CN104569210A - Method for determining SYP-9080 residue in fruits and vegetables by employing gas chromatography-electron impact ion source-mass spectrum (GC-EI-MS) - Google Patents
Method for determining SYP-9080 residue in fruits and vegetables by employing gas chromatography-electron impact ion source-mass spectrum (GC-EI-MS) Download PDFInfo
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Abstract
The invention discloses a method for determining a SYP-9080 residue in fruits and vegetables by employing gas chromatography-electron impact ion source-mass spectrum (GC-EI-MS). The method comprises the following steps: extracting residual SYP-9080 from a sample with acetonitrile or an acetonitrile solution containing 1% acetic acid in a manner of homogenization; dispersing and purifying extract liquid with ethidene diamine-N-propyl silane (PSA) and octadecyl silane bonded-phase (C18) matrix, and then carrying out GC-EI-MS detection; and building a corrected standard curve with a blank matrix solution free of a to-be-detected pesticide, and quantifