CN107037149A - Ethiprole and its metabolite residue amount method for measuring in a kind of egg - Google Patents
Ethiprole and its metabolite residue amount method for measuring in a kind of egg Download PDFInfo
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Abstract
The present invention relates to ethiprole in a kind of egg and its metabolite residue amount method for measuring.Ethiprole and its assay method of metabolite residue amount include in egg of the present invention：Sample preparation；Sample pre-treatments；Organic solvent is extracted；Solid-phase extraction column removes pigment impurity, and nitrogen, which is blown to, closely to be done, and with mobile phase dissolved residue, solution is analyzed through membrane filtration for UPLC TQD；The preparation of standard liquid；High performance liquid chromatography tandem mass spectrum instrument determine, etc. process.The method of the present invention, simple to operate, quickly, automaticity is high, and extraction efficiency is fast, the rate of recovery and reproducible, can be achieved in egg to determine while ethiprole and its metabolite residue amount.
Description
Technical field
The present invention relates to ethiprole in a kind of egg and its metabolite residue quantity measuring method, and in particular in a kind of egg
The high performance liquid chromatography-tandem mass instrument method of 4 kinds of pesticide residue determinations, belongs to the physico-chemical examination technique field of residues of pesticides.
Background technology
In recent years, with the development of Chinese national economy, the people are food-safe in life gradually to be carried with quality requirement
Height, but for current social situation development, food security accident present in it still happens occasionally.Food security is
One concern national economy big problem, be to be related to everyone the most basic health problem, be even more following food industries hair
The core link of exhibition.Therefore the detection of various content of chemical substances just seems particularly heavy in strengthening to food in current work
Will.
Ethiprole and its metabolin are a kind of Phenylpyrazole insecticides, to a series of insects such as aphid, Ye Chan and flies
There is very high insecticidal activity.Research shows that such medical instrument has chronic neurotoxicity effect, is decided to be C class carcinogens.Phenyl
Pyrazoles medicine is extra-high to the toxicity of aquatic shellfish fish, shrimp, crab（Severe toxicity）, the toxicity to honeybee is also higher.Ethiprole pair
Light is more sensitive, and the Photolysis Half in water is 3.6h, and the Photolysis Half in soil is 34 days.Ethiprole is through photodissociation or oxygen
Change and 4 kinds of toxic metabolites are formed after reduction.The toxicity for wherein having 2 kinds of metabolins is higher by parent active compound to the 10 of mammalian toxicity
More than times, and fat has enrichment in vivo.In view of the excessive risk and its high destructiveness of ethiprole and its metabolin, I
State on October 1st, 2009 starts that the medicine is prohibited/limited the use of, in view of the excessive risk and its high destructiveness of ethiprole and its metabolin,
Ethiprole remains the attention for also having caused the states such as America and Europe, Japan in food, and has formulated strict limit standard.
At present, it is domestic to there is no ethiprole and its metabolin in egg while the Liquid Chromatography-Tandem Mass Spectrometry analysis side determined
Method, document report mainly has gas chromatography, gas chromatographymass spectrum, liquid-mass chromatography method to determine one of which agricultural chemicals, does not report also
Determine the ethiprole and its metabolin in egg simultaneously by high performance liquid chromatography tandem mass spectrum instrument.The foreign literature reported
In, the ethiprole in vegetables is detected using gas chromatography-mass spectrometry (GC/MS), but be not yet used for egg sample.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art there is provided one kind is simple to operate, and quickly, automaticity is high,
Extraction efficiency is high, the rate of recovery and reproducible, while determining the side of the ethiprole and its metabolin persticide residue in egg
Method.
