CN107860841A - A kind of method of ethiprole and its metabolin in detection birds, beasts and eggs - Google Patents
A kind of method of ethiprole and its metabolin in detection birds, beasts and eggs Download PDFInfo
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Abstract
The present invention provides a kind of method of ethiprole and its metabolin in detection birds, beasts and eggs, and selection is optimized to extraction cushioning liquid, after the ethiprole and its metabolin in extraction cushioning liquid extraction eggs sample, then with ethanol purification sample.Purified with purifying with QuEChERS methods after the concentrated removal ethanol of sample liquid, determined for gas-chromatography triple quadrupole bar mass spectrum (GC MS/MS) method.Whether the method energy effective detection birds, beasts and eggs sample of the present invention, discriminating receive the pollution of insecticide ethiprole.The detection method of the present invention can meet the requirement of ethiprole and its metabolite determination in birds, beasts and eggs.Standard items in this research are added in blank eggs, and its processing procedure is consistent with sample to be tested processing procedure, to eliminate due to error caused by matrix effect.
Description
Technical field
The invention belongs to technical field of food detection, and in particular to the side of ethiprole and its metabolin in a kind of detection birds, beasts and eggs
Method.
Background technology
The egg of in July, 2017 Holland outlet is found containing ethiprole composition at first, thus " malicious egg " event breaks out,
Ferment and involve rapidly Europe it is multinational, and undercarriage largely by insecticide ethiprole pollute egg, butchered problem hen, economy
Suffer heavy losses.Hong-Kong also detects ethiprole composition in two egg samples from imported from Holland.Due to China not yet
Clearly the limitation of ethiprole in eggs is made stipulations, and does not provide the detection method of ethiprole in eggs, government is related
The eggs quality safety that department also can not just be directed to China native country certainly is effectively assessed, and is directly influenced to China native country
In market eggs whether by the risk of ethiprole pollution carry out in real time, the understanding of depth, controls with supervising.
Due to the official method that China also determines without ethiprole in birds, beasts and eggs, can only join during this work of each labs
The determination method of ethiprole or Fluorine in Foods worm nitrile determination method in fruits and vegetables are examined, such as SN/T 1982-2007.But due to the detection of sample,
Detected according to existing method, effect is simultaneously bad, and this method is just for ethiprole, not comprising ethiprole metabolin (such as fluorine
Formonitrile HCN, ethiprole thioether, ethiprole sulfone), therefore, it is necessary to more perfect detection method.
The content of the invention
The present invention provides a kind of method of ethiprole and its metabolin in detection birds, beasts and eggs, so as to effectively detect birds, beasts and eggs sample
Whether product, discriminating receive the pollution of insecticide ethiprole.
The method of the present invention, includes the steps：
1) preparation of detected sample
The eggshell of birds, beasts and eggs to be detected is broken into pieces, content is used as testing sample after crushing；
2) preparation of extract solution
Testing sample is added in extraction buffer solution, after carrying out concussion extraction；Absolute ethyl alcohol is added in extract solution to carry out
Contamination precipitation, it is then centrifuged for obtaining supernatant；Supernatant is transferred in heart bottle, gone in a manner of water-bath decompression rotary evaporation
Except ethanol；After rotary evaporation terminates, the aqueous solution is transferred in centrifuge tube, is merged into acetonitrile rinse heart bottle in centrifuge tube,
After addition magnesium sulfate and sodium acetate carry out concussion processing, excess chlorination sodium is added, is shaken, so that water component saturation, after centrifugation
Aspirate supernatant is added in the purifying pipe containing magnesium sulfate and PSA, after vortex concussion, centrifugally operated is carried out again, in transfer
Layer liquid carries out concussion dehydration in the centrifuge tube for added anhydrous sodium sulfate, then again through 0.22 μm of organic phase pin type filter membrane mistake
Filter, detection liquid is obtained for gas chromatography-mass spectrometry analysis；
Described centrifugation, it is that 5min is centrifuged with 4000r/min；
Described magnesium sulfate and the mass ratio of sodium acetate are 4:1；
