CN104678043B - A kind of GC-EI-MS assay method of fluorine ether bacterium amide residual quantity - Google Patents
A kind of GC-EI-MS assay method of fluorine ether bacterium amide residual quantity Download PDFInfo
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Abstract
The invention discloses the GC EI MS assay method of a kind of fluorine ether bacterium amide residual quantity, the method is mainly used in measuring the method for the fluorine ether bacterium amide content of residual in the complex matrices food agricultural product such as Cereals, animal derived food.The fluorine ether bacterium amide of residual, C in sample is extracted with acetonitrile or the acetonitrile solution homogenizing containing 1% acetic acid18After/PSA Solid-Phase Extraction column purification concentrates, gas chromatogram electron impact ion source mass spectrum (GC EI MS) detects, and uses the vehicle solution without pesticide to be measured to set up the standard curve of correction, quantified by external standard method.This method average recovery rate is 82.5%～87.4%, and average relative standard's deviation (RSD) is 4.4%～6.4%, detection limit be less than 0.56 μ g/kg, have easy and simple to handle, quick, roguing is effective, highly sensitive, reproducible, qualitative, quantitative advantage accurately." uniform limit " technology requirement of 0.01mg/kg residue limits can be met, for ensureing that our people's food safety, export abroad trade sound development provide strong technical support.
Description
Technical field
The present invention relates to the GC-EI-MS assay method of a kind of fluorine ether bacterium amide residual quantity, more specifically use gas chromatogram
-electron impact ion source-mass spectrum (GC-EI-MS) qualitative, quantitative measures the animal fleshes such as Cereals, Carnis Sus domestica, beef, Carnis caprae seu ovis, Carnis Gallus domesticus
In the animals and plants derived food of the complex matrices such as meat and goods, the method for the fluorine ether bacterium amide content of residual, belongs to persticide residue
Determination techniques field.
Background technology
Fluorine ether bacterium amide (LH-2010A) is that Shandong United Pesticide Industry Co., Ltd. is new in the one of innovation synthesis in 2010
Type fluorine-containing Benzoylamide series bactericidal agent, chemical name is: N-(3-chloro-5-(trifluoromethyl) pyridine-2-methyl)-2,3,5,6-tetrafluoros
-4-methoxy benzamide, structural formula is:
Containing 7 fluorine atoms in fluorine ether bacterium amide structure formula.The C-F key bond energy that fluorine atom is formed is much larger than c h bond, hence it is evident that
Add stability and the physiologically active of organofluorine compound.Fluorinated organic compound has higher fat-soluble and hydrophobicity, energy
Enough promote that it absorbs and transmission in vivo, strengthen the binding ability with organism, make the physiological action of organism change.
Fluoro-containing pesticide has such effect equally, and pathogen or the suppression of insect or toxic action are also greatly improved by fluoro-containing pesticide.According to grinding
Studying carefully discovery, fluorine ether bacterium amide is to cotton rhizoctonia solani, botrytis cinerea, apple anthrax bacteria, Fulvia fulva, Fructus Mali pumilae
Target spot pathogen, phytophthora infestans, Leaf Spot Caused by Corynespora cassiicola on Cucumber bacterium, phytophthora blight of pepper, Strawberry Fusarium Wilt and Pyricularia oryzae 10 kinds are planted
The virulence of thing pathogen is the highest, it is seen then that fluorine ether bacterium amide sterilizes more wide spectrum, can be as a kind of New-type wide-spectrum type antibacterial
Using, development prospect is wide.
Along with fluorine ether bacterium amide registration, promote and use, relevant fluorine ether bacterium amide Residue Degradation is dynamically and final residue etc.
The research of environmental behaviour certainly will increase, meanwhile, if European Union, Japan and other countries regulation field as China's main exit market make
Do not register in this country with pesticide, when not formulating corresponding residue limits standard, be exported to the food agricultural product bag of its country
Include residue limits in the animal derived foods such as livestock meat and all carry out " uniform limit " of 0.01mg/L.
Up to now, have no and be related to the report of fluorine ether bacterium amide residues detection method in food agricultural product both at home and abroad, be equipped with
The gaschromatographic mass spectrometry (GC-EI-MS) in electron impact ionization source is analyzed food Residual Pesticides in Farm Produce tool and is had great advantage, by
It is versatility detector in electron impact ionization source mass spectrum, the multi-residue analysis of hundreds of kind of pesticide can be realized, can be the most qualitative and fixed
Amount, moderate, therefore existing various testing agencies and enterprise are equipped with gas chromatogram-electron impact ion source-mass spectrograph
(GC-EI-MS) pesticide residues in food agricultural product are detected, due to the food agricultural product such as Cereals, animal derived food
Substrate is more complicated, must set up the good sample-pretreating method of clean-up effect and could meet testing requirement, therefore, set up gas phase
The detection method of fluorine ether bacterium amide residual quantity in chromatographic mass spectrometry (GC-EI-MS) qualitative and quantitative analysis Cereals and animal derived food
Significant.
Summary of the invention
It is an object of the invention to provide the GC-EI-MS assay method of a kind of fluorine ether bacterium amide residual quantity, be mainly used in measuring grain
Fluorine ether bacterium amide residual quantity in the complex matrices food agricultural product such as paddy, animal derived food.
For realizing object above, the technical solution adopted in the present invention is: the GC-EI-MS of a kind of fluorine ether bacterium amide residual quantity
Assay method, comprises the steps:
(1) extract
Weigh mixing sample in tool plug centrifuge tube, after adding suitable quantity of water recovery, be quantitatively adding acetonitrile or equal containing the acetonitrile solution of 1% acetic acid
Matter or oscillating ultrasonic extract, and are subsequently 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 C18/ PSA Solid-Phase Extraction column purification, acetonitrile eluting, collection is washed
De-liquid, after being concentrated to dryness, dissolves constant volume with the acetone that volume ratio is 1/1/normal hexane mixed solvent, after crossing film, treat gas chromatogram-
Electron impact ion source-mass spectrum (GC-EI-MS) detects.
(3) preparation of standard working solution
When the same kind matrix blank sample of not fluorine-containing ether bacterium amide is processed by above-mentioned steps (1), (2), obtain sample extraction and purify
Residue, adds appropriate solvent and mixed standard solution, and vortex mixes, and is configured to the fluorine ether bacterium amide series mixing of at least 3 concentration
Standard working solution.
(4) gas chromatogram-electron impact ion source-mass spectrography (GC-EI-MS) measures
The standard working solution of each Concentraton gradient in step (3) is carried out GC-EI-MS mensuration, with the chromatographic peak area of standard working solution
Its respective concentration is carried out regression analysis, obtains standard working curve；Sample after purifying in step (2) under the same conditions
Liquid injects GC-EI-MS and is measured, and records the chromatographic peak area of fluorine ether bacterium amide in sample liquid, substitutes into standard curve, obtains sample
Fluorine ether bacterium amide content in product liquid, then obtains fluorine ether bacterium amide residual in sample according to the Mass Calculation of sample representated by sample liquid
Amount.
Step (1) if in the sample of the moisture content less such as sample Cereals and animal livers, suitable quantity of water must be added before extraction abundant
Infiltration.
Add sodium chloride when step (1) uses acetonitrile extraction to saltout, use the acetonitrile solution containing 1% acetic acid to add when extracting
Sodium acetate is saltoutd.
Step carries out C in (2)18/ PSA Solid phase extraction, during acetonitrile eluting, elution volume is 6～8mL.
In step (4), GC conditions is: chromatographic column: HP-5MS capillary chromatographic column, column length 30m, internal diameter 0.25
Mm, thickness 0.25 μm；Injector temperature 250 DEG C；Carrier gas: He, not shunt mode sample introduction, sample size: 1 μ L；Constant current mould
Formula, flow velocity 1.0mL/min；Heating schedule: initial temperature 60 DEG C keeps 2min, rises to 200 DEG C with the speed of 20 DEG C per minute, so
After rise 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, keep 10min；Transmission line temperature
Degree: 280 DEG C.
In step (4), Mass Spectrometry Conditions is: ion source temperature 230 DEG C；Quadrupole rod temperature 150 DEG C；Ionization pattern: electronics bangs
Hit ionization, i.e. EI pattern, energy 70eV；Scan mode: Salbutamol Selected Ion Monitoring (SIM) pattern, the ion of monitoring is: 381,
382、397、211。
When step (4) measures sample liquid and extraction standard working solution, if sample liquid Pesticides chromatographic peak retention time and standard
In solution, corresponding pesticide retention time is consistent, and in the sample mass spectrum after background correction, selected ion all occurs,
And abundance of ions is more consistent than the abundance of ions ratio with standard solution, then can determine whether sample liquid exists this pesticide；If above-mentioned two
Individual condition can not meet simultaneously, then judge without this kind of pesticide.
The beneficial effects of the present invention is:
The present invention utilizes dispersive solid-phase extraction technology, establishes simplicity, quickly and can be prevented effectively from the sample of sample mesostroma interference
Product pre-treating method, this pre-treating method combines GC-EI-MS, and to be applied to fluorine ether bacterium amide in Cereals, animal derived food qualitative
Confirmation and detection by quantitative, average recovery rate is 82.5%～87.4%, and average relative standard's deviation (RSD) is 4.4%～6.4%,
Detection limit is less than 0.56 μ g/kg, has easy and simple to handle, quick, accurate, highly sensitive and reproducible advantage.0.01 can be met
" uniform limit " technology requirement of mg/kg residue limits, for ensureing that our people's food safety, export abroad trade develop in a healthy way
Strong technical support is provided.
Accompanying drawing explanation
Fig. 1 is that the GC-NCI-MS being added on the fluorine ether bacterium amide in blank rice substrate selects chromatography of ions figure.
Fig. 2 is that the GC-NCI-MS of the rice blank sample of not fluorine-containing ether bacterium amide selects chromatography of ions figure.
Fig. 3 is the fluorine ether bacterium amide standard working curve with the rice blank sample of not fluorine-containing ether bacterium amide as substrate preparation.
Detailed description of the invention
Now with following embodiment, the present invention is described, but is not to limit the scope of the present invention.
The instrument used in embodiment and reagent
T18Basic homogenizer (IKA, Germany)；CR21G III centrifuge (Hitachi, Japan)；MS3 basic model is revolved
Whirlpool blender (IKA, Germany)；TurboVap LV pattern product automatic concentration instrument (Caliper, USA)；7890N gas phase color
Spectrum-5975C mass spectrograph (Agilent, USA)；C18/ PSA solid-phase extraction column (6mL, 500mg/500mg) is purchased from Tianjin and wins
Na Aijieer Science and Technology 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 analytical pure, are purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
Standard substance: purity 97.8%, purchased from Shandong United Pesticide Industry Co., Ltd..
Embodiment 1: the detection of fluorine ether bacterium amide residual quantity in Carnis Sus domestica
(1) sample pre-treatments
Extract
Weigh through the abundant 5g Carnis Sus domestica sample mixed in 50mL centrifuge tube, add the mixing of 5mL water, place 30min, accurately add
20mL acetonitrile, homogenizing extracts 2min, adds 3g anhydrous magnesium sulfate and 2g sodium chloride, and after vortex 1min, 7000r/min is centrifuged
5min.After Li Xin, take 8mL acetonitrile extraction liquid and be blown to about 1mL in 40 DEG C of rotation steamings or nitrogen, to be clean.
Purify
With 5mL acetonitrile prewashing C18/ PSA solid-phase extraction column, when liquid level arrives the top of adsorbent, proceeds to post by said extracted solution
In, wash test tube with 2mL acetonitrile, and cleaning mixture is moved in SPE post, when solution reaches adsorbent top, add 4mL
Acetonitrile carries out eluting to pillar, and eluent all receives in quantitative test tube, after nitrogen dries up, is the third of 1/1 by volume ratio
Ketone/normal hexane mixed solvent is settled to 1mL, after crossing 0.22 μm filter membrane, treats that GC-EI-MS measures.
