CN104730191B - A kind of LC-MS/MS assay method of fluorine ether bacterium amide residual quantity - Google Patents
A kind of LC-MS/MS assay method of fluorine ether bacterium amide residual quantity Download PDFInfo
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Abstract
The invention discloses the LC MS/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, Liquid Chromatography-Tandem Mass Spectrometry (LC MS/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 83.1%～89.5%, and average relative standard's deviation (RSD) is 4.0%～6.3%, detection limit be less than 0.12 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 0.01 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 LC-MS/MS assay method of a kind of fluorine ether bacterium amide residual quantity, more specifically use liquid phase color
Spectrum tandem mass spectrum (LC-MS/MS) qualitative, quantitative measures animal muscle and the goods such as Cereals, Carnis Sus domestica, beef, Carnis caprae seu ovis, Carnis Gallus domesticus
Deng the method for the fluorine ether bacterium amide content of residual in the animals and plants derived food of complex matrices, belong to the determination techniques of persticide residue
Field.
Background technology
Bisamide insecticides is the pesticide product that the whole world is popular in recent years, can be widely applied to Oryza sativa L., vegetable, Cotton Gossypii etc.
The injurious insect control of crop, has the advantages such as low toxicity, Environmental security, high activity, including Rynaxypyr, cyanogen insect amide, fluorine
The kinds such as worm bisamide, fluorine ether bacterium amide (LH-2010A) is by the research and development of China National Chemicals Import(Sinochem) subordinate Shenyang Chemical Engineering Inst, middleization agriculture
Change the new product that company limited manages, the first bisamide insecticides with independent intellectual property right of China, obtain National agricultural
The interim registration in portion.
Fluorine ether bacterium amide (LH-2010A) belongs to ryanodine receptor activator insecticides, its by with ryania in pest body
Receptor combines, and opens calcium channel, makes to be stored in intracellular calcium ion and be sustained release in sarcoplasm, in calcium ion and sarcoplasm
Stromatin combines, and causes muscle contracts last.Insect bodies Symptoms is tic, refusing to eat, finally dead.Fluorine ether bacterium amide
For low toxicity, broad spectrum pesticide, lepidoptera pest is respectively provided with good activity.Controlling object include rice leaf roller, striped rice borer,
Diamondback moth, beet armyworm, Pyrausta nubilalis (Hubern)., sugarcane borer, steinernema, heart-eating worm etc..
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, use
LC-MS/MS measures food Residual Pesticides in Farm Produce and has quick, easy, sensitivity advantages of higher, due to Cereals, animal
The food agricultural product substrate such as derived food are more complicated, must set up the good sample-pretreating method of clean-up effect and could meet detection
Requirement, hence sets up fluorine ether bacterium amide in simplicity, quick, accurate, durable, energy accurately qualitative and quantitative analysis vegetable and fruit
The LC-MS/MS detection method of residual quantity is significant.
Summary of the invention
It is an object of the invention to provide the LC-MS/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 LC-MS/MS of a kind of fluorine ether bacterium amide residual quantity
Assay method, comprises the steps:
(1) extract
Weigh pulverizing 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, uses acetonitrile constant volume, takes after constant volume liquid crosses film, treats that Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/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 scavenging solution,
The fluorine ether bacterium amide series hybrid standard working solution of at least 3 concentration it is configured to blank extraction and cleaning liquid；
(4) liquid chromatography tandem mass spectrometry (LC-MS/MS) measures
The standard working solution of each Concentraton gradient in step (3) is carried out LC-MS/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 LC-MS/MS and is measured, and records the chromatographic peak area of fluorine ether bacterium amide in sample liquid, substitutes into standard curve, obtains
Fluorine ether bacterium amide content in sample liquid, then obtains fluorine ether bacterium amide in sample according to the Mass Calculation of sample representated by sample liquid residual
Allowance.
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), the flowing of liquid chromatograph is mutually: aqueous solution and the acetonitrile containing 5mmol/L ammonium acetate, flow velocity 0.2-0.4
ML/min, sample size 5 μ L.
The method that in step (4), liquid chromatograph uses gradient elution, gradient elution program is:
In step (4), the chromatographic column filler of liquid chromatograph is C18, column temperature is 30 DEG C.
In step (4), Mass Spectrometer Method uses Electrospray Mass Spectrometry (ESI) detection, and electron spray voltage is-3500 to-4500V,
Atomization gas pressure is 275.9kPa, is dried gas and sheath gas is nitrogen, and dry temperature is 300 DEG C, and dry gas stream speed is 5.0
L/min, sheath temperature is 250 DEG C, and sheath gas velocity is 11.0L/min, spray nozzle voltage 500V.
In step (4), Mass Spectrometer Method uses multiple-reaction monitoring (MRM) anion scan pattern；The mother of fluorine ether bacterium amide from
Son is 414.4～415.4, and daughter ion is respectively 163.3～164.3 and 178.4～179.4.
