CN108802215A - The assay method of Rynaxypyr residual quantity in a kind of vegetables - Google Patents
The assay method of Rynaxypyr residual quantity in a kind of vegetables Download PDFInfo
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- CN108802215A CN108802215A CN201810432934.0A CN201810432934A CN108802215A CN 108802215 A CN108802215 A CN 108802215A CN 201810432934 A CN201810432934 A CN 201810432934A CN 108802215 A CN108802215 A CN 108802215A
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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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
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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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/14—Preparation by elimination of some components
- G01N2030/146—Preparation by elimination of some components using membranes
Abstract
The present invention provides a kind of assay methods of Rynaxypyr residual quantity in vegetables, remaining Rynaxypyr in sample is extracted with acetonitrile homogeneous, anhydrous magnesium sulfate is added and removes water, sodium chloride is saltoutd, supernatant is taken after vortex, oscillation, centrifugation, water constant volume is used after acetonitrile is added, 0.22 μm of filter membrane is crossed after mixing, using the high performance liquid chromatography-tandem mass instrument detection equipped with electric spray ion source, it is segmented multiple affair monitoring, quantified by external standard method, standard series working curve use the bare substrate liquid without component to be measured to prepare.This method TIANZHU XINGNAO Capsul is between 97.6% ~ 117.9%, average relative standard's deviation（RSD）Between 1.5% ~ 6.0%, when addition detection is limited to 0.001mg/kg, instrument signal to noise ratio is all higher than 3.By verification, this method is easy to operate fast and reliable, and qualitative, quantitative is accurate, and high sensitivity is reproducible, and is easily achieved large batch of sample analysis.China is 0.01mg/kg to the minimum Limited Doses of Rynaxypyr residual quantity in vegetables, and this method meets its requirement.
Description
Technical field
The present invention relates to the detection method fields of edible pesticide residue in agricultural products, specifically use efficient liquid phase
Chromatography-tandem mass spectrometry measures the residual quantity of Rynaxypyr in vegetables, have reached it is easy to operate quickly, qualitative, quantitative is accurate
Purpose.Belong to the determination techniques field of persticide residue.
Background technology
Rynaxypyr is a kind of efficient, wide spectrum novel O-formammidotiazol-benzamide insecticide, to Lepidoptera
Noctuidae, Pyralidae, Carposinidae, tortricid, miller section, diamond-back moth section, Gelechidae, Gracilariidae etc. all have good control
Effect processed, moreover it is possible to control coleoptera Culculionidae, Chrysomelidae；Diptera Agromyzidae；A variety of non-lepidoptera pests such as Bemisia tabaci.Due to
The chemical constitution of Rynaxypyr has the completely new desinsection principle that other insecticides do not have, can efficient activation insect fish mud fourth
（Muscle）Receptor.Calcium ion excessively in release intracellular calcium store, causes insect paralysis dead, lives to the larva of lepidoptera pest
Property it is high.Rynaxypyr worm is general wide, and lasting effect is good, resistance of rainwater washing against, and research has shown that it can reduce a variety of Noctuidae evils
The spawning rate of worm, synthesis embody its permeability, conductibility, chemical stability, high insecticidal activity and pest are caused to stop immediately
The effects that feeding, determines that it has longer, more stable protective effect to crop.
With the registration, popularization and use of Rynaxypyr, China《National food safety standard Pesticide is most
Big residue limits》（GB 2763-2016）Middle regulation, limitation is respectively young corn 0.01mg/kg temporarily in vegetables；Tubers and
0.02 mg/kg of tuber and tuberous rooted vegetables；Melon vegetables 0.3mg/kg；Solanaceous vegetables are 0.6 mg/kg；Brassica genus class vegetables, balling
Wild cabbage, cauliflower are 2 mg/kg；Celery is 7 mg/kg；Leaf vegetables（Except celery）20 mg/kg.