Described extraction buffer solution, the wherein volume ratio of absolute ethyl alcohol, lavation buffer solution and ammoniacal liquor are 10:10:1,
The composition and ratio of wherein lavation buffer solution are as follows：0.004moL/L two hypophosphite monohydrate sodium dihydrogens
(NaH2PO4.2H2O), 0.016moL/L disodium hydrogen phosphate dodecahydrate (Na2HPO4.12H2O), 0.15moL/L sodium chloride
(NaCl)；0.1% polysorbas20；
3) gas chromatography-mass spectrometry analysis
Use HP -5MS capillary chromatographic columns, injector temperature：280℃；Not shunt mode；Carrier gas：He；Constant voltage mode；
The μ L of sample size 1.0；Post case temperature：Initial 80 DEG C of maintenances 1min, 20 DEG C/min to 200 DEG C of temperature programming, maintains 4min；Continue journey
Sequence heats up 20 DEG C/min to 280 DEG C, again 10 DEG C/min to 310 DEG C of temperature programming, maintains 2min；Ion source temperature：300℃；
Ionization voltage：70ev；Level Four bar temperature：180℃；Accessory channel temperature：280℃；Emitting voltage：1500ev；Scan mode：It is more
Reactive ion monitoring pattern (MRM)；Solvent delay：5min；Detect ion determination and the retention time of ethiprole and its metabolin；
By the retention time of sample chromatogram and the retention time of standard liquid, the characteristic ion of chromatographic peak with it is corresponding dense
The characteristic ion of degree each chromatographic peak of standard items contrasts qualitative judgement；
Ion relative abundance in sample solution is compared with the ion relative abundance in matrix matching standard liquid, according to fixed
Measure ion and carry out external standard method, rational judgment is carried out by the formula obtained from standard curve；
4) standard curve making
Ethiprole is diluted with acetone and its standard mixed solution is made in metabolin standard items, and standard mixed solution is added in sky
The standard items testing sample of various criterion concentration point is made in white eggs sample；Examined according to the order of step 1) to step 3)
Survey；
Described each normal concentration is 5ng/mL, 10ng/mL, 20ng/mL, 40ng/mL, 60ng/mL, 80ng/mL,
100ng/mL；
5) calculation formula and data processing
Curvilinear regression is carried out in the response of each concentration point with ethiprole and its metabolin standard liquid, as quantitative mark
Standard, calculate the pesticide concentration of sample liquid automatically according to sample response value, then result of calculation is converted into mass fraction, ethiprole is residual
Allowance is that ethiprole and its metabolin (fluorine formonitrile HCN, ethiprole thioether and ethiprole sulfone) remain sum, is represented with ethiprole, with W
Meter, unit represent that its calculation formula is with milligrams per kilogram (mg/kg)：
W=ρ × V/ (m × 1000)
Wherein ρ-returned according to standard curve, the concentration (ng/mL) of obtained tested sample liquid；
The quality (g) of m- samples
V- constant volumes (mL).
The detection method of the present invention can meet the requirement of ethiprole and its metabolite determination in birds, beasts and eggs.Standard in this research
Product are added in blank eggs, and its processing procedure is consistent with sample to be tested processing procedure, to eliminate by matrix effect is brought
Error.
Brief description of the drawings
Fig. 1：According to the acetonitrile extraction centrifugation figure of SN/T 1982-2007 methods；
Fig. 2：The centrifugation figure of extracting method of the present invention；
Fig. 3：The GC-MS/MS total ion chromatograms of ethiprole and its metabolite standard items；
Fig. 4：Fluorine formonitrile HCN canonical plotting；
Fig. 5：Ethiprole canonical plotting；
Fig. 6:Ethiprole sulfone canonical plotting；
Fig. 7：Ethiprole thioether canonical plotting；
Fig. 8：Compound mass spectrogram；
Embodiment
When according to ethiprole in the method measure birds, beasts and eggs in SN/T 1982-2007 and its metabolin, it is found by the applicant that
The interference of lipid and phosphatide to object in Poultry and Eggs sample is very big.A large amount of lipid matters can be allowed using the extraction of existing acetonitrile
Dissolving wherein, can allow follow-up purification work to bring very big pressure, degree of purification is low to pollute chromatographic column, influence to use the longevity
Life.The sample after acetonitrile extraction is still in flocculence simultaneously, and the inside includes many objects, causes the rate of recovery low.For upper
Problem is stated, applicant extraction cushioning liquid is optimized selection, and extraction cushioning liquid extracts the ethiprole in eggs sample
And its after metabolin, then with ethanol purify sample.Purified after the concentrated removal ethanol of sample liquid with QuEChERS methods and net
Change, determined for gas-chromatography-triple quadrupole bar mass spectrum (GC-MS/MS) method.