Step (4) detects parent ion and the daughter ion pair of described filtrate Pesticides, if its chromatography of ions peak retention time with
Standard working solution is consistent；And the sky that in filtrate (sample), the relative abundance of two daughter ions of target compound is suitable with concentration
When the ion relative abundance deviation of white extraction standard solution is less than 30%, then judge this sample exists this kind of pesticide；If it is above-mentioned
Two conditions 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 LC-MS/MS, and to be applied in Cereals, animal derived food fluorine ether bacterium amide fixed
Property confirmation and detection by quantitative, average recovery rate is 83.1%～89.5%, and average relative standard's deviation (RSD) is 4.0%～6.3%,
Detection limit is less than 0.12 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 the LC-MS/MS multiple-reaction monitoring being added on the 5.0ng/mL fluorine ether bacterium amide mark liquid in blank rice substrate
Chromatogram.
Fig. 2 is the LC-MS/MS multiple-reaction monitoring chromatogram of the rice blank sample of not fluorine-containing ether bacterium amide.
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)；1290 is the highest
Effect liquid phase chromatogram-6460 triple quadrupole mass spectrometer (Agilent, USA)；C18/ PSA solid-phase extraction column (6mL, 500mg/500
Mg) it is purchased from Tianjin Bonaaijieer Technology Co., Ltd.
Reagent: acetonitrile (HPLC level, Merke, Germany)；Acetic acid (HPLC level, CNW, Germany)；Nothing
Water 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, is settled to 10mL with acetonitrile, will purify constant volume
After liquid crosses 0.22 μm filter membrane, treat that LC-MS/MS measures.
(2) preparation of standard working solution
Accurately weighing appropriate 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 is placed in 100mL volumetric flask, obtains 10.0 μ g/mL standard intermediate liquids with acetonitrile constant volume；Weigh 10g
Carnis Sus domestica blank sample, prepares vehicle solution by above-mentioned pre-treatment step, is diluted by standard intermediate liquid vehicle solution
Be configured to 0.5,1,2,5,10,20,50ng/mL series standard working solution, standard working solution is entered LC-MS/MS and analyzes,
With gained peak area, its respective concentration is carried out regression analysis, obtain standard working curve.
(3) liquid chromatography tandem mass spectrometry (LC-MS/MS) measures
The standard working solution of variable concentrations gradient is injected separately into LC-MS/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 LC-MS/MS it be measured, record the chromatographic peak area of fluorine ether bacterium amide in sample liquid, substitute into mark
Directrix curve, obtains fluorine ether bacterium amide content in sample liquid, then obtains in sample according to the Mass Calculation of sample representated by sample liquid
Fluorine ether bacterium amide residual quantity.
Wherein chromatographic condition is:
Chromatographic column: Agilent, Eclipse plus C18, 2.1mm × 100mm, particle diameter 3.5 μm；
Flowing phase: aqueous solution and the acetonitrile containing 5mmol/L ammonium acetate；
Flow velocity: 0.3mL/min；
Sample size: 5 μ L；
Column temperature: 30 DEG C；
Gradient elution program such as table 1.
Table 1: the gradient elution program of embodiment 1
| Time (min) | The aqueous solution (%) of 5mmol/L ammonium acetate | Acetonitrile (%) |
| 0 | 95 | 5 |
| 0.5 | 95 | 5 |
| 2.0 | 5 | 95 |
| 5.0 | 5 | 95 |
| 5.2 | 95 | 5 |
| 8.0 | 95 | 5 |
Wherein, mass spectrometry parameters is:
Scan mode: many reactive ions monitoring (MRM) anion scanning；
Electron spray voltage :-4000V；Spray nozzle voltage 500V；
Atomization gas pressure: 275.9kPa；
It is dried gas: nitrogen, 300 DEG C, flow velocity is 5.0L/min；
Sheath gas: nitrogen, 250 DEG C, flow velocity is 11.0L/min；
MRM detection parameter is shown in Table 2.
The MRM of table 2 embodiment 1 detects parameter
*For quota ion pair.
Qualitative Identification: for parent ion and the daughter ion pair of pesticide, at identical conditions, if the chromatography of ions in sample
Peak consistent with bare substrate standard working solution (excursion is within ± 2.5%)；Two daughter ions of target compound in sample
The relative abundance deviation of relative abundance and the fairly standard solution of concentration less than 30% time, then judge this sample exists this kind of agriculture
Medicine；If above-mentioned two condition can not meet simultaneously, 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 3.