(2) preparation of standard working solution
Accurately weighing 25 ± 0.1mg standard substance in 25mL volumetric flask, dissolve with acetonitrile, constant volume obtains 1000.0 μ g/mL standard reserving solutions；
Pipette 1.0mL standard reserving solution to be placed in 100mL volumetric flask, obtain with the acetone that volume ratio is 1/1/normal hexane mixed solvent constant volume
10.0 μ g/mL standard intermediate liquids；10 μ g/mL standard solution dilutions are made into 5,2,1,0.5,0.2,0.1 μ g/mL standard
Solution.The Carnis Sus domestica blank sample of not fluorine-containing ether bacterium amide is processed by above-mentioned pre-treatment step, obtains sample extraction and purify residue,
Adding acetone/normal hexane mixed solvent and the 100 above-mentioned mixed standard solutions of μ L that 900 μ L volume ratios are 1/1 in this residue, vortex mixes
Even, it is made into 10,20,50,100,200,500 μ g/L extraction standard working solutions.
(3) gas chromatogram-electron impact ion source-mass spectrography (GC-EI-MS) measures
The standard working solution of variable concentrations gradient is injected separately into GC-EI-MS, carries out quantitatively dividing of fluorine ether bacterium amide content with external standard method
Analysis, i.e. carries out regression analysis with the chromatographic peak area of standard working solution to its respective concentration, obtains standard curve；At the same terms
Lower sample extracting solution is injected GC-EI-MS it be measured, record the chromatographic peak area of fluorine ether bacterium amide in sample liquid, substitute into standard
Curve, obtains fluorine ether bacterium amide content in sample liquid, then obtains fluorine in sample according to the Mass Calculation of sample representated by sample liquid
Ether bacterium amide residual quantity.
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.
Furnace box heating schedule: initial temperature 60 DEG C keeps 2min, rises to 200 DEG C with the speed of 20 DEG C per minute, then with per minute
The speed of 2 DEG C rises to 220 DEG C, then rises to 280 DEG C with the speed of 20 DEG C per minute, keeps 10min.
Transmission line temperature: 280 DEG C.
Wherein, mass spectrometry parameters is:
Ionization pattern: electron impact ionization, i.e. EI pattern, energy 70eV.
Ion source temperature: 230 DEG C；Quadrupole rod temperature 150 DEG C.
Scan mode: Salbutamol Selected Ion Monitoring (SIM) pattern, the solvent delay time is that the ion of 10min, SIM monitoring is:
381、382、397、211；Quota ion is 381；
Qualitative Identification: at identical conditions, if sample liquid Pesticides chromatographic peak retention time pesticide corresponding to standard solution
Retention time is consistent, and in the sample mass spectrum after background correction, selected ion all occurs, and abundance of ions
Ratio is consistent with the abundance of ions ratio of standard solution, then can determine whether to exist in sample liquid this pesticide；If above-mentioned two condition can not be same
Time meet, then judge without this kind of pesticide.
With the chromatographic peak area of standard working solution, its respective concentration is carried out regression analysis, obtain standard working curve such as table 1.
The standard curve of fluorine ether bacterium amide in table 1 Carnis Sus domestica bare substrate
| Title | Retention time (min) | Regression equation | Correlation coefficient |
| Fluorine ether bacterium amide LH-2010A | 18.14 | Y=16505X-263053 | 0.9994 |
Recovery of standard addition and repeatability:
The fluorine ether bacterium amide standard of 10,20 and 200 g/kg3 concentration levels of μ is added in the Carnis Sus domestica of not fluorine-containing ether bacterium amide
Solution, carries out the determination of residual amount by above-mentioned process step after pesticide adds 30min.Mensuration concentration is added dense with pesticide theory
Degree compares, and obtains pesticide TIANZHU XINGNAO Capsul, each pitch-based sphere parallel assay 6 times, obtains its relative standard deviation, measures
The results are shown in Table 2.As can be seen from Table 2, in 3 mark-on levels, the average recovery rate of fluorine ether bacterium amide is 83.8%～87.4%,
Average relative standard's deviation (RSD) is 4.4%～6.4%, illustrates that the response rate of the inventive method is higher, reproducible.