The reagent used in the inventive method and instrument are specific as follows：
1st, ethiprole, fluorine formonitrile HCN, ethiprole thioether and ethiprole sulfone standard items are purchased from Beijing Zhen Xiang Co., Ltds, model
Specification is respectively：Ethiprole sulfone 100 μ g/mL, 1.2mL in methanol；Ethiprole thioether 101 μ g/mL, 1.1mL in acetone；In acetone
Fluorine formonitrile HCN 100 μ g/mL, 1mL；Ethiprole 100 μ g/mL, 1.5mL in n-hexane；Acetonitrile (chromatographically pure, Wo Kai, Chinese medicines group chemistry
Reagent Co., Ltd)；
2nd, absolute ethyl alcohol (analyzing pure, Chemical Reagent Co., Ltd., Sinopharm Group), concentrated ammonia liquor (analyzes pure, Chinese medicines group
Learn reagent Co., Ltd).
3rd, the preparation of lavation buffer solution：Hypophosphite monohydrate sodium dihydrogen (the NaH of 0.622g bis- are weighed respectively2PO4.2H2O)、5.735g
Disodium hydrogen phosphate dodecahydrate (Na2HPO4.12H2O), 9g sodium chloride (NaCl) plus distilled water dissolving, full dose are transferred to 1000mL
In volumetric flask, 1mL polysorbas20s are added, are settled to scale, mixed.
4th, the preparation of buffer solution is extracted：100mL absolute ethyl alcohols, 100mL lavation buffer solutions and the mixing of 10mL concentrated ammonia liquors.
5th, QuEChERS extractions bag, brand CNW, article No.：2.CA8115.B000, content：Magnesium sulfate 6g, sodium acetate
1.5g。
6th, QuEChERS purifying pipe, brand CNW, article No.：2.CA8321.0001, content：Magnesium sulfate 1.2g, PSA
400mg。
7th, ceramics proton (Agilent company of the U.S.) article No.：5982-9313.
8th, gas chromatograph-mass spectrometer, (Agilent 7890B-7000C Agilent company of the U.S.)；
9th, Rotary Evaporators (Hei-VAP Precision types, German heidolph)；
10th, centrifuge (centrifuge, German eppendorf)；
11st, turbula shaker (MS3basic, German IKA companies).
Embodiment 1：The foundation of extracting method
1) prepared by sample
Eggshell is broken into pieces, content is put into multi-functional broken wall cooking machine and crushed, and is made and treats test sample.It is put into separation container,
Preserved under the conditions of -18 DEG C, it is standby.
2) sample pre-treatments
Ethiprole and its metabolin in birds, beasts and eggs are determined by the method in SN/T 1982-2007：Weigh 10.00g samples in
In 100mL tool plug plastic centrifuge tubes, 10mL water is added, 40mL acetonitriles is accurately added, acutely vibrates 10 minutes, add after lid plug
5g sodium chloride, acutely shakes 10min, and 10min is centrifuged with 3000r/min.Upper strata extract solution 20mL is taken to be transferred to 50mL tool plug centrifugations
Guan Zhong, 10mL n-hexanes are added, shake 3min, static layering discards upper strata n-hexane phase, and lower floor's acetonitrile is mutually collected in 100mL
In heart bottle, near dry, addition 1.0mL acetone+n-hexane (3+7) dissolved residue is concentrated into 40 DEG C of water-baths.Sample liquid is poured into
The PSA posts washed in advance through 5mL acetone+n-hexane (3+7) pre-leaching, are eluted with 10mL acetone+n-hexane (3+7), are collected
Whole eluents are concentrated near do in 100mL heart bottles in 40 DEG C of water-baths.With acetone+n-hexane (3+7) dissolving and constant volume
To 1.0mL, determined for gas chromatograph-mass spectrometer.
As a result display SN/T 1982-2007 methods, after acetonitrile extraction centrifugation, egg sample floats in large area flocculence
(Fig. 1) is floated in solution, and this is directly connected to recovery of standard addition.Sample finds that recovery of standard addition is only 50% -70% after testing
Left and right, the flocculence of this and sample have relation, show that object may be included in flocculence sample.