It is in recent years, many to the research of Rynaxypyr determination of residual amount method in varieties of food items, agricultural product, environment,
There are gas chromatography, high performance liquid chromatography, gas chromatography tandem mass spectrometry method, high performance liquid chromatography-tandem mass method etc..Liquid
Although phase chromatography is ripe, easily promotes, solvent consumption is big, of high cost, and purified treatment requirement of the first three methods to sample
It is very high, the sample of matrix complexity is difficult to measure, and Liquid Chromatography-Tandem Mass Spectrometry has easy to operate, qualitative, quantitative standard
Really, high sensitivity, degree of purification requires low advantage, therefore, by high performance liquid chromatography-tandem mass method to chlorine worm in vegetables
The quantitative and qualitative detection of benzamide is of great significance.
Invention content
For the drawbacks described above of the prior art, the measurement of Rynaxypyr residual quantity in a kind of vegetables provided by the invention
Method, simple and quick, high sensitivity, stability are good, the low survey for Rynaxypyr residual quantity in vegetables of use cost
Determine method.
In order to achieve the above object, the present invention provides the following technical solutions：
The assay method of Rynaxypyr residual quantity, is as follows in a kind of vegetables：
1) it extracts
Homogenate is made in vegetable sample chopping mixing homogenization, weighs 15g（It is accurate to 0.01g）The sample prepared in tool plug from
It is accurate that high-speed homogenization extraction 2 minutes on homogenizer are added after 15mL acetonitriles in heart pipe, 6.0g anhydrous magnesium sulfates are added and remove water,
1.5g sodium chloride is saltoutd, and after being vortexed, vibrating, is centrifuged 5min with 6000r/min, is taken 1.0mL supernatants to 10mL volumetric flasks, add
Enter and be settled to scale with water after 4mL acetonitriles, 0.22 μm of organic filter membrane is crossed after mixing, using the efficient liquid equipped with electric spray ion source
Phase chromatography-tandem mass spectrometer detection.
2) preparation of standard series working solution
Rynaxypyr standard solution in the commercially available methanol for having card (μ of ρ=100 g/mL) is bought, refrigeration is kept in dark place.
Accurate a concentration of 100 μ g/mL Rynaxypyrs standard solution of 1mL of drawing is fixed with methanol in 10mL volumetric flasks
Hold to scale, is configured to the Standard Stock solutions of a concentration of 10 μ g/mL, refrigeration is kept in dark place.
Accurate a concentration of 10 μ g/mL Rynaxypyrs Standard Stock solutions of 1mL of drawing use methanol in 10mL volumetric flasks
It is settled to scale, is configured to the standard intermediate solution of a concentration of 1 μ g/mL, refrigeration is kept in dark place.
The same type matrix blank sample without component to be measured is chosen, chopping mixing homogenization is made homogenate, weighs 15g
（It is accurate to 0.01g）It is filled in centrifuge tube in tool, it is accurate that high-speed homogenization extraction 2 minutes on homogenizer are added after 15mL acetonitriles, add
Entering 6.0g anhydrous magnesium sulfates goes water, 1.5g sodium chloride to saltout, and after being vortexed, vibrating, centrifuges 5min with 6000r/min, takes 1.0mL
Supernatant is added after 4mL acetonitriles to 10mL volumetric flasks and is settled to scale with water, cross 0.22 μm of organic filter membrane after mixing, sky is made
White matrix liquid is used for the preparation of standard curve, to reduce matrix effect.A certain amount of standard intermediate solution is accurately drawn, respectively
With vehicle solution dilution and constant volume is at standard working solution, matching while using.
3) solution is prepared
0.1% formic acid solution：Accurate measurement 500mL water, 500 μ L formic acid of addition, mixing, for use.
4) Instrument measuring condition
High-efficient liquid phase chromatogram condition：Chromatographic column：C181.7 μ m 2.1mm × 100mm of column；Mobile phase：+ 0.1% formic acid of acetonitrile is molten
Liquid gradient elution；Flow velocity：0.3mL/min；Column temperature：40℃；Sampling volume：10μL.
Mass Spectrometry Conditions：Ion source：The sources ESI；Ionization mode：Electron spray ionisation positive ion mode；Scan mode：More reactions
Monitoring；Capillary voltage：0.5kV；Atomization gas, blowback air are high pure nitrogen, and collision gas is high-purity argon gas；It should be adjusted before use
Each parameter makes sensitivity of mass spectrometry reach testing requirements.