To realize the purpose of foregoing invention, the technical scheme that the present invention takes is as follows：Ethiprole and its generation in a kind of egg
The method for thanking to the thing determination of residual amount, comprises the following steps：
（1）Sample preparation：Egg sample is rubbed, is homogenized, freezen protective；
（2）Sample pre-treatments：Accurately weigh through step（1）Uniform egg sample 2g is homogenized, 50mL polypropylene centrifuge tubes are placed in
In, 5 mL acetonitriles are added as crude extract, after homogeneous 1min, 10 min are vibrated, and at 4 DEG C, are centrifuged, extracted with 8000 r/min
Supernatant obtains extract solution in heart bottle；Sediment is repeated to extract 1 time with 5 mL acetonitriles, merges extract solution twice, adds 2mL
Isopropanol, is concentrated near dry in 50 DEG C of Rotary Evaporators, obtains concentrate；Added in concentrate 2.0mL methanol+with dichloromethane
Mixed solution dissolved residue, mixes, obtains solution to be clean；Solid-phase extraction column is used to 5mL methanol, 5mL methanol+dichloromethane successively
The mixed solution of alkane is eluted in advance, conditioning, and when solvent liquid level reaches solid-phase extraction column absorption layer surface, above-mentioned treat is poured into immediately
Purified solution, eluent is received with 15mL graduated centrifuge tubes, is rinsed with the mixed solution of 5mL methanol+dichloromethane after beaker,
Solid-phase extraction column is eluted, and is repeated once；The graduated centrifuge tube for filling 10mL eluents is placed on nitrogen evaporator, in bath temperature
Under the conditions of 50 DEG C, nitrogen drying is settled to 1.0mL with the mixed solution of acetonitrile+ultra-pure water, mixed on vortex mixer, warp
0.22 μm of organic membrane filtration, is determined for high performance liquid chromatography-tandem mass instrument；The mixed solution of the methanol+dichloromethane
Middle methanol is 1 with methylene chloride volume ratio：99；Acetonitrile is with ultrapure water volume ratio in the mixed solution of the acetonitrile+ultra-pure water
1：1；
（3）The preparation of standard liquid：Hybrid standard working solution dilution in acetonitrile, is configured to the mixing mark with graded series concentration
Quasi- working solution, with acetonitrile+ultrapure water mixed solution constant volume；Acetonitrile and ultrapure water body in the mixed solution of the acetonitrile+ultra-pure water
Product is than being 1：1；
（4）High performance liquid chromatography-tandem mass instrument is determined：By working solution inject equipped with triple level Four bars high performance liquid chromatography-
In tandem mass spectrometer instrument, carry out ultra performance liquid chromatography-tandem mass spectrum and determine；
（5）It is qualitative：When carrying out sample measure, if the chromatographic peak retention time of detection is consistent with the retention time of standard items, and
And after background correction in sample mass spectrum, selected ion occurs and the abundance of ions of abundance ratio and standard items compares one
Cause, then can determine whether there is this agricultural chemical compound in sample；
（6）It is quantitative：It is quantitative with external standard calibration curve method, to reduce influence of the matrix effect to dosing accuracy, using matrix
Standard curve is done with working solution, and ensures surveyed compound response within the scope of instrument is linear；
（7）Residual quantity calculation formula is as follows：
In formula：Persticide residue in w- samples（mg/kg）；The upper machines of M- determine concentration（ng/mL）；V- constant volumes（mL）；
V1- extract volume（mL）；V2- point take volume（mL）；M- sample sample weighting amounts V1- extract volume（g）.
Step（2）The neutral alumina column is the chromatographic column using acidic oxidation aluminium powder as solid phase extraction filler, solid phase
In extraction column, the addition of neutral alumina aluminium powder adds 1 gram of neutral alumina aluminium powder for every gram of sample；The neutral alumina
Powder is before use, in drying in Muffle furnace 400 DEG C.
Step（3）The graded series concentration of the hybrid standard working solution is 1.0 ng/mL, 2.0 ng/mL, 5.0 ng/
ML, 10.0 ng/mL, 20.0 ng/mL and 50.0 ng/mL.
It is preferred that, the step（1）Freezen protective temperature is -18 DEG C.
Further, step（2）The volume for adding acetonitrile adds 5.0 mL for every gram of sample.
Ethiprole and its method for the metabolite residue amount determination of residual amount are applied in detection egg in the egg of the present invention
Persticide residue；In particular for detecting the residual quantity of ethiprole and its metabolin in egg simultaneously.
Step（3）The graded series concentration of the hybrid standard working solution is 1.0 ng/mL, 2.0 ng/mL, 5.0 ng/
ML, 10.0 ng/mL, 20.0 ng/mL and 50.0 ng/mL.