The response rate of table 2 fluorine ether bacterium amide and repeatability (n=6)
Detection limit:
The fluorine ether bacterium amide substrate standard working solution of variable concentrations is injected GC-EI-MS, molten with least concentration extraction standard
3 times of signal to noise ratios at liquid chromatography peak and the cycles of concentration (cycles of concentration of Carnis Sus domestica is 2.0 times) of sample handling processes calculate detection limit,
The detection of fluorine ether bacterium amide is limited to 0.41 μ g/kg.
Embodiment 2: the detection of fluorine ether bacterium amide residual quantity in rice
(1) sample pre-treatments
Extract
Weigh through the abundant 5g rice sample (grinding to form flour) mixed in 50mL centrifuge tube, after adding 20mL water recovery 30min,
Accurately add the 20mL acetonitrile solution containing 1% acetic acid, mechanical shaking extraction 20min, supersound extraction 5min, add 3g anhydrous magnesium sulfate
With 2g sodium acetate, after vortex 1min, 7000r/min is centrifuged 5min.After Li Xin, take 8mL extracting solution and steam or nitrogen in 40 DEG C of rotations
It is blown near dry, after adding 1mL acetonitrile vortex, to be clean.
Purify
With 5mL acetonitrile prewashing C18/ PSA solid-phase extraction column, when liquid level arrives the top of adsorbent, proceeds to post by said extracted solution
In, wash test tube with 2mL acetonitrile, and cleaning mixture is moved in SPE post, when solution reaches adsorbent top, add 4mL
Acetonitrile carries out eluting to pillar, and eluent all receives in quantitative test tube, nitrogen dry up after with the acetone that volume ratio is 1/1/
Normal hexane mixed solvent is settled to 1mL, after crossing 0.22 μm filter membrane, treats that GC-EI-MS measures.
(2) preparation of standard working solution
Acetone/normal hexane mixed solvent that 1000ng/mL standard reserving solution volume ratio is 1/1 is diluted to 10ng/mL standard intermediate liquid,
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 not fluorine-containing ether bacterium amide
Rice blank sample is processed by above-mentioned pre-treatment step, obtains sample extraction and purifies residue, adds 900 μ L volume ratios in this residue
Being acetone/normal hexane mixed solvent and the 100 above-mentioned mixed standard solutions of μ L of 1/1, vortex mixes, be made into 10,20,50,100,
200,500 μ g/L extraction standard working solution.
(3) gas chromatogram-electron impact ion source-mass spectrography (GC-EI-MS) measures
Operating procedure, chromatograph are consistent with the mensuration of fluorine ether bacterium amide in above-mentioned Carnis Sus domestica sample with Mass Spectrometry Conditions.
Qualitative Identification: consistent with the mensuration of fluorine ether bacterium amide in above-mentioned Carnis Sus domestica sample.
Linear relationship:
With the chromatographic peak area of standard working solution, its respective concentration being carried out regression analysis, obtaining standard working curve is
Y=11985X-183822, correlation coefficient is 0.9993.
Recovery of standard addition and repeatability:
The fluorine ether bacterium amide standard of 10,20 and 200 3 concentration levels of μ g/kg is added in the rice of not fluorine-containing ether bacterium amide
Solution, carries out the determination of residual amount by above-mentioned process step after pesticide adds 30min, adds dense by mensuration concentration with pesticide theory
Degree compares, and obtains pesticide TIANZHU XINGNAO Capsul, each pitch-based sphere parallel assay 6 times, obtains its relative standard deviation, measures
The results are shown in Table 3.As can be seen from Table 3, in 3 mark-on levels, the average recovery rate of fluorine ether bacterium amide is 82.5%～85.9%,
Average relative standard's deviation (RSD) is 4.5%～5.9%, illustrates that the response rate of the inventive method is high, reproducible.