Monitor ion pair：483.82 > 452.88,483.82 > 285.96,483.82 > 177.05.
5) it measures and result calculates
When carrying out sample measurement under identical experiment condition, if the retention time and mark of the chromatographic peak detected in sample solution
Quasi- sample is consistent, and the ion selected occurs, and selected abundance of ions is than the abundance of ions with standard sample than one
It causes, then it can be qualitative.Standard working solution injection instrument is drawn into standard curve, obtains the concentration of Rynaxypyr in sample,
Substitute into the content that following equation obtains Rynaxypyr in sample：
X=
In formula：Rynaxypyr content, mg/kg in X-sample；The concentration of Rynaxypyr in ρ-sample preparation liquid,
ng/mL；
The final constant volumes of v-, mL；F-extension rate；The sampling amount of m-sample, g.
Related content is explained as follows in above-mentioned technical proposal：
1) when standard series working solution is prepared, the bare substrate of not containing chlorantraniliprole in sample is chosen first, is passed through
It is settled to 10mL after a series of above-mentioned pretreatment process, to reduce matrix effect, using constant volume liquid as constant volume medium, using preparing
Standard Stock solutions or standard intermediate solution, be configured to respectively a concentration of 1ng/mL, 5ng/mL, 10ng/mL, 20ng/mL,
The standard series working curve of 50ng/mL, 100ng/mL.
2) reagent material involved in experimentation is as follows：Acetonitrile：Chromatographically pure；Anhydrous magnesium sulfate（Using first 400 DEG C ~
600 DEG C of high temperature sintering 4h）：It analyzes pure；Sodium chloride：It analyzes pure；Formic acid：Chromatographically pure；Experimental water is to meet the regulations of GB/T 6682
Two level water.
3) instrument and equipment involved in experimentation is as follows：With electric spray ion source（ESI）Liquid chromatography-tandem
Mass spectrograph；Sensibility reciprocal is the electronic balance of 0.01g；Maximum centrifugal rotating speed is not less than the centrifuge of 8000r/min；High speed homogenization device.
The beneficial effects of the present invention are：
1) this method compared to traditional QuEChERS methods for, under the premise of meeting sensitivity for analysis, do not use PSA etc.
Dispersion extraction filler purifies, and directly dilutes sample introduction, reduces analysis time, analysis cost greatly reduces, and be easily achieved
Large batch of sample analysis.
2) this method is extracted with homogenate method and is extracted instead of extraction of ocean eddies and concussion, and the Rynaxypyr in vegetables is made to obtain
To abundant extraction, speed is fast, efficient.
By verification, TIANZHU XINGNAO Capsul of the invention is between 97.6% ~ 117.9%, average relative standard's deviation（RSD）?
Between 1.5% ~ 6.0%, when addition detection is limited to 0.001mg/kg, instrument signal to noise ratio is all higher than 3, it can be seen that its sensitivity
Height, it is reproducible, and also qualitative, quantitative is accurate.
For further understanding of the features and technical contents of the present invention, it please refers to below in connection with the detailed of the present invention
Illustrate and attached drawing, however, the drawings only provide reference and explanation, is not intended to limit the present invention.
Description of the drawings
Below in conjunction with the accompanying drawings, it is described in detail by the specific implementation mode to the present invention, technical scheme of the present invention will be made
And other beneficial effects are apparent.
Attached drawing 1 is blank sample（Wild cabbage）Chromatography of ions figure；
Attached drawing 2 is the mark-on sample for adding detection limit concentration（Wild cabbage）Characteristic ion mass chromatogram；
Attached drawing 3 is the mark-on sample for adding ten times of detection limits（Wild cabbage）Characteristic ion mass chromatogram；
Attached drawing 4 is bare substrate（Wild cabbage）The standard series curve that solution is prepared；
Attached drawing 5 is the characteristic ion mass chromatography of the Rynaxypyr standard solution for the 100ng/mL that vehicle solution is prepared
Figure；
Attached drawing 6 is the mark-on sample that additive amount is 0.033mg/kg（Cucumber）Characteristic ion mass chromatogram；
Attached drawing 7 is the mark-on sample that additive amount is 0.067mg/kg（Cucumber）Characteristic ion mass chromatogram.
