CN104678024B - The ECD assay method of fluorine ether bacterium amide residual quantity in a kind of vegetable and fruit - Google Patents
The ECD assay method of fluorine ether bacterium amide residual quantity in a kind of vegetable and fruit Download PDFInfo
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- CN104678024B CN104678024B CN201510109393.4A CN201510109393A CN104678024B CN 104678024 B CN104678024 B CN 104678024B CN 201510109393 A CN201510109393 A CN 201510109393A CN 104678024 B CN104678024 B CN 104678024B
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Abstract
The invention discloses the ECD assay method of fluorine ether bacterium amide residual quantity in a kind of vegetable and fruit, extracting the fluorine ether bacterium amide of residual in sample with acetonitrile or the acetonitrile solution homogenizing containing 1% acetic acid, extracting solution is through ethylenediamine N propyl silane (PSA) and octadecylsilane Bonded Phase (C18) substrate dispersion purify after, gas chromatogram electron capture detector (GC ECD) detect, quantified by external standard method.This method average recovery rate is 93.3%～98.3%, and average relative standard's deviation (RSD) is 4.1%～6.5%, and detection limit is less than 3.16 μ g/kg, has advantage the most accurately easy and simple to handle, quick, highly sensitive, reproducible, quantitative." uniform limit " technology requirement of 0.01 mg/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 ECD assay method of fluorine ether bacterium amide residual quantity in a kind of vegetable and fruit, more specifically use
Gas chromatography-electron capture detector (GC-ECD) measures the method for the fluorine ether bacterium amide content of residual in vegetable and fruit, belongs to
Determination techniques field in persticide residue.
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, fluorine ether in food agricultural product both at home and abroad
Containing 1 chlorine atom of 7 fluorine in bacterium amide molecule, belong to electronegativity compound, gas chromatogram electron capture detector can be used it
Residual quantity is analyzed, and has good capacity of resisting disturbance, and selectivity is good, highly sensitive, therefore, sets up gas chromatogram-electronics
It is significant that acquisition detector (GC-ECD) analyzes the detection method of fluorine ether bacterium amide residual quantity in vegetable and fruit.
Summary of the invention
It is an object of the invention to provide the ECD assay method of fluorine ether bacterium amide residual quantity in a kind of vegetable and fruit.
For realizing object above, the technical solution adopted in the present invention is: fluorine ether bacterium amide residual quantity in a kind of vegetable and fruit
ECD assay method, comprise the steps:
(1) extract
Weigh sample in tool plug centrifuge tube, add acetonitrile or the acetonitrile solution homogenizing containing 1% acetic acid extracts 1min, add sodium chloride or second
One in acid sodium and anhydrous magnesium sulfate, centrifugal after vibration.
(2) purify
Pipette sample extracting solution supernatant in centrifuge tube, add Dispersive solid phase extraction agent, vortex oscillation, centrifugal, draw certain
After amount scavenging solution nitrogen dries up, dissolve constant volume with the acetone that volume ratio is 1/1/normal hexane mixed solvent, after crossing film, treat gas chromatogram
-electron capture detector (GC-ECD) detects.
(3) preparation of standard working solution
Accurately preparing certain density standard reserving solution and standard intermediate liquid, the fluorine ether bacterium amide series being then configured at least 3 concentration is mixed
Standardization working solution；
(4) gas chromatography-electron capture detector (GC-ECD) measures
The standard working solution of each Concentraton gradient in step (3) is carried out GC-ECD mensuration, with the chromatographic peak area pair of standard working solution
Its respective concentration carries out regression analysis, obtains standard working curve；Sample liquid after purifying in step (2) under the same conditions
Inject GC-ECD to be measured, record the chromatographic peak area of fluorine ether bacterium amide in sample liquid, substitute into standard curve, obtain sample
Fluorine ether bacterium amide content in liquid, then obtains fluorine ether bacterium amide residual quantity in sample according to the Mass Calculation of sample representated by sample liquid.
Step (1) if in sample dehydrated vegetables and fruit, need to reduce sample weighting amount, and add suitable quantity of water and fully infiltrate.
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；A certain amount of water need to be added when the sample of moisture content less is saltoutd.
The dispersive solid-phase extraction agent of step (2) mesostroma is by anhydrous magnesium sulfate, C18Form with PSA, nothing in every volume extracting solution
Water magnesium sulfate, C18It is respectively 150mg, 50mg and 25mg with PSA addition.
In step (4), GC conditions is: chromatographic column: DB-5 capillary chromatographic column, column length 30m, internal diameter 0.32mm,
Thickness 0.25 μm；Injector temperature 250 DEG C；Carrier gas: high pure nitrogen, post flow is 1.5mL/min；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, with 20 DEG C per minute
Speed rise to 200 DEG C, then 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.
In step (4), electron capture detector condition is: detector temperature is 300 DEG C, and make-up gas flow is 30mL/min.