The response rate of table 3 fluorine ether bacterium amide and repeatability (n=6)
Detection limit:
The fluorine ether bacterium amide substrate standard working solution of variable concentrations is injected GC-EI-MS, with least concentration extraction standard solution chromatograph
3 times of signal to noise ratios at peak and the cycles of concentration (cycles of concentration of rice is 2.0 times) of sample handling processes calculate detection limit, fluorine ether
The detection of bacterium amide is limited to 0.56 μ g/kg.
Above embodiment is only to be described the preferred embodiment of the present invention, not limits the scope of the present invention
Fixed, on the premise of designing spirit without departing from the present invention, it is each that technical scheme is made by this area ordinary skill technology
Plant modification and improvement, all should fall in the protection domain that claims of the present invention determines.
Claims (4)
1. the GC-EI-MS assay method of a fluorine ether bacterium amide residual quantity, it is characterised in that said method comprising the steps of:
(1) extract
Weigh mixing sample in tool plug centrifuge tube, after adding suitable quantity of water, add acetonitrile or containing the acetonitrile solution homogenizing of 1% acetic acid or shake
After swinging supersound extraction, 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 C18/ PSA Solid-Phase Extraction column purification, acetonitrile eluting, receive
Collection eluent, after being concentrated to dryness, dissolves constant volume with the acetone that volume ratio is 1/1/normal hexane mixed solvent, after crossing film, treats gas phase color
Spectrum-electron impact ion source-mass spectrum (GC-EI-MS) detects；
(3) preparation of standard working solution
The same kind matrix blank sample of not fluorine-containing ether bacterium amide is processed by above-mentioned steps (1), (2), obtains sample extraction clean
Changing residue, add appropriate solvent and standard solution, vortex mixes, and is configured to the fluorine ether bacterium amide series standard work of at least 3 concentration
Make liquid；
(4) measure and result calculates
GC-EI-MS analysis condition is: chromatographic column: HP-5MS capillary chromatographic column, column length 30m, internal diameter 0.25mm, film
Thick 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 keep 2min, rise to 200 DEG C with the speed of 20 DEG C per minute, then with
The speed of 2 DEG C per minute rises to 220 DEG C, then rises to 280 DEG C with the speed of 20 DEG C per minute, keeps 10min；Transmission line temperature:
280℃；Ionization pattern: electron impact ionization, i.e. EI pattern, energy 70eV；Ion source temperature 230 DEG C；Scan mode: choosing
Selecting ion monitoring (SIM) pattern, the ion of monitoring is: 381,382,397,211；
The standard working solution of each Concentraton gradient in step (3) is carried out GC-EI-MS mensuration, with the chromatographic peak of standard working solution
Area carries out regression analysis to its respective concentration, obtains extraction standard working curve；Step (2) will be purified under the same conditions
After sample liquid inject GC-EI-MS and be measured, record the chromatographic peak area of fluorine ether bacterium amide in sample liquid, substitute into extraction standard
Working curve, obtains fluorine ether bacterium amide content in sample liquid, then obtains sample according to the Mass Calculation of sample representated by sample liquid
Middle fluorine ether bacterium amide residual quantity.
The GC-EI-MS assay method of a kind of fluorine ether bacterium amide residual quantity the most according to claim 1, it is characterised in that step
Suddenly (1) if in sample Cereals and animal livers sample, suitable quantity of water must be added before extraction and fully infiltrate.
The GC-EI-MS assay method of a kind of fluorine ether bacterium amide residual quantity the most according to claim 1, it is characterised in that step
Sodium chloride need to be added when (1) uses acetonitrile extraction suddenly to saltout, use the acetonitrile solution containing 1% acetic acid need to add acetic acid when extracting
Sodium salt is analysed.
The GC-EI-MS assay method of a kind of fluorine ether bacterium amide residual quantity the most according to claim 1, it is characterised in that step
Suddenly (2) carry out C18/ PSA Solid-Phase Extraction column purification, during acetonitrile eluting, elution volume is 6～8mL.
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