In order to solve this problem, selection is optimized to extraction cushioning liquid, concrete scheme is as follows：
Take 2.00g eggs sample to have in 50mL in plug plastic centrifuge tube, add 10mL extraction buffer solutions, vortex shakes after lid plug
Swing 2 minutes.30mL absolute ethyl alcohols are added, are acutely shaken 5 minutes after lid plug, 5min is centrifuged with 4000r/min, Fig. 2 is seen, compares
Photo after the extraction centrifugation of SN/T 1982-2007 methods, after settling the technologies such as protein with extract dissolving extraction, ethanol, egg
Sample is located at solution bottom in small size is solid-state like, and recovery of standard addition significantly improves.Supernatant is poured into 100mL heart bottles
In.By sample liquid in heart bottle with 51 DEG C of water-bath decompression rotation hairs, to remove ethanol.Rotation hair terminates, and the aqueous solution is transferred to another
In 50mL centrifuge tubes, 5mL acetonitrile rinse jungle fowl heart bottles are added, merges washing lotion in the 50mL centrifuge tubes, repeats once.It is past
An equal proton of ceramics is put into centrifuge tube, the content added in extraction bag, lid shakes 2 minutes after filling in, and adds 3 grams of chlorinations
Sodium, lid are shaken 2 minutes after filling in, and 5min is centrifuged with 4000r/min.Draw 6mL upper liquids to enter to purify in pipe, on vortex mixer
Mix 1 minute, 5min is centrifuged with 4000r/min.Transfer upper liquid has been added in the centrifuge tube of 2 grams of anhydrous sodium sulfates in one, is covered
2 minutes fully dehydration, sample liquids are shaken after plug gas-chromatography-matter is supplied in sample bottle through 0.22 μm of organic phase pin type membrane filtration again
Spectrum analysis is used.Sample is detection indicate that recovery of standard addition is 88.1% -117.6%.
3) gas chromatography-mass spectrum condition
Capillary chromatographic column：HP -5MS (Crolinked 5%Phenyl Methyl Siloxane 30m × 0.32mm
×0.25μm).Injector temperature：280℃；Not shunt mode；Carrier gas：He；Constant voltage mode；The μ L of sample size 1.0.Post case temperature：
Initial 80 DEG C of maintenances 1min, 20 DEG C/min to 200 DEG C of temperature programming, maintains 4min；Continue temperature programming 20 DEG C/min to 280
DEG C, 10 DEG C/min to 310 DEG C of temperature programming, maintains 2min again.Ion source temperature：300℃；Ionization voltage：70ev；Level Four bar
Temperature：180℃；Accessory channel temperature：280℃；Emitting voltage：1500ev；Scan mode：More reactive ion monitoring patterns
(MRM)；Solvent delay：5min.Monitoring ion determines to be shown in Table 1 with the retention time of ethiprole and its metabolin.
Retention time, detection limit, monitoring ion and the collision energy of each component of table 1
* quota ion
The tolerance scope of the sample solution intermediate ion relative abundance of table 2
| Relative abundance % | Tolerance % |
| ＞ 50 | ±20 |
| ＞ 20~50 | ±25 |
| ＞ 10~20 | ±30 |
| ≤10 | ±50 |
4) standard liquid preparation and standard curve making
Ethiprole and its metabolin standard liquid are diluted into 10 μ g/mL mixed mark with acetone, and standard items are added in blank egg
In class sample, each standard point response is obtained with the operation consistent with sample pre-treatments, so as to avoid by matrix effect institute
The error brought influences.In this experiment, the mixed mark of 5 μ L, 10 μ L, 20 μ L, 40 μ L, 60 μ L, 80 μ L, 100 μ L is separately added into, is obtained
Each normal concentration point is：5ng/mL, 10ng/mL, 20ng/mL, 40ng/mL, 60ng/mL, 80ng/mL, 100ng/mL.Fig. 3 is
The GC-MS/MS total ion chromatograms of 80ng/mL concentration points ethiprole and its metabolite standard items；Its compound mass spectrogram
See Fig. 8.Fig. 4 is fluorine formonitrile HCN canonical plotting；Fig. 5：Ethiprole canonical plotting；Fig. 6:Ethiprole sulfone canonical plotting；Fig. 7:
Ethiprole thioether canonical plotting.
5) calculation formula and data processing
Curvilinear regression is carried out with the response of ethiprole and its each concentration point of metabolin standard liquid, as quantitative criterion,
Calculate the pesticide concentration of sample liquid automatically according to sample response value, then result of calculation is converted into mass fraction, ethiprole residual
Measure and remain sum for ethiprole and its metabolin (fluorine formonitrile HCN, ethiprole thioether and ethiprole sulfone), represented with ethiprole, in terms of W,
Unit represents that its calculation formula is with milligrams per kilogram (mg/kg)：
W=ρ × V/ (m × 1000)
Wherein ρ-returned according to standard curve, the concentration (ng/mL) of obtained tested sample liquid；
The quality (g) of m- samples
V- constant volumes (mL)
6) range of linearity and detection limit
Ethiprole and its metabolin are used into quantified by external standard method.Each series standard working solution is in concentration point：5ng/mL,
Good linear relation (r is presented when 10ng/mL, 20ng/mL, 40ng/mL, 60ng/mL, 80ng/mL, 100ng/mL2>
0.995).By sample through pre-treatment, upper machine, 3 times and 10 times of signal-noise ratio computation method detection limits and quantitative limit, method detection are obtained
Limit and quantitative limit are respectively：0.005mg/kg and 0.015mg/kg.
