CN110426467A - The method for measuring quinoxyfen residual quantity in cow's milk - Google Patents
The method for measuring quinoxyfen residual quantity in cow's milk Download PDFInfo
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- CN110426467A CN110426467A CN201910641539.8A CN201910641539A CN110426467A CN 110426467 A CN110426467 A CN 110426467A CN 201910641539 A CN201910641539 A CN 201910641539A CN 110426467 A CN110426467 A CN 110426467A
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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
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Abstract
The invention discloses a kind of methods of quinoxyfen residual quantity in measurement cow's milk, and acetonitrile, magnesium sulfate, sodium chloride are added in cow's milk, is centrifuged after dissolution the present invention, extract supernatant, by the supernatant addition PSA of said extracted,Powder, anhydrous magnesium sulfate, dissolution, centrifugation, purified supernatant water-bath is evaporated to dryness, the residue after being evaporated with n-hexane dissolution and constant volume are vortexed and mix, cross 0.22 μm of organic filter membrane, sample solution is obtained, is measured for gas chromatograph-mass spectrometer, the residual quantity of quinoxyfen in cow's milk is judged by qualitative determination and quantitative determination.The acetonitrile that the present invention consumes is few, easy to operate, time saving, the residual quantity of quinoxyfen in energy Accurate Determining cow's milk, the methods of quinoxyfen residual quantity suitable for all measurement cow's milk.
Description
Technical field
The invention belongs to bioengineering field, it is related to measuring the residual quantity of quinoxyfen in cow's milk, specifically a kind of survey
Determine the method for quinoxyfen residual quantity in cow's milk.
Background technique
Quinoxyfen (quinoxyfen) also known as fast promise sweet smell, quinoxyfen, are that The Dow Agrosciences, LLC. newly releases in recent years
A kind of quinolines fungicide.It is currently widely used for various cereal crops, after foliage application, medicament can be rapidly infiltrated into
It is spread into plant tissue, and to top, the lasting period is up to 70 days, GB 2763.1-2018 " national food safety standard food
43 kinds of pesticide maximum residue limit such as middle paraquat " in clear stipulaties lactogenesis quinoxyfen maximum residue limit be 0.01mg/kg,
If the quinoxyfen remained in crop is entered in human body and increasingly accumulative by multiple food chains beyond this limitation, it will
Threaten the health of human body.In the prior art, also fewer for the research of quinoxyfen detection method both at home and abroad, P, Cabras etc.
Have studied grape, in grape wine and its fabricated product quinoxyfen residual quantity detection method；Yang Fang etc. has studied soybean, flower coconut palm
The detection method of quinoxyfen residual quantity in the matrixes such as dish, cherry, agaric, grape wine；Priscila Ferri etc. passes through efficient liquid
The phase chromatograph-mass spectrometer coupling technical research light path for transformation of quinoxyfen；HadynDuncan etc. is prepared by enzyme linked immune assay
Quinoxyfen analyzes immunoreagent.But pertinent literature, which is reported, to be had no for the research of quinoxyfen detection method in cow's milk.
" the detection side of quinoxyfen residual quantity in national food safety standard food prior art GB 23200.56-2016
Method " in using ethyl acetate as extractant, purified after gel permeation chromatography purifies, then through solid phase extraction column, upper liquid matter
It is detected, process is cumbersome, and verified, this method is not suitable for cow's milk matrix, and emulsification is serious, and recovery of standard addition only has 10%
Left and right；GB/T 23210-2008 " the measurement gas-chromatography-of 511 kinds of pesticides and related chemicals residual quantity in milk and milk powder
Mass spectrography " in using acetonitrile as extractant, by the small column purification of SPE, upper makings carries out detection quinoxyfen, and process is cumbersome, time-consuming consumption
Power, object loss are excessive.
Summary of the invention
The technical problems to be solved by the invention are to provide for a kind of method for measuring quinoxyfen residual quantity in cow's milk, lead to
The residual quantity for crossing quinoxyfen in gas chromatograph-mass spectrometer measurement cow's milk, realizes easy to operate, time saving and energy saving purpose.