The standard curve of fluorine ether bacterium amide in table 3 Carnis Sus domestica bare substrate
| Title | Retention time (min) | Regression equation | Correlation coefficient |
| Fluorine ether bacterium amide LH-2010A | 3.05 | Y=1299.9X-204.22 | 0.9998 |
Recovery of standard addition and repeatability:
In the Carnis Sus domestica of not fluorine-containing ether bacterium amide, add the fluorine ether bacterium amide standard solution of 10,20 and 200 g/kg3 concentration levels of μ, treat
Pesticide carries out the determination of residual amount by above-mentioned process step after adding 30min.Mensuration concentration and pesticide theory are added concentration compare
Relatively, obtaining pesticide TIANZHU XINGNAO Capsul, each pitch-based sphere parallel assay 6 times, obtain its relative standard deviation, measurement result is shown in Table
4.As can be seen from Table 4, in 3 mark-on levels, the average recovery rate of fluorine ether bacterium amide is 85.3%～89.5%, averagely
Relative standard deviation (RSD) is 4.1%～6.3%, illustrates that the response rate of the inventive method is higher, reproducible.
The response rate of table 4 fluorine ether bacterium amide and repeatability (n=6)
Detection limit:
The fluorine ether bacterium amide substrate standard working solution of variable concentrations is injected LC-MS/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 Carnis Sus domestica is 0.2 times) of sample handling processes calculate detection limit, fluorine ether
The detection of bacterium amide is limited to 0.12 μ g/kg.
Embodiment 2: the detection of fluorine ether bacterium amide residual quantity in rice
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, is settled to 10mL with acetonitrile, crosses 0.22 μm
After filter membrane, treat that LC-MS/MS measures.
The preparation of standard working solution, Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) measure and the operation step of Qualitative Identification
Suddenly, chromatograph is consistent with the mensuration of fluorine ether bacterium amide in above-mentioned Carnis Sus domestica sample with Mass Spectrometry Conditions.
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=1645.7X-469.68, correlation coefficient is 0.9998.
Recovery of standard addition and repeatability:
The fluorine ether bacterium amide standard solution of 10,20 and 200 3 concentration levels of μ g/kg is added in the rice of not fluorine-containing ether bacterium amide,
After pesticide adds 30min, carry out the determination of residual amount by above-mentioned process step, mensuration concentration and pesticide theory are added concentration and carries out
Relatively, obtaining pesticide TIANZHU XINGNAO Capsul, each pitch-based sphere parallel assay 6 times, obtain its relative standard deviation, measurement result is shown in
Table 5.As can be seen from Table 5, in 3 mark-on levels, the average recovery rate of fluorine ether bacterium amide is 83.1%～86.7%, flat
All relative standard deviations (RSD) are 4.0%～5.5%, illustrate that the response rate of the inventive method is high, reproducible.
The response rate of table 5 fluorine ether bacterium amide and repeatability (n=6)
Detection limit:
The fluorine ether bacterium amide substrate standard working solution of variable concentrations is injected LC-MS/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 0.2 times) of sample handling processes calculate detection limit, fluorine ether
The detection of bacterium amide is limited to 0.086 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 LC-MS/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, uses acetonitrile constant volume, takes after constant volume liquid crosses film, treats that Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/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
Change liquid, be configured to the fluorine ether bacterium amide series standard working solution of at least 5 concentration with blank extraction and cleaning liquid；
(4) measure and result calculates
In step (4), the liquid-phase chromatographic analysis condition of LC-MS/MS is: filler is C18Chromatographic column, column temperature is 30 DEG C；Sample introduction
Volume is 5 μ L；Flowing is mutually: aqueous solution and the acetonitrile containing 5mmol/L ammonium acetate, gradient elution；Gradient elution program is:
Mass Spectrometry Conditions is: Electrospray Mass Spectrometry detects；Electron spray voltage is-3500 to-4500V；Atomization gas pressure is 275.9kPa；
It is dried gas and sheath gas is nitrogen；Dry temperature is 300 DEG C；Dry gas stream speed is 5.0L/min；Sheath temperature is 250 DEG C,
Sheath gas velocity is 11.0L/min, spray nozzle voltage 500V, multiple-reaction monitoring (MRM) anion scan pattern；Fluorine ether bacterium amide
Parent ion be 414.4～415.4, daughter ion is respectively 163.3～164.3 and 178.4～179.4；
The standard working solution of each Concentraton gradient in step (3) is carried out LC-MS/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 LC-MS/MS and be measured, record the chromatographic peak area of fluorine ether bacterium amide in sample liquid, substitute into substrate mark
Quasi-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
Fluorine ether bacterium amide residual quantity in product.
The LC-MS/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 LC-MS/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 LC-MS/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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| CN112444591B (en) * | 2019-08-30 | 2024-01-30 | 谱尼测试集团上海有限公司 | Liquid chromatography tandem mass spectrometry for determining residual quantity of flumetsulam in vegetable food |
| CN115032300A (en) * | 2022-06-08 | 2022-09-09 | 浙江省农业科学院 | Method for simultaneously detecting fluopyram and 2- (trifluoromethyl) benzamide |
| CN115015425B (en) * | 2022-06-15 | 2024-02-23 | 山东省农业科学院 | Method for determining fluoroether bacteria amide residues in red sage root by combining solid phase extraction with UPLC-MS/MS |
| CN115047109B (en) * | 2022-06-17 | 2024-05-31 | 三明海关综合技术服务中心 | Method for detecting novel fentanyl mental active substances in food |
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