Embodiment 2：Submitted sample detects
The measure of ethiprole content is carried out to 15 eggs and duck's egg sample using the method that embodiment 1 is established, finds it
In detect ethiprole sulfone composition in an egg sample, specific implementation process is as follows：First by the sample with multi-functional broken wall
The thorough homogeneous of cooking machine blends into liquid.Weigh the 2.00g samples in 50mL to have in plug plastic centrifuge tube, add 10mL extractions
Buffer solution, vortex vibrates 2 minutes after lid is filled in.Add 30mL absolute ethyl alcohols, lid plug after acutely shaking 5 minutes, with 4000r/min from
Heart 5min, supernatant is poured into 100mL heart bottles.By sample liquid in heart bottle with 51 DEG C of water-bath decompression rotation hairs, to remove second
Alcohol.Rotation hair terminate, the aqueous solution is transferred in another 50mL centrifuge tubes, add 5mL acetonitrile rinse jungle fowl heart bottles, merge washing lotion in
In the 50mL centrifuge tubes, repeat once.An equal proton of stirring ceramics is put into toward centrifuge tube, is added in extraction bag
Content (magnesium sulfate 6g, sodium acetate 1.5g), lid shake 2 minutes after filling in, and add about 3 grams of sodium chloride, 2 points are shaken after lid plug
Clock, 5min is centrifuged with 4000r/min.Draw 6mL upper liquids to enter to purify in pipe, mixed 1 minute on vortex mixer, with
4000r/min centrifuges 5min.Transfer upper liquid has been added in the centrifuge tube of about 2 grams of anhydrous sodium sulfates in one, and 2 points are shaken after lid plug
Clock is fully dehydrated, sample liquid again through 0.22 μm of organic phase pin type membrane filtration in sample bottle for gas chromatography-mass spectrometry analysis.Two
Secondary parallel sample introduction result is shown：It is 4.3652ng/mL that ethiprole sulfone determines concentration at retention time 12.863 minutes, calculates and ties
Fruit is 0.0218mg/kg；It is 4.3403ng/mL that concentration is determined at retention time 12.864 minutes, and result of calculation is
0.0217mg/kg, average result 0.022mg/kg, survey deviation：0.46%.Its excess-three parameter：Fluorine formonitrile HCN, ethiprole sulphur
Ether, ethiprole are not detect, therefore the ethiprole content of the Final Report egg sample is 0.022mg/kg.
Claims (7)
1. a kind of method of ethiprole and its metabolin in detection birds, beasts and eggs, it is characterised in that described method includes following
Step：
1) preparation of detected sample
The eggshell of birds, beasts and eggs to be detected is broken into pieces, content is used as testing sample after crushing；
2) preparation of extract solution
Testing sample is added in extraction buffer solution, after carrying out concussion extraction；Absolute ethyl alcohol is added in extract solution and carries out impurity
Precipitation, be then centrifuged for obtain supernatant；Supernatant is inclined and is moved into heart bottle, is removed in a manner of water-bath decompression rotary evaporation
Ethanol；After rotary evaporation terminates, the aqueous solution is transferred in centrifuge tube, is merged into centrifuge tube, added with acetonitrile rinse heart bottle
Enter magnesium sulfate and after sodium acetate carries out concussion processing, add excess chlorination sodium, shake, so that water component saturation, inhales after centrifugation
Take supernatant to be added in the purifying pipe containing magnesium sulfate and PSA, after vortex concussion, carry out centrifugally operated again, shift upper strata
Solution carries out concussion dehydration in the centrifuge tube for added anhydrous sodium sulfate, then filters sample liquid through 0.22 μm of organic phase pin type again
Membrane filtration, detection liquid is obtained for gas chromatography-mass spectrometry analysis；
3) gas chromatography-mass spectrometry analysis
Use HP -5MS capillary chromatographic columns, injector temperature：280℃；Not shunt mode；Carrier gas：He；Constant voltage mode；Sample introduction
Measure 1.0 μ L；Post case temperature：Initial 80 DEG C of maintenances 1min, 20 DEG C/min to 200 DEG C of temperature programming, maintains 4min；Continue program liter
20 DEG C/min to 280 DEG C of temperature, 10 DEG C/min to 310 DEG C of temperature programming, maintains 2min again；Ion source temperature：300℃；Ionization
Voltage：70ev；Level Four bar temperature：180℃；Accessory channel temperature：280℃；Emitting voltage：1500ev；Scan mode：More reactions
Ion monitoring mode (MRM)；Solvent delay：5min；Monitor ion determination and the retention time of ethiprole and its metabolin；
Pass through the retention time and the retention time of standard liquid of sample chromatogram, the characteristic ion of chromatographic peak and respective concentration mark
The characteristic ion of quasi- each chromatographic peak of product contrasts qualitative judgement；
Ion relative abundance in sample solution compared with the ion relative abundance in matrix matching standard liquid, according to it is quantitative from
Son carries out external standard method, and rational judgment is carried out by the formula determined from standard curve.