To achieve the above object, used technical solution is as follows by the present invention: quinoxyfen residual quantity in a kind of measurement cow's milk
Method, method includes the following steps:
Step 1: sample extraction
Cow's milk is measured, acetonitrile, magnesium sulfate, sodium chloride is added, is dissolved, centrifugation extracts supernatant, by the residue acetonitrile after centrifugation
The supernatant primary, merging is repeatedly extracted at least is extracted again, it is to be clean；
Step 2: sample purification
Will in the supernatant of said extracted be added PSA,Powder, anhydrous magnesium sulfate dissolve, and supernatant, water-bath are extracted in centrifugation
It is evaporated to dryness, the residue after being evaporated with n-hexane dissolution and constant volume are vortexed and mix, and cross 0.22 μm of organic filter membrane, it is molten to obtain sample
Liquid is measured for gas chromatograph-mass spectrometer；
Step 3: qualitative determination
By sample solution under the conditions of the gas chromatograph-mass spectrometer of setting sample introduction, when being measured to sample solution, if sample
The retention time of chromatographic peak is consistent with quinoxyfen standard items in solution, and in sample solution mass spectrogram, selected ion
Occur, at the same selected abundance of ions than the abundance of ions with quinoxyfen standard items than it is consistent (or it is maximum allowable partially
In difference), then it can determine whether that there are the chemicals in sample；
Step 4: quantitative determination
Sample is measured using quantified by external standard method, it is quantitative by standard items with blank sample substrate preparation at standard series working solution,
The abundance ratio of the retention time of quinoxyfen, quota ion, qualitative ion is measured.
As the restriction to the method for quinoxyfen residual quantity in present invention measurement cow's milk: in the step 1, the second of addition
Nitrile is 20-25mL, magnesium sulfate 3-5g, sodium chloride 1-2g.
The step 1 and step are further defined that as the method to quinoxyfen residual quantity in present invention measurement cow's milk
Two dissolution is the concussion 2-3min that is vortexed on the oscillator.
As the further restriction to the method for quinoxyfen residual quantity in present invention measurement cow's milk: the step 1 and step
Centrifugation in rapid two is to carry out in 4000-7000r/min condition, and be centrifuged 5-15min.
As the further restriction to the method for quinoxyfen residual quantity in present invention measurement cow's milk: in the step 2,
The temperature of water-bath evaporation is 40-45 DEG C.
As a kind of restriction to the method for quinoxyfen residual quantity in present invention measurement cow's milk: in the step 2, water-bath
When evaporation, nitrogen is blown to dry.
It is limited as the another of method to quinoxyfen residual quantity in present invention measurement cow's milk: chromatography in the step 3
Separation condition are as follows:
Chromatographic column: HP-5MS (14% cyanogen propvl-phenvl)-methyl polysiloxane, quartz capillary column (mm of 30 m × 0.25 ×
0.25 μm)；
Chromatogram column temperature: then 40 DEG C of 1 min of holding are warming up to 130 DEG C with 30 DEG C/min, then be warming up to 6 DEG C/min
250 DEG C, keep the temperature 5 min；
Carrier gas: helium, purity >=99.999%, flow velocity, 1.2 mL/min；
Sample volume: 1.0 μ L；
Input mode: Splitless injecting-Sample；
Electron bombardment ionization source: 70eV；
Injector temperature: 290 DEG C；
Ion source temperature: 300 DEG C；
Level four bars temperature: 180 DEG C；
GC-MS interface temperature: 280 DEG C；
Solvent delay: 8 min；Salbutamol Selected Ion Monitoring mode.
As still another restriction to the method for quinoxyfen residual quantity in present invention measurement cow's milk: fixed in the step 3
Property measurement when, the maximum allowable offset of relative ion abundance are as follows:
Relative abundance > 50%, ± 10% deviation of tolerance；
Relative abundance > 20%~50% allows ± 15% deviation；
Relative abundance > 10%~20% allows ± 20% deviation；
Relative abundance≤10% allows ± 50% deviation.
Due to the adoption of the above technical solution, compared with prior art, the present invention acquired technological progress is:
For the rate of recovery obtained by sample extraction of the invention and purification process in 83.2% ~ 97.2 %, standard deviation is 6.3 %.The rate of recovery
It significantly improves, and precision is more accurate；Used acetonitrile is a kind of toxic organic solvent in experimentation, and the present invention disappears
The acetonitrile of consumption is few, easy to operate, time saving, the residual quantity of quinoxyfen in energy Accurate Determining cow's milk, suitable for all measurement cow's milk
The method of quinoxyfen residual quantity.
Detailed description of the invention
Fig. 1 of the invention is the canonical plotting of quinoxyfen；
Fig. 2 of the invention is the peak shape figure of quinoxyfen.