The beneficial effects of the present invention is: the present invention utilizes dispersive solid-phase extraction technology, establish simplicity, quickly and can be effective
Avoid the sample-pretreating method that sample mesostroma disturbs, this pre-treating method is combined GC-ECD and is applied in vegetable and fruit
Fluorine ether bacterium amide residue detection, average recovery rate is 93.3%～98.3%, and average relative standard's deviation (RSD) is 4.1%～6.5%,
Detection limit is less than 3.16 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 and carry
For strong technical support.
Accompanying drawing explanation
Fig. 1 is the chromatogram of 50ng/mL fluorine ether bacterium amide mark liquid.
Fig. 2 is the chromatogram of the Fructus Mali pumilae blank sample of not fluorine-containing ether bacterium amide.
Fig. 3 is fluorine ether bacterium amide standard working curve.
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)；5810R centrifuge (Eppendorf, Germany)；MS3 is basic
Type vortex mixer (IKA, Germany)；7890N gas chromatograph (is equipped with electron capture detector, Agilent, USA)；
Primary secondary amine (PSA) adsorbent (40～60 μm), octadecylsilane Bonded Phase (C18) cleanser (40～
60 μm) all it is purchased from Anjelen Sci. & Tech. Inc of the U.S..
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 Fructus Mali pumilae
(1) sample pre-treatments
Weighing through the abundant Fructus Mali pumilae 10.0g mixed in 50mL centrifuge tube, accurately add 20mL acetonitrile, homogenizing extracts 1min, addition 3
G anhydrous magnesium sulfate and 2g sodium chloride, after vortex 1min, 7000r/min is centrifuged 5min.After Li Xin, take 6mL acetonitrile extraction liquid
It is transferred to equipped with 900mg anhydrous magnesium sulfate, 300mg C18With in the centrifuge tube of 150mg PSA, vortex 1min, 5000r/min
Centrifugal 5min.Take 4mL supernatant in nitrogen blowpipe, dry up in 40 DEG C of nitrogen, add acetone/normal hexane that volume ratio is 1/1 and mix
Bonding solvent dissolved residue, after vortex mixed film, moves in sample injection bottle and treats that GC-ECD 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
To 10.0 μ g/mL standard intermediate liquids；10 μ g/mL standard solution are progressively diluted and is made into 10,20,50,100,200,500 μ g/L
Standard solution.
(3) gas chromatography-electron capture detector (GC-ECD) measures
The standard working solution of variable concentrations gradient is injected separately into GC-ECD, carries out the quantitative analysis of fluorine ether bacterium amide content with external standard method,
I.e. with the chromatographic peak area of standard working solution, its respective concentration is carried out regression analysis, obtain standard curve；Under the same conditions will
Sample extracting solution injects GC-ECD and is measured, and records the chromatographic peak area of fluorine ether bacterium amide in sample liquid, substitutes into standard curve,
Obtain fluorine ether bacterium amide content in sample liquid, then obtain fluorine ether bacterium acyl in sample according to the Mass Calculation of sample representated by sample liquid
Amine residual quantity.
Wherein chromatographic condition is:
Chromatographic column: DB-5 capillary chromatographic column, column length 30m, internal diameter 0.32mm, thickness 0.25 μm.
Injector temperature: 250.0 DEG C, sample introduction pattern: Splitless injecting samples, sample size: 1 μ L.
Carrier gas: high pure nitrogen, constant current mode, flow velocity 1.5mL/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；
ECD detector: temperature 300 DEG C, make-up gas flow is 30mL/min.
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 table 1 fluorine ether bacterium amide
| Title | Retention time (min) | Regression equation | Correlation coefficient |
| Fluorine ether bacterium amide LH-2010A | 17.39 | Y=131.64X-945.19 | 0.9992 |
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 Fructus Mali pumilae 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 94.8%～98.3%,
Average relative standard's deviation (RSD) is 4.1%～6.5%, 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 standard working solution of variable concentrations is injected GC-ECD, with least concentration standard solution chromatographic peak
The cycles of concentration (cycles of concentration of Fructus Mali pumilae is 2.0 times) of 3 times of signal to noise ratios and sample handling processes calculates detection limit, fluorine ether bacterium amide
Detection be limited to 0.82 μ g/kg.
Embodiment 2: the detection of fluorine ether bacterium amide residual quantity in dehydration Capsicum annuum L.
(1) sample pre-treatments
Weigh through the abundant dehydration Capsicum annuum L. 2.0g mixed in 50mL centrifuge tube, after adding 5mL water recovery 30min, accurately add 20
The mL acetonitrile solution containing 1% acetic acid, homogenizing extracts 1min, adds 3g anhydrous magnesium sulfate, 2g sodium acetate and 2mL water, vortex 1
After min, 7000r/min is centrifuged 5min.After Li Xin, take 6mL acetonitrile extraction liquid be transferred to equipped with 900mg anhydrous magnesium sulfate, 300
mg C18With in the centrifuge tube of 150mg PSA, vortex 1min, 5000r/min are centrifuged 5min.Take 4mL supernatant in nitrogen blowpipe
In, dry up in 40 DEG C of nitrogen, add acetone/normal hexane mixed solvent dissolved residue that volume ratio is 1/1, after vortex after mixing, move
Enter and sample injection bottle being treated, GC-ECD measures.
