in excessive release cells in calcium storehouse, insect is caused to be paralysed dead, high to the larva activity of lepidoptera pest, insecticidal spectrum is wide, and lasting effect is good.10-100 is exceeded doubly according to the specific activity other products of current test findings to target pest. and some lepidopterous insects mating process can be caused disorderly, research proves that it can reduce the spawning rate of multiple noctuidae pests, the biological characteristics of and resistance of rainwater washing against good due to its lasting effect, these characteristics are actually perviousness, conduction, chemical stability, high insecticidal activity and cause insect to stop the comprehensive embodiment of effects such as taking food immediately.Therefore determine its than at present most other pesticide have longer and more stable and to crop protective effect.To the biting mouth parts insect in harm field crops, fruit tree, other special crops of vegetables and turf, can provide long-acting, the preventive and therapeutic effect of wide spectrum.
Along with the registration of Rynaxypyr, popularization and use, as U.S. in China's veterinary antibiotics main exit market, European Union, Canada and Japan and other countries, residue limits standard is formulated to it.On October 19th, 2009, the U.S. sends No. G/SPS/N/USA/1935 circular, and Environmental Protection Agency formulates Final Rule to pesticide Rynaxypyr (Chlorantraniliprole) license limitation.Content comprises: the residue limits of Rynaxypyr on Pericarppium Armeniacae Amarum is 5.0ppm; Residue limits on American pistachios is: 0.04ppm; Residue limits on spring onion is: 0.20ppm; Residue limits on strawberry is: 1.2ppm etc.On May 4th, 2010, the U.S. issues circular, intends extending pesticide Rynaxypyr (Chlorantraniliprole) and permits limitation in limited time.What this Final Rule prolongation pesticide Rynaxypyr (Chlorantraniliprole) remained indirectly or unintentionally permits limitation in limited time: Cereals 16 groups of forages, feed, culms; Leek; Green onion; Shallot; Peanut hay; Verdant; Bean feed; Soybean hay and 2 groups of leaf class rhizomes, tuberous vegetable: 0.20ppm.Canada to the maximum residue limit of Rynaxypyr (Chlorantraniliprole) is:
European Union and Japan have also formulated the maximum residue limit of Rynaxypyr in a lot of food agricultural product, to the food agricultural product not formulating maximum permission residue limits, all carry out " uniform limit " of 0.01mg/L.
In recent years, a lot of to the research of Rynaxypyr residues detection method in varieties of food items agricultural product, the detection method of report all adopts liquid chromatography (LC) or Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) to measure the detection method of cyanogen insect amide 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.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, Rynaxypyr belongs to electronegativity compound, but have no the report of the GC-NCI-MS detection method of Rynaxypyr residual quantity in vegetables and fruit 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 Rynaxypyr residual quantity 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 Rynaxypyr residual quantity, be mainly used in measuring Rynaxypyr 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-NCI-MS assay method of Rynaxypyr 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, 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
During by the same kind matrix blank sample of not containing chlorantraniliprole by above-mentioned steps (1), (2) process, obtain sample extraction purification residue, add appropriate solvent and mixed standard solution, vortex mixes, and is mixed with the Rynaxypyr series hybrid standard working fluid 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 Rynaxypyr in sample liquid, substitute into typical curve, obtain Rynaxypyr content in sample liquid, then the Mass Calculation of sample representated by liquid obtains Rynaxypyr residual quantity 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: 278,279,280.
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 Rynaxypyr in conjunction with GC-NCI-MS and quantitatively to detect, average recovery rate is 86.8% ~ 96.9%, average relative standard's deviation (RSD) is 4.0% ~ 9.7%, detection limit, lower than 1.41 μ g/kg, has easy and simple to handle, quick, accurate, highly sensitive and reproducible advantage.The 0.01mg/kg residue limits of the countries such as the U.S., Japan, European Union, Canada to corresponding food safety detection can be met, the i.e. technical requirement of " uniform limit ", provides strong technical support by for ensureing that our people's food security and export abroad trade develop in a healthy way.
Accompanying drawing explanation
The GC-NCI-MS Selective ion mode chromatogram of Fig. 1 to be concentration be Rynaxypyr mark liquid of 100ng/mL.
Fig. 2 is the GC-NCI-MS Selective ion mode chromatogram of the wheat blank sample of not containing chlorantraniliprole.
Fig. 3 is the GC-NCI-MS Selective ion mode chromatogram of the Rynaxypyr be added in blank wheat matrix.
The Rynaxypyr standard working curve that Fig. 4 is is substrate preparation with the wheat blank sample of not containing chlorantraniliprole.
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); TurboVap LV 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 >=98.0%, purchased from German Dr.Ehrenstorfer company.