Specific embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
The method that embodiment 1 measures quinoxyfen residual quantity in cow's milk
Step 1: sample extraction
10mL cow's milk is measured in 50 mL centrifuge tubes, 22mL acetonitrile, 4.0g magnesium sulfate, 1.3g sodium chloride is added, on oscillator
Concussion 2.5min be vortexed to dissolving, is centrifuged 8mim under the conditions of 5284r/min, until residue and supernatant layering, take supernatant to wait for only
Change.
Step 2: sample purification
The addition of above-mentioned supernatant is pre-loaded with 0.25gPSA, 0.5gPowder, 0.75g anhydrous magnesium sulfate centrifuge tube in, in
It is vortexed concussion 2.3min on oscillator to dissolving, is centrifuged 12mim under the conditions of 4960r/min, until supernatant and residue are layered completely,
It extracts supernatant, 42 DEG C of water-bath rotary evaporations, and nitrogen and is blown to dry, residue after being then evaporated with n-hexane dissolution is simultaneously settled to
1mL is vortexed and mixes, and crosses 0.22 μm of organic filter membrane, obtains sample solution, measures for gas chromatograph-mass spectrometer.
Step 3: qualitative determination
By sample solution under the conditions of the gas chromatograph-mass spectrometer of setting sample introduction, when being measured to sample solution, if sample
The retention time of chromatographic peak is consistent with quinoxyfen standard items in solution, and in sample solution mass spectrogram, selected ion
Occur, while selected abundance of ions is more consistent than with the abundance of ions of quinoxyfen standard items ratio, then can determine whether to deposit in sample
In the chemicals；Or selected abundance of ions than the abundance of ions with quinoxyfen standard items than the maximum deviation in permission
It is interior, then it can determine whether that there are the chemicals, the maximum allowable offsets of abundance ratio in sample are as follows: relative abundance > 50%, tolerance ±
10% deviation；Relative abundance > 20%~50% allows ± 15% deviation；Relative abundance > 10%~20% allows ± 20% deviation；Phase
To abundance≤10%, allow ± 50% deviation.
Step 4: quantitative determination
Sample is measured using quantified by external standard method, it is quantitative by standard items with blank sample substrate preparation at standard series working solution,
The abundance ratio of the retention time of quinoxyfen, quota ion, qualitative ion is measured, measurement result such as table 1:
Retention time, quota ion, qualitative ion and the quota ion of 1 quinoxyfen of table and the abundance ratio of qualitative ion
。
In continuous mode, the parameters that gas chromatograph-mass spectrometer is adjusted are as follows:
Chromatographic column: HP-5MS (14% cyanogen propvl-phenvl)-methyl polysiloxane, quartz capillary column (mm of 30 m × 0.25 ×
0.25 μm)；
Chromatogram column temperature: then 40 DEG C of 1 min of holding are warming up to 130 DEG C with 30 DEG C/min, then be warming up to 6 DEG C/min
250 DEG C, keep the temperature 5 min；
Carrier gas: helium, purity >=99.999%, flow velocity, 1.2 mL/min；
Sample volume: 1.0 μ L；
Input mode: Splitless injecting-Sample；
Electron bombardment ionization source: 70eV；
Injector temperature: 290 DEG C；
Ion source temperature: 300 DEG C；
Level four bars temperature: 180 DEG C；
GC-MS interface temperature: 280 DEG C；
Solvent delay: 8 min；Salbutamol Selected Ion Monitoring mode.
The method that embodiment 2-8 measures quinoxyfen residual quantity in cow's milk
Embodiment 2-8 is the method for measuring quinoxyfen residual quantity in cow's milk, the basic phase of measuring method difference of they and embodiment 1
Together, it the difference is that only the selection in table 2 in listed step 1 and step 2 between parameter:
。
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (8)
1. a kind of method of quinoxyfen residual quantity in measurement cow's milk, it is characterised in that: method includes the following steps:
Step 1: sample extraction
Cow's milk is measured, acetonitrile, magnesium sulfate, sodium chloride is added, is dissolved, supernatant is extracted in centrifugation, to be clean；
Step 2: sample purification
Will in the supernatant of said extracted be added PSA,Powder, anhydrous magnesium sulfate dissolve, centrifugation, extract supernatant, and water-bath is steamed
It is sent to dry, residue and constant volume after being evaporated with n-hexane dissolution, vortex mixing crosses 0.22 μm of organic filter membrane, obtains sample solution,
It is measured for gas chromatograph-mass spectrometer；
Step 3: qualitative determination
By sample solution under the conditions of the gas chromatograph-mass spectrometer of setting sample introduction, when being measured to sample solution, if sample
The retention time of chromatographic peak is consistent with quinoxyfen standard items in solution, and in sample solution mass spectrogram, selected ion
Occur, at the same selected abundance of ions than the abundance of ions with quinoxyfen standard items than it is consistent (or it is maximum allowable partially
In difference), then it can determine whether that there are the chemicals in sample；
Step 4: quantitative determination
Sample is measured using quantified by external standard method, it is quantitative by standard items with blank sample substrate preparation at standard series working solution,
The abundance ratio of the retention time of quinoxyfen, quota ion, qualitative ion is measured.