(2) preparation of standard working solution
Acetone/normal hexane mixed solvent that 10ng/mL standard intermediate liquid solution volume ratio is 1/1 is diluted in the middle of 1ng/mL standard
Liquid, is made into 10,20,50,100,200,500 μ g/L standard working solution by 1 μ g/mL standard solution dilution.
(3) gas chromatography-electron capture detector (GC-ECD) measures
Operating procedure, chromatograph are consistent with the mensuration of fluorine ether bacterium amide in above-mentioned Fructus Mali pumilae sample with Mass Spectrometry Conditions.
Recovery of standard addition and repeatability:
The fluorine ether bacterium amide of 50,100 and 200 3 concentration levels of μ g/kg is added in the dehydration Capsicum annuum L. of not fluorine-containing ether bacterium amide
Standard solution, carries out the determination of residual amount by above-mentioned process step after pesticide adds 30min, mensuration concentration is added with pesticide theory
Add concentration to compare, obtain pesticide TIANZHU XINGNAO Capsul, each pitch-based sphere parallel assay 6 times, obtain its relative standard deviation,
Measurement result is 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 be 93.3%～
97.0%, average relative standard's deviation (RSD) is 4.2%～5.1%, 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 standard working solution of variable concentrations is injected GC-ECD, with least concentration standard solution chromatographic peak
The cycles of concentration (cycles of concentration of dehydration Capsicum annuum L. is 0.4 times) of 3 times of signal to noise ratios and sample handling processes calculates detection limit, fluorine ether bacterium
The detection of amide is limited to 3.16 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 ECD assay method of fluorine ether bacterium amide residual quantity in a vegetable and fruit, it is characterised in that described method include with
Lower step:
(1) extract
Weigh vegetable and fruit sample in tool plug centrifuge tube in, add acetonitrile or containing 1% acetic acid acetonitrile solution homogenizing extract 1min,
It is centrifuged after adding the one in sodium chloride or sodium acetate and anhydrous magnesium sulfate vibration；
(2) purify
Pipette sample extracting solution supernatant in centrifuge tube, add Dispersive solid phase extraction agent, vortex oscillation, centrifugal, take one
After decontamination dosing liquid nitrogen air-blowing is dry, dissolve constant volume with the acetone that volume ratio is 1/1/normal hexane mixed solvent, after crossing film, treat gas phase color
Spectrum-electron capture detector (GC-ECD) detects；
(3) preparation of standard working solution
Accurately prepare certain density standard reserving solution and standard intermediate liquid, be then configured to the fluorine ether bacterium amide system of at least 3 concentration
Row standard working solution；
(4) measure and result calculates
GC-ECD analysis condition is: chromatographic column: DB-5 capillary chromatographic column, column length 30m, internal diameter 0.32mm, thickness 0.25
μm；Injector temperature 250 DEG C；Carrier gas: high pure nitrogen, post flow is 1.5mL/min；Not shunt mode sample introduction, sample size:
1μL；Constant current mode, flow velocity 1.0mL/min；Heating schedule: initial temperature 60 DEG C keeps 2min, with the speed liter of 20 DEG C per minute
To 200 DEG C, then 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,
Detector temperature is 300 DEG C, and make-up gas flow is 30mL/min；The standard working solution of each Concentraton gradient in step (3) is entered
Row GC-ECD measures, and with the chromatographic peak area of standard working solution, its respective concentration is carried out regression analysis, obtains standard work song
Line；Sample liquid after purifying in step (2) under the same conditions is injected GC-ECD and is measured, and records fluorine ether in sample liquid
The chromatographic peak area of bacterium amide, substitutes into standard curve, obtains fluorine ether bacterium amide content in sample liquid, then according to sample liquid institute's generation
The Mass Calculation of table sample obtains fluorine ether bacterium amide residual quantity in sample.
The ECD assay method of fluorine ether bacterium amide residual quantity, its feature in a kind of vegetable the most according to claim 1 and fruit
Be, step (1) if in vegetable and fruit sample dehydrated sample, need to reduce sample weighting amount, and add suitable quantity of water and fully infiltrate.
The ECD assay method of fluorine ether bacterium amide residual quantity, its feature in a kind of vegetable the most according to claim 1 and fruit
It is, sodium chloride need to be added when step (1) uses acetonitrile extraction and saltout, use the acetonitrile solution containing 1% acetic acid to need when extracting
Add sodium acetate to saltout.
The ECD assay method of fluorine ether bacterium amide residual quantity, its feature in a kind of vegetable the most according to claim 1 and fruit
Being, the dispersive solid-phase extraction agent of step (2) mesostroma is by anhydrous magnesium sulfate, C18Form with PSA, nothing in every milliliter of extracting solution
Water magnesium sulfate, C18It is respectively 150mg, 50mg and 25mg with PSA addition.
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| CN110824060A (en) * | 2019-11-26 | 2020-02-21 | 江苏韵沣检测有限公司 | Method for determining pesticide residue in vegetables by gas chromatography |
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