Specific implementation mode
Further to illustrate the technological means and its effect of the invention taken, below in conjunction with the preferred implementation of the present invention
Example and its attached drawing are described in detail.
It please refers to Fig.1 to 7, the assay method of Rynaxypyr residual quantity is as follows in a kind of vegetables：
1) it extracts
Homogenate is made in vegetable sample chopping mixing homogenization, weighs 15g（It is accurate to 0.01g）The sample prepared in tool plug from
It is accurate that high-speed homogenization extraction 2 minutes on homogenizer are added after 15mL acetonitriles in heart pipe, 6.0g anhydrous magnesium sulfates are added and remove water,
1.5g sodium chloride is saltoutd, and after being vortexed, vibrating, is centrifuged 5min with 6000r/min, is taken 1.0mL supernatants to 10mL volumetric flasks, add
Enter and be settled to scale with water after 4mL acetonitriles, 0.22 μm of organic filter membrane is crossed after mixing, using the efficient liquid equipped with electric spray ion source
Phase chromatography-tandem mass spectrometer detection.
2) preparation of standard series working solution
Rynaxypyr standard solution in the commercially available methanol for having card (μ of ρ=100 g/mL) is bought, refrigeration is kept in dark place.
Accurate a concentration of 100 μ g/mL Rynaxypyrs standard solution of 1mL of drawing is fixed with methanol in 10mL volumetric flasks
Hold to scale, is configured to the Standard Stock solutions of a concentration of 10 μ g/mL, refrigeration is kept in dark place.
Accurate a concentration of 10 μ g/mL Rynaxypyrs Standard Stock solutions of 1mL of drawing use methanol in 10mL volumetric flasks
It is settled to scale, is configured to the standard intermediate solution of a concentration of 1 μ g/mL, refrigeration is kept in dark place.
The same type matrix blank sample without component to be measured is chosen, chopping mixing homogenization is made homogenate, weighs 15g
（It is accurate to 0.01g）It is filled in centrifuge tube in tool, it is accurate that high-speed homogenization extraction 2 minutes on homogenizer are added after 15mL acetonitriles, add
Entering 6.0g anhydrous magnesium sulfates goes water, 1.5g sodium chloride to saltout, and after being vortexed, vibrating, centrifuges 5min with 6000r/min, takes 1.0mL
Supernatant is added after 4mL acetonitriles to 10mL volumetric flasks and is settled to scale with water, cross 0.22 μm of organic filter membrane after mixing, sky is made
White matrix liquid is used for the preparation of standard curve, to reduce matrix effect.Among prepared Standard Stock solutions or standard
Solution is configured to the standard series of a concentration of 1ng/mL, 5ng/mL, 10ng/mL, 20ng/mL, 50ng/mL, 100ng/mL respectively
Working curve.
3) solution is prepared
0.1% formic acid solution：Accurate measurement 500mL water, 500 μ L formic acid of addition, mixing, for use.
4) Instrument measuring condition
High-efficient liquid phase chromatogram condition：
Chromatographic column：C181.7 μ m 2.1mm × 100mm of column；
Mobile phase：+ 0.1% formic acid solution (B) of acetonitrile (A)；Gradient elution program is as follows：
Flow velocity：0.3mL/min
Column temperature：40℃；
Sampling volume：10μL.
Mass Spectrometry Conditions：
Ion source：The sources ESI；
Ionization mode：Electron spray ionisation positive ion mode；
Scan mode：Multiple-reaction monitoring；
Capillary voltage：0.5kV；
Atomization gas, blowback air are high pure nitrogen, and collision gas is high-purity argon gas；Each parameter should be adjusted before use makes sensitivity of mass spectrometry
Reach testing requirements.
Monitor ion pair：
。
* the ion for quantitative analysis is indicated
5) it measures and result calculates
| Relative ion demeanour/% | >50 | 20~50 | 10~20 | <10 |
| Relative deviation/% of permission | ±20 | ±25 | ±30 | ±50 |
When carrying out sample measurement under identical experiment condition, if the retention time and mark of the chromatographic peak detected in sample solution
Quasi- sample is consistent, and the ion selected occurs, and selected abundance of ions is than the abundance of ions with standard sample than one
It causes, then it can be qualitative.