Embodiment 1: the detection of Rynaxypyr residual quantity in wheat
(1) sample pre-treatments
Extract
Take 5g wheat samples 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.Strawberry 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 Rynaxypyr 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 Rynaxypyr in sample liquid, substitute into typical curve, obtain Rynaxypyr content in sample liquid, then the Mass Calculation of sample representated by liquid obtains Rynaxypyr 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 1.0mL/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: 278,279,280;
Quota ion is 278;
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 Rynaxypyr in table 1 wheat bare substrate
| Title | Retention time (min) | Regression equation | Related coefficient |
| Rynaxypyr Chlorantraniliprole | 23.39 | Y＝59.505X-280.78 | 0.9998 |
Recovery of standard addition and repeatability:
In the wheat of not containing chlorantraniliprole, add the Rynaxypyr 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 Rynaxypyr is 86.8% ~ 90.0%, and average relative standard's deviation (RSD) is 6.2% ~ 9.7%, illustrates that the recovery of the inventive method is higher, reproducible.
The recovery of table 2 Rynaxypyr and repeatability (n=6)
Detection limit:
The Rynaxypyr extraction standard working solution of variable concentrations is injected GC-NCI-MS, calculate detection limit with the cycles of concentration (cycles of concentration of wheat 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 Rynaxypyr is limited to 1.07 μ g/kg.
Embodiment 2: the detection of Rynaxypyr residual quantity 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
10 μ g/mL standard solution dilutions are made into 5,2,1,0.5,0.2,0.1 μ g/mL standard solution.By the pork blank sample of not containing chlorantraniliprole by 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 Rynaxypyr in above-mentioned pork sample with Mass Spectrometry Conditions.
Qualitative Identification: consistent with the mensuration of Rynaxypyr 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=174.7X-2149, and related coefficient is 0.9992.
Recovery of standard addition and repeatability:
The Rynaxypyr standard solution of 10,20 and 200 μ g/kg, 3 concentration levels is added in the pork of not containing chlorantraniliprole, 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 Rynaxypyr is 88.6% ~ 96.9%, and average relative standard's deviation (RSD) is 4.0% ~ 6.7%, illustrates that the recovery of the inventive method is high, reproducible.
The recovery of table 3 Rynaxypyr and repeatability (n=6)
Detection limit:
The Rynaxypyr extraction standard working solution of variable concentrations is 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 Rynaxypyr is limited to 1.41 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-NCI-MS assay method for Rynaxypyr 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, is concentrated into after doing, and dissolves constant volume with acetone/normal hexane mixed solvent that volume ratio is 1/1, after crossing film, treats that gas chromatography-electron impact ion source-mass spectrum (GC-NCI-MS) detects;
(3) preparation of standard working solution
By the same kind matrix blank sample of not containing chlorantraniliprole by above-mentioned steps (1), (2) process, obtain sample extraction purification residue, add appropriate solvent and mixed standard solution, vortex mixes, and is mixed with the Rynaxypyr series hybrid 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-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 Rynaxypyr in sample liquid, substitute into extraction standard curve, obtain Rynaxypyr content in sample liquid, then the Mass Calculation of sample representated by liquid obtains Rynaxypyr residual quantity in sample per sample.
2. the GC-NCI-MS assay method of a kind of Rynaxypyr residual quantity according to claim 1, is characterized in that, 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.
3. the GC-NCI-MS assay method of a kind of Rynaxypyr 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-NCI-MS assay method of a kind of Rynaxypyr residual quantity according to claim 1, 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-NCI-MS assay method of a kind of Rynaxypyr residual quantity according to claim 1, it is characterized in that, in step (4), 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: 278,279,280.
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| CN105223285A (en) * | 2015-08-28 | 2016-01-06 | 刘永强 | The GC-NCI-MS detection method of dibromochloropropane residual quantity in a kind of complex matrices |
| CN105223285B (en) * | 2015-08-28 | 2017-07-14 | 刘永强 | The GC NCI MS detection methods of dibromochloropropane residual quantity in a kind of complex matrices |
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| CN106546675A (en) * | 2016-10-24 | 2017-03-29 | 苏州市农业科学院 | The quantitative detecting method of Rynaxypyr residual quantity in a kind of tealeaves |
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| 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 |
| CN107607656B (en) * | 2017-08-07 | 2020-05-05 | 浙江省农业科学院 | Method for detecting cyantraniliprole and metabolite J9Z38 in fish |
| CN113406248A (en) * | 2021-06-03 | 2021-09-17 | 湖南省植物保护研究所 | Method for detecting residual quantity of tebuconazole amide and metabolite thereof and application thereof |
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