2. the method for quinoxyfen residual quantity in measurement cow's milk according to claim 1, it is characterised in that: the step 1
In, the acetonitrile of addition is 20-25mL, magnesium sulfate 3-5g, sodium chloride 1-2g.
3. it is according to claim 2 measurement cow's milk in quinoxyfen residual quantity method, it is characterised in that: the step 1 and
The dissolution of step 2 is the concussion 2-3min that is vortexed on the oscillator.
4. the method for quinoxyfen residual quantity in cow's milk is measured described in any one of -3 according to claim 1, it is characterised in that:
Centrifugation in the step 1 and step 2 is to carry out in 4000-7000r/min condition, and be centrifuged 5-15min.
5. the method for quinoxyfen residual quantity in measurement cow's milk according to claim 4, it is characterised in that: the step 2
In, the temperature of water-bath evaporation is 40-45 DEG C.
6. the method for quinoxyfen residual quantity in measurement cow's milk according to claim 5, it is characterised in that: the step 2
In, when water-bath is evaporated, nitrogen is blown to dry.
7. the method for measuring quinoxyfen residual quantity in cow's milk described in any one of -3,5,6 according to claim 1, feature
It is: chromatographic separation condition in the step 3 are as follows:
Chromatographic column: HP-5MS (14% cyanogen propvl-phenvl)-methyl polysiloxane, quartz capillary column (mm of 30 m × 0.25 ×
0.25 μm)；
Chromatogram column temperature: then 40 DEG C of 1 min of holding are warming up to 130 DEG C with 30 DEG C/min, then be warming up to 6 DEG C/min
250 DEG C, keep the temperature 5 min；
Carrier gas: helium, purity >=99.999%, flow velocity, 1.2 mL/min；
Sample volume: 1.0 μ L；
Input mode: Splitless injecting-Sample；
Electron bombardment ionization source: 70eV；
Injector temperature: 290 DEG C；
Ion source temperature: 300 DEG C；
Level four bars temperature: 180 DEG C；
GC-MS interface temperature: 280 DEG C；
Solvent delay: 8 min；Salbutamol Selected Ion Monitoring mode.
8. the method for quinoxyfen residual quantity in measurement cow's milk according to claim 7, it is characterised in that: in the step 3
When qualitative determination, the maximum allowable offset of relative ion abundance are as follows:
Relative abundance > 50%, ± 10% deviation of tolerance；
Relative abundance > 20%~50% allows ± 15% deviation；
Relative abundance > 10%~20% allows ± 20% deviation；
Relative abundance≤10% allows ± 50% deviation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113533590A (en) * | 2020-04-14 | 2021-10-22 | 内蒙古伊利实业集团股份有限公司 | Pretreatment method for detecting pesticide residue in milk, dairy products and grain powder |
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2019
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| CN101246149A (en) * | 2008-03-25 | 2008-08-20 | 中国检验检疫科学研究院 | Fast high-precision detecting method for animal medicine residue in food |
| CA3018608A1 (en) * | 2016-03-23 | 2017-09-28 | Anaquant | Soluble balls for preparing solutions |
| CN108896694A (en) * | 2018-07-05 | 2018-11-27 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of remaining LC-QToF-MS Screening analysis method of pesticide in animal food |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113533590A (en) * | 2020-04-14 | 2021-10-22 | 内蒙古伊利实业集团股份有限公司 | Pretreatment method for detecting pesticide residue in milk, dairy products and grain powder |
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Address after: 050000 No. 68 stone Copper Road, Hebei, Shijiazhuang Applicant after: JUNLEBAO Dairy Group Co.,Ltd. Address before: 050000 No. 68 stone Copper Road, Hebei, Shijiazhuang Applicant before: THE SHIJIAZHUANG JUNLEBAO DAIRY Co.,Ltd. |
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Application publication date: 20191108 |