Standard working solution injection instrument is drawn into standard curve, the concentration of Rynaxypyr in sample is obtained, substitutes into
Following equation obtains the content of Rynaxypyr in sample：
X=
In formula：Rynaxypyr content, mg/kg in X-sample；The concentration of Rynaxypyr in ρ-sample preparation liquid,
ng/mL；
The final constant volumes of v-, mL；F-extension rate；The sampling amount of m-sample, g.
Embodiment 1：The measurement of Rynaxypyr residual quantity in wild cabbage
This method detection is limited to 0.001mg/kg.
Sample pre-treatments：
Weigh 15g（It is accurate to 0.01g）It is blank sample that the wild cabbage sample prepared, which is filled in tool in centrifuge tube, weighs 15g（Accurately
To 0.01g）It is mark-on sample that the wild cabbage sample prepared, which is filled in tool in centrifuge tube,（15ng, 150ng standard substance are added respectively）,
It is accurate that high-speed homogenization extraction 2 minutes on homogenizer are added after 15mL acetonitriles, 6.0g anhydrous magnesium sulfates are added and go water, 1.5g chlorinations
Sodium salt is analysed, and after being vortexed, vibrating, 5min is centrifuged with 6000r/min, takes 1.0mL supernatants to 10mL volumetric flasks, 4mL second is added
It is settled to scale with water after nitrile, 0.22 μm of organic filter membrane is crossed after mixing, using the high performance liquid chromatography-equipped with electric spray ion source
Tandem mass spectrometer detects.
The chromatography of ions figure of blank sample is as shown in Fig. 1.
The chromatography of ions figure for adding the mark-on sample of detection limit concentration is as shown in Fig. 2.
The chromatography of ions figure for adding the mark-on sample of ten times of detection limit concentration is as shown in Fig. 3.
The preparation of standard series working solution：
Rynaxypyr standard solution in the commercially available methanol for having card (μ of ρ=100 g/mL) is bought, refrigeration is kept in dark place.
Accurate a concentration of 100 μ g/mL Rynaxypyrs standard solution of 1mL of drawing is fixed with methanol in 10mL volumetric flasks
Hold to scale, is configured to the Standard Stock solutions of a concentration of 10 μ g/mL, refrigeration is kept in dark place.
Accurate a concentration of 10 μ g/mL Rynaxypyrs Standard Stock solutions of 1mL of drawing use methanol in 10mL volumetric flasks
It is settled to scale, is configured to the standard intermediate solution of a concentration of 1 μ g/mL, refrigeration is kept in dark place.
The same type matrix blank sample without component to be measured is chosen, chopping mixing homogenization is made homogenate, weighs 15g
（It is accurate to 0.01g）It is filled in centrifuge tube in tool, it is accurate that high-speed homogenization extraction 2 minutes on homogenizer are added after 15mL acetonitriles, add
Entering 6.0g anhydrous magnesium sulfates goes water, 1.5g sodium chloride to saltout, and after being vortexed, vibrating, centrifuges 5min with 6000r/min, takes 1.0mL
Supernatant is added after 4mL acetonitriles to 10mL volumetric flasks and is settled to scale with water, cross 0.22 μm of organic filter membrane after mixing, sky is made
White matrix liquid is used for the preparation of standard curve, to reduce matrix effect.Among prepared Standard Stock solutions or standard
Solution is configured to the standard series of a concentration of 1ng/mL, 5ng/mL, 10ng/mL, 20ng/mL, 50ng/mL, 100ng/mL respectively
Working curve.
The standard solution chromatography of ions figure for the 100ng/mL that bare substrate is prepared is as shown in Fig. 4.
The standard series curve that bare substrate is prepared is as shown in Fig. 5, r2=0.9978。
High-efficient liquid phase chromatogram condition：
Chromatographic column：C181.7 μ m 2.1mm × 100mm of column；
Mobile phase：+ 0.1% formic acid solution (B) of acetonitrile (A)；Gradient elution program is as follows：
Flow velocity：0.3mL/min
Column temperature：40℃；
Sampling volume：10μL.