It is preferred that, the ultra performance liquid chromatography condition determination used is as follows：UPLC ACQUITY BEHC18 posts, 50 ×
2.1 mm, 1.7 μm；Mobile phase A is acetonitrile, and Mobile phase B is 5mmol/L ammonium acetate solution；Flow velocity：0.3mL/min；Column temperature：
40℃；Sample size：10μL；The eluent gradient and time conditions used is shown in Table 1；
The eluent gradient of table 1 and time
。
It is preferred that, the Mass Spectrometry Conditions used are as follows：Ion gun：ESI, negative ion mode；Capillary voltage：4.0 kv ；
Ion source temperature：110 ℃；350 DEG C of desolvation temperature；Desolventizing gas flow：800 L/ hr；Taper hole blowback throughput 50
L/ hr；Taper hole voltage：40 v；Scan mode：Multiple-reaction monitoring（MRM）；The monitoring ion pair that is used, taper hole voltage and touch
Hit energy condition and be shown in Table 2, wherein band * is quantitative fragment ion；
The ethiprole of table 2 and its metabolin monitoring ion pair, taper hole voltage and collision energy
。
The beneficial effects of the invention are as follows：With ethiprole and its metabolite residue amount, processing operation in this method detection egg
Simply, quickly, automaticity is high, and extraction efficiency is high, is a kind of rate of recovery and reproducible measure egg Pesticide Residues
The method of amount；The inventive method can determine ethiprole in egg, fluorine formonitrile HCN, four kinds of agricultural chemicals of ethiprole sulfone and ethiprole sulfoxide simultaneously
Residual quantity.
Brief description of the drawings
Fig. 1：Ethiprole, fluorine formonitrile HCN, the standard liquid chromatograph figure of 4 kinds of agricultural chemicals of ethiprole sulfone and ethiprole sulfoxide（Concentration is
20.0 ng/mL）, monitored according to the MRM of ethiprole and its metabolin in condition, mass spectrogram and be followed successively by ethiprole sulfone, fluorine from 1 to 4
Worm nitrile, ethiprole sulfoxide and fluorine formonitrile HCN.
Fig. 2：Egg sample blank spectrogram.
Fig. 3：Egg sample mark-on spectrogram（Concentration is 20.0 ng/mL）.
Embodiment
The present invention is described in further details below by example, these examples are only used for illustrating the present invention, do not limit
The scope of the present invention processed.
Embodiment 1 is using the method for the present invention, ethiprole as follows respectively in 5 egg samples of measure, fluorine first
Nitrile, ethiprole sulfone and ethiprole sulfoxide residual quantity：
（1）Sample preparation：5 egg samples are rubbed into freezen protective under the conditions of homogenate, -18 DEG C respectively, frozen samples are obtained；
（2）Sample pre-treatments：Accurately weigh through step（1）Uniform egg sample 2g is homogenized, 50mL polypropylene centrifuge tubes are placed in
In, 5 mL acetonitriles are added as crude extract, after homogeneous 1min, 10 min are vibrated, and at 4 DEG C, are centrifuged, extracted with 8000 r/min
Supernatant obtains extract solution in heart bottle；Sediment is repeated to extract 1 time with 5 mL acetonitriles, merges extract solution twice, adds 2mL
Isopropanol, is concentrated near dry in 50 DEG C of Rotary Evaporators, obtains concentrate；Added in concentrate 2.0mL methanol+with dichloromethane
Mixed solution（Volume ratio is 1:99）Dissolved residue, mixes, obtains solution to be clean；By solid-phase extraction column successively with 5mL methanol,
The mixed solution of 5mL methanol+dichloromethane（Volume ratio is 1:99）Pre- elution, conditioning, when solvent liquid level reaches SPE
When post adsorbs layer surface, above-mentioned solution to be clean is poured into immediately, eluent is received with 15mL graduated centrifuge tubes, with 5mL methanol+
The mixed solution of dichloromethane（Volume ratio is 1:99）Rinse after beaker, elute solid-phase extraction column, and be repeated once；It will fill
The graduated centrifuge tube of 10mL eluents is placed on nitrogen evaporator, under the conditions of 50 DEG C of bath temperature, nitrogen drying, with acetonitrile+ultrapure
The mixed solution of water is settled to 1.0mL, is mixed on vortex mixer, through 0.22 μm of organic membrane filtration, for high-efficient liquid phase color
Spectrum-tandem mass spectrometer is determined；
（3）The preparation of standard liquid：Hybrid standard working solution dilution in acetonitrile, is configured to the mixing mark with graded series concentration
Quasi- working solution, with acetonitrile：Ultra-pure water（Volume ratio is 1:1）Mixed solution constant volume；
（4）High performance liquid chromatography-tandem mass instrument is determined：By working solution inject equipped with triple level Four bars high performance liquid chromatography-
In tandem mass spectrometer instrument, high performance liquid chromatography-tandem mass measure is carried out；
（5）It is qualitative：When carrying out sample measure, if the chromatographic peak retention time of detection is consistent with the retention time of standard items, and
And after background correction in sample mass spectrum, selected ion occurs and the abundance of ions of abundance ratio and standard items compares one
Cause, then can determine whether there is this agricultural chemical compound in sample；
（6）It is quantitative：It is quantitative with external standard calibration curve method, to reduce influence of the matrix effect to dosing accuracy, using matrix
Standard curve is done with working solution, and ensures surveyed compound response within the scope of instrument is linear；As a result in 2 egg samples
2 kinds of agricultural chemicals are detected in product, 3 are the results are shown in Table；
（7）Residual quantity calculation formula is as follows：
In formula：Persticide residue in w- samples（mg/kg）；The upper machines of M- determine concentration（ng/mL）；V- constant volumes（mL）；
V1- extract volume（mL）；V2- point take volume（mL）；M- sample sample weighting amounts.