2. method as claimed in claim 1, it is characterised in that described formula, the method that it is established are as follows：
1) standard curve making
Ethiprole is diluted with acetone and its standard mixed solution is made in metabolin standard items, and standard mixed solution is added in blank egg
The working curve with various criterion concentration point is made in class sample；Standard items are as testing sample, according to claim 1 institute
The step 1-3 stated order is detected；
2) calculation formula and data processing
Curvilinear regression is carried out with the response of ethiprole and its each concentration point of metabolin standard liquid, as quantitative criterion, according to
Sample response value calculates the pesticide concentration of sample liquid automatically, then result of calculation is converted into mass fraction, and ethiprole residual quantity is
Ethiprole and its metabolite residue sum, are represented with ethiprole, and in terms of W, unit is milligrams per kilogram to represent, its calculation formula
For：
W=ρ × V/ (m × 1000)
Wherein ρ-returned according to standard curve, the concentration ng/mL of obtained tested sample liquid；
The quality g of m- samples,
V- constant volumes mL.
3. the method as described in claim 1, it is characterised in that the centrifugation described in described step 2), be with 4000r/min
Centrifuge 5min.
4. the method as described in claim 1, it is characterised in that the mass ratio of magnesium sulfate and sodium acetate is in described step 2)
4:1。
5. the method as described in claim 1, it is characterised in that extraction buffer solution in described step 2) is absolute ethyl alcohol,
The volume ratio of the mixed solution of lavation buffer solution and ammoniacal liquor, wherein absolute ethyl alcohol, lavation buffer solution and ammoniacal liquor is 10:10:1.
6. method as claimed in claim 5, it is characterised in that the composition and ratio of described lavation buffer solution are as follows：
The chlorination of 0.004moL/L two hypophosphite monohydrate sodium dihydrogens, 0.016moL/L disodium hydrogen phosphate dodecahydrate, 0.15moL/L
Sodium, 0.1% polysorbas20.
7. method as claimed in claim 2, it is characterised in that described ethiprole and its concentration of metabolin standard liquid are
5ng/mL, 10ng/mL, 20ng/mL, 40ng/mL, 60ng/mL, 80ng/mL, 100ng/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711078533.1A CN107860841B (en) | 2017-11-06 | 2017-11-06 | Method for detecting fipronil and its metabolite in poultry egg |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711078533.1A CN107860841B (en) | 2017-11-06 | 2017-11-06 | Method for detecting fipronil and its metabolite in poultry egg |
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| CN113295784A (en) * | 2021-05-08 | 2021-08-24 | 湖南新程检测有限公司 | Food detection device and method based on gas chromatography-ionization-mass spectrometry |
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| CN103512993A (en) * | 2013-10-12 | 2014-01-15 | 崔淑华 | Hot pepper and determining method for 96 pesticide residues in product of hot pepper |
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| CN103512993A (en) * | 2013-10-12 | 2014-01-15 | 崔淑华 | Hot pepper and determining method for 96 pesticide residues in product of hot pepper |
| CN105866272A (en) * | 2016-03-31 | 2016-08-17 | 青岛正方元信公共卫生检测有限公司 | A method of detecting pesticide residues in a healthcare product |
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| CN113295784A (en) * | 2021-05-08 | 2021-08-24 | 湖南新程检测有限公司 | Food detection device and method based on gas chromatography-ionization-mass spectrometry |
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