Mass Spectrometry Conditions：
Ion source：The sources ESI；
Ionization mode：Electron spray ionisation positive ion mode；
Scan mode：Multiple-reaction monitoring；
Capillary voltage：0.5kV；
Atomization gas, blowback air are high pure nitrogen, and collision gas is high-purity argon gas；Each parameter should be adjusted before use makes sensitivity of mass spectrometry
Reach testing requirements.
Monitor ion pair：
。
* the ion for quantitative analysis is indicated
It measures and result calculates
| Relative ion demeanour/% | >50 | 20~50 | 10~20 | <10 |
| Relative deviation/% of permission | ±20 | ±25 | ±30 | ±50 |
When carrying out sample measurement under identical experiment condition, the retention time and standard sample of the chromatographic peak detected in sample solution
Condition is consistent, and the ion selected occurs, and selected abundance of ions is more consistent than with the abundance of ions of standard sample ratio, then
It can be qualitative.
Standard working solution injection instrument is drawn into standard curve, the concentration of Rynaxypyr in sample is obtained, substitutes into
Following equation obtains the content of Rynaxypyr in sample：
X=
In formula：Rynaxypyr content, mg/kg in X-sample；The concentration of Rynaxypyr in ρ-sample preparation liquid,
ng/mL；
The final constant volumes of v-, mL；F-extension rate；The sampling amount of m-sample, g.
When additive amount is 0.001mg/kg, signal-to-noise ratio is all higher than 3.
When additive amount is 0.01mg/kg, the rate of recovery is between 97.6% ~ 115.4%, precision 6.0%.
Embodiment 2：The measurement of Rynaxypyr residual quantity in cucumber
This method detection is limited to 0.001mg/kg.
Sample pre-treatments：
Weigh 15g（It is accurate to 0.01g）It is blank sample that the cucumber sample prepared, which is filled in tool in centrifuge tube, weighs 15g（Accurately
To 0.01g）It is mark-on sample that the cucumber sample prepared, which is filled in tool in centrifuge tube,（500ng, 1000ng are added respectively）, accurate to add
Enter after 15mL acetonitriles that high-speed homogenization extracts 2 minutes on homogenizer, 6.0g anhydrous magnesium sulfates are added and remove water, 1.5g sodium chloride salts
Analysis centrifuges 5min after being vortexed, vibrating with 6000r/min, takes 1.0mL supernatants to 10mL volumetric flasks, after 4mL acetonitriles are added
It is settled to scale with water, 0.22 μm of organic filter membrane is crossed after mixing, using high performance liquid chromatography-series connection equipped with electric spray ion source
Mass spectrograph detects.
The chromatography of ions figure of the mark-on sample of concentration is as shown in Fig. 6 in addition.
The chromatography of ions figure for adding the mark-on sample of higher concentration is as shown in Fig. 7.
Preparation, instrument condition, measurement and the result of standard series working solution are calculated with embodiment 1.
When additive amount is 0.033mg/kg, the rate of recovery is between 113.4% ~ 117.6%, precision 1.5%.