The content of remains of pesticide in the egg sample of table 3
The measure of repeatability and the rate of recovery：Negative egg sample is respectively adopted（The feminine gender refer in the sample 4 kinds of agricultural chemicals without inspection
Go out）It is measured, the test limit of analyte is determined with 3 times of signal to noise ratio, the quantitative limit of analyte is determined with 10 times of signal to noise ratio, with reference to
The rate of recovery and sample size, the quantitative detection of method are limited to 0.01mg/kg, using the method that standard liquid is added in sample, same
Recovery of standard addition experiment is carried out to two kinds of agricultural chemicals under the sample treatment of sample, 4 are the results are shown in Table.
4 kinds of agricultural chemicals carry out recovery of standard addition and standard deviation in the egg of table 4（n=5）
。
The linear and detection limit that Ultra Performance Liquid Chromatography instrument tandem mass spectrometer determines 5 kinds of target compounds in egg sample is shown in
Table 5.
The Ultra Performance Liquid Chromatography instrument tandem mass spectrometer of table 5 determines the linear and detection of 5 kinds of target compounds in egg sample
Limit（n=5）
Embodiment described above is only that the preferred embodiment of the present invention is described, and is not to the scope of the present invention
It is defined, on the premise of design spirit of the present invention is not departed from, those of ordinary skill in the art are to technical scheme
In the various modifications made and improvement, the protection domain that claims of the present invention determination all should be fallen into.
Claims (8)
1. ethiprole and its metabolite residue amount method for measuring in a kind of egg, it is characterised in that：Comprise the following steps：
（1）Sample preparation：Egg sample is rubbed, is homogenized, freezen protective；
（2）Sample pre-treatments：Accurately weigh through step（1）Uniform egg sample 2g is homogenized, 50mL polypropylene centrifuge tubes are placed in
In, 5 mL acetonitriles are added as crude extract, after homogeneous 1min, 10 min are vibrated, and at 4 DEG C, are centrifuged, extracted with 8000 r/min
Supernatant obtains extract solution in heart bottle；Sediment is repeated to extract 1 time with 5 mL acetonitriles, merges extract solution twice, adds 2mL
Isopropanol, is concentrated near dry in 50 DEG C of Rotary Evaporators, obtains concentrate；Added in concentrate 2.0mL methanol+with dichloromethane
Mixed solution dissolved residue, mixes, obtains solution to be clean；Solid-phase extraction column is used to 5mL methanol, 5mL methanol+dichloromethane successively
The mixed solution of alkane is eluted in advance, conditioning, and when solvent liquid level reaches solid-phase extraction column absorption layer surface, above-mentioned treat is poured into immediately
Purified solution, eluent is received with 15mL graduated centrifuge tubes, is rinsed with the mixed solution of 5mL methanol+dichloromethane after beaker,
Solid-phase extraction column is eluted, and is repeated once；The graduated centrifuge tube for filling 10mL eluents is placed on nitrogen evaporator, in bath temperature
Under the conditions of 50 DEG C, nitrogen drying is settled to 1.0mL with the mixed solution of acetonitrile+ultra-pure water, mixed on vortex mixer, warp
0.22 μm of organic membrane filtration, is determined for high performance liquid chromatography-tandem mass instrument；The mixed solution of the methanol+dichloromethane
Middle methanol is 1 with methylene chloride volume ratio：99；Acetonitrile is with ultrapure water volume ratio in the mixed solution of the acetonitrile+ultra-pure water
1：1；
（3）The preparation of standard liquid：Hybrid standard working solution dilution in acetonitrile, is configured to the mixing mark with graded series concentration
Quasi- working solution, with acetonitrile+ultrapure water mixed solution constant volume；Acetonitrile and ultrapure water body in the mixed solution of the acetonitrile+ultra-pure water
Product is than being 1：1；
（4）High performance liquid chromatography-tandem mass instrument is determined：By working solution inject equipped with triple level Four bars high performance liquid chromatography-
In tandem mass spectrometer instrument, carry out ultra performance liquid chromatography-tandem mass spectrum and determine；Ultra performance liquid chromatography condition determination is as follows：
UPLC ACQUITY BEHC18 posts, 50 × 2.1 mm, 1.7 μm；Mobile phase A is acetonitrile, and Mobile phase B is 5mmol/L ammonium acetate
Solution；Flow velocity：0.3mL/min；Column temperature：40℃；Sample size：10μL；The eluent gradient and time conditions used is as follows：Stream
The dynamic time：0 min, 0.50 min, 3.00 min, 3.10 min, 5.00min, eluent gradient is successively, mobile phase A：20%、
20%th, 80%, 20%, 20%, Mobile phase B：80%、80%、20%、80%、80%；Mass Spectrometry Conditions are as follows：Ion gun：ESI, anion mould
Formula；Capillary voltage：4.0 kv ；Ion source temperature：110 ℃；350 DEG C of desolvation temperature；Desolventizing gas flow：800
L/ hr；The L/ hr of taper hole blowback throughput 50；Taper hole voltage：40 v；Scan mode：Multiple-reaction monitoring（MRM）；Wherein, adopted
Monitoring ion pair, taper hole voltage and collision energy condition are specific as follows：
A. ethiprole：Parent ion 434.8, quantitative fragment ion 250.0, the v of taper hole voltage -35, collision energy -25v；Parent ion
434.8, daughter ion 330.0, taper hole voltage -35, collision energy -15v；
B. fluorine formonitrile HCN：Parent ion 386.9, quantitative fragment ion 351.0, taper hole voltage -30v, collision energy -15v；Parent ion
386.9, daughter ion 282.0, taper hole voltage -30v, collision energy -30v；
C. ethiprole sulfone：Parent ion 450.9, quantitative fragment ion 282.0, taper hole voltage -35v, collision energy -25v；It is female from
Son 450.9, daughter ion 415.0, taper hole voltage -35v, collision energy -15v；
D. ethiprole sulfoxide：Parent ion 418.9, quantitative fragment ion 262.0, taper hole voltage -30v, collision energy -25v；It is female
Ion 418.9, daughter ion 314.0, taper hole voltage -30v, collision energy -20v；
（5）The calculating of determination of residual amount result：With retention time to ethiprole, fluorine formonitrile HCN, ethiprole sulfone, ethiprole sulfoxide four
Plant agricultural chemicals and carry out qualitative analysis, the quantitative analysis of four kinds of agricultural chemicals is carried out with peak area, external standard method result of calculation is used.
2. ethiprole and its metabolite residue amount method for measuring in a kind of egg according to claim 1, it is characterised in that：
The egg sample crude extract is acetonitrile, extracts volume 10mL.
3. ethiprole and its metabolite residue amount method for measuring in a kind of egg according to claim 1, it is characterised in that：
Step（2）The solid-phase extraction column be homemade neutral alumina column, be using neutral alumina aluminium powder as solid phase extraction filler, Gu
In phase extraction column, the addition of neutral alumina aluminium powder adds 1 gram of neutral alumina aluminium powder for every gram of sample；The neutral alumina
Aluminium powder is before use, in drying in Muffle furnace 400 DEG C.
4. ethiprole and its metabolite residue amount method for measuring in a kind of egg according to claim 1, it is characterised in that：
Step（3）It is described with the hybrid standard working solution of graded series concentration its concentration be respectively 1.0 ng/mL, 2.0 ng/mL,
5.0 ng/mL, 10.0 ng/mL, 20.0 ng/mL and 50.0 ng/mL.
5. ethiprole and its metabolite residue amount method for measuring in a kind of egg according to claim 1, it is characterised in that：
The step（1）Freezen protective temperature is -18 DEG C.