When additive amount is 0.067mg/kg, the rate of recovery is between 108.7% ~ 117.9%, precision 3.5%.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (4)
1. according to the assay method of Rynaxypyr residual quantity in a kind of vegetables described in claim 1, it is characterised in that packet
Include following steps：
Extraction
Homogenate is made in vegetable sample chopping mixing homogenization, 15g is weighed and is accurate to sample that 0.01g is prepared and centrifuged in tool plug
Guan Zhong, it is accurate that high-speed homogenization extraction 2 minutes on homogenizer are added after 15mL acetonitriles, 6.0g anhydrous magnesium sulfates are added and remove water,
1.5g sodium chloride is saltoutd, and after being vortexed, vibrating, is centrifuged 5min with 6000r/min, is taken 1.0mL supernatants to 10mL volumetric flasks, add
Enter and be settled to scale with water after 4mL acetonitriles, 0.22 μm of organic filter membrane is crossed after mixing, using the efficient liquid equipped with electric spray ion source
Phase chromatography-tandem mass spectrometer detection；
The preparation of standard series working solution
Rynaxypyr standard solution ρ=100 μ g/mL, refrigeration in the commercially available methanol for having card is bought to be kept in dark place；
Accurate a concentration of 100 μ g/mL Rynaxypyrs standard solution of 1mL of drawing is in 10mL volumetric flasks, extremely with methanol constant volume
Scale, is configured to the Standard Stock solutions of a concentration of 10 μ g/mL, and refrigeration is kept in dark place；
Accurate a concentration of 10 μ g/mL Rynaxypyrs Standard Stock solutions of 1mL of drawing use methanol constant volume in 10mL volumetric flasks
To scale, it is configured to the standard intermediate solution of a concentration of 1 μ g/mL, refrigeration is kept in dark place；
The same type matrix blank sample without component to be measured is chosen, chopping mixing homogenization is made homogenate, weighs 15g and be accurate to
0.01g is filled in tool in centrifuge tube, accurate to be added after 15mL acetonitriles that high-speed homogenization extracts 2 minutes on homogenizer, be added 6.0g without
Water magnesium sulfate goes water, 1.5g sodium chloride to saltout, and after being vortexed, vibrating, centrifuges 5min with 6000r/min, 1.0mL supernatants is taken to arrive
10mL volumetric flasks are added after 4mL acetonitriles and are settled to scale with water, cross 0.22 μm of organic filter membrane after mixing, bare substrate liquid is made,
For the preparation of standard curve, to reduce matrix effect；A certain amount of standard intermediate solution is accurately drawn, uses bare substrate respectively
Solution dilutes and constant volume is at standard working solution, matching while using；
Solution is prepared
0.1% formic acid solution：Accurate measurement 500mL water, 500 μ L formic acid of addition, mixing, for use；
Instrument measuring condition
High-efficient liquid phase chromatogram condition：Chromatographic column：C181.7 μ m 2.1mm × 100mm of column；Mobile phase：+ 0.1% formic acid solution of acetonitrile
Gradient elution；Column temperature：40℃；Sampling volume：10μL；
Mass Spectrometry Conditions：Ion source：The sources ESI；Ionization mode：Electron spray ionisation positive ion mode；Scan mode：More reaction prisons
It surveys；Capillary voltage：0.5kV；Atomization gas, blowback air are high pure nitrogen, and collision gas is high-purity argon gas；It should be adjusted before use each
Parameter makes sensitivity of mass spectrometry reach testing requirements；
Monitor ion pair：483.82 > 452.88,483.82 > 285.96,483.82 > 177.05；
It measures and result calculates
When carrying out sample measurement under identical experiment condition, if the retention time and mark of the chromatographic peak detected in sample solution
Quasi- sample is consistent, and the ion selected occurs, and selected abundance of ions is than the abundance of ions with standard sample than one
It causes, then it can be qualitative；Standard working solution injection instrument is drawn into standard curve, obtains the concentration of Rynaxypyr in sample,
Substitute into the content that following equation obtains Rynaxypyr in sample：
X=
In formula：Rynaxypyr content, mg/kg in X-sample；The concentration of Rynaxypyr in ρ-sample preparation liquid,
ng/mL；
The final constant volumes of v-, mL；F-extension rate；The sampling amount of m-sample, g.
2. according to the assay method of Rynaxypyr residual quantity in a kind of vegetables described in claim 1, which is characterized in that
Detection is limited to 0.001 mg/kg.
3. according to the assay method of Rynaxypyr residual quantity in a kind of vegetables described in claim 1, which is characterized in that
The standard working solution is prepared by the bare substrate liquid Jing Guo pre-treatment, and the gradient mass concentration for preparing curve is：1ng/mL,
5ng/mL、10ng/mL、20ng/mL、50ng/mL、100ng/mL。
4. the assay method of Rynaxypyr residual quantity, feature exist in a kind of vegetables according to claim 1 or 2
In when the detection is limited to 0.001mg/kg, instrument signal to noise ratio is all higher than 3, and TIANZHU XINGNAO Capsul is between 97.6% ~ 117.9%, phase
To standard deviation RSD between 1.5% ~ 6.0%.
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