6. ethiprole and its metabolite residue amount method for measuring in a kind of egg according to claim 1, it is characterised in that：
Step（2）It is described add elution solid-phase extraction column eluting solvent be methanol+dichloromethane mixed solution, wherein, methanol with
Methylene chloride volume ratio is 1:99.
7. the application of ethiprole and its metabolite residue amount method for measuring in a kind of egg, it is characterised in that：Detect in egg
Ethiprole and its metabolin residual quantity.
8. the application of ethiprole and its metabolite residue quantity measuring method in a kind of egg, it is characterised in that：Egg is detected simultaneously
Middle ethiprole, fluorine formonitrile HCN, the residual quantity of four kinds of agricultural chemicals of ethiprole sulfone and ethiprole sulfoxide.
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|---|---|---|---|---|
| CN107505421A (en) * | 2017-09-25 | 2017-12-22 | 重庆市农业科学院 | The rapid extraction and purification method of ethiprole and its metabolite residue in a kind of birds, beasts and eggs |
| CN107917974A (en) * | 2017-11-10 | 2018-04-17 | 韩超 | The detection method of ethiprole and its metabolite residue amount in egg |
| CN108287152A (en) * | 2018-04-03 | 2018-07-17 | 江南大学 | A method of quickly detecting ethiprole using illumination and surface-enhanced Raman |
| CN108362812A (en) * | 2018-02-11 | 2018-08-03 | 梁雪琪 | Ethiprole and its metabolism object detecting method in a kind of animal-derived food |
| CN108445128A (en) * | 2018-03-01 | 2018-08-24 | 中国热带农业科学院农产品加工研究所 | A kind of method of carbamates determination of drug residues in birds, beasts and eggs |
| CN108535379A (en) * | 2018-04-12 | 2018-09-14 | 韩超 | The detection method of test quantity of fluoride in tea worm nitrile and its metabolite fluorine formonitrile HCN, ethiprole thioether, ethiprole sulfone |
| CN109239248A (en) * | 2018-09-14 | 2019-01-18 | 河源出入境检验检疫局综合技术服务中心 | The LC-Q-TOF detection method of Fipronil in egg and egg products |
| CN110261515A (en) * | 2019-07-31 | 2019-09-20 | 江西省农业科学院农产品质量安全与标准研究所 | A method of Fipronil residual quantity in detection livestock and poultry hair |
| CN113009057A (en) * | 2020-10-22 | 2021-06-22 | 重庆医科大学 | Method for detecting neonicotinoid insecticides and metabolites in urine by solid phase extraction-ultra-high performance liquid chromatography-tandem mass spectrometry |
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| CN108445128B (en) * | 2018-03-01 | 2020-05-26 | 中国热带农业科学院农产品加工研究所 | Method for measuring residual amount of carbamate drugs in eggs |
| CN108445128A (en) * | 2018-03-01 | 2018-08-24 | 中国热带农业科学院农产品加工研究所 | A kind of method of carbamates determination of drug residues in birds, beasts and eggs |
| CN108287152B (en) * | 2018-04-03 | 2020-11-24 | 江南大学 | Method for rapidly detecting fipronil by utilizing illumination and surface enhanced Raman spectroscopy |
| CN108287152A (en) * | 2018-04-03 | 2018-07-17 | 江南大学 | A method of quickly detecting ethiprole using illumination and surface-enhanced Raman |
| CN108535379A (en) * | 2018-04-12 | 2018-09-14 | 韩超 | The detection method of test quantity of fluoride in tea worm nitrile and its metabolite fluorine formonitrile HCN, ethiprole thioether, ethiprole sulfone |
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| CN110261515A (en) * | 2019-07-31 | 2019-09-20 | 江西省农业科学院农产品质量安全与标准研究所 | A method of Fipronil residual quantity in detection livestock and poultry hair |
| CN113009057A (en) * | 2020-10-22 | 2021-06-22 | 重庆医科大学 | Method for detecting neonicotinoid insecticides and metabolites in urine by solid phase extraction-ultra-high performance liquid chromatography-tandem mass spectrometry |
| CN113009057B (en) * | 2020-10-22 | 2023-11-07 | 重庆医科大学 | Method for detecting neonicotinoid insecticides and metabolites in urine by solid phase extraction-ultra-high performance liquid chromatography-tandem mass spectrometry |
| CN114414321A (en) * | 2021-12-02 | 2022-04-29 | 浙江省农业科学院 | Fipronil sulfone residue analysis standard substance candidate in egg powder and preparation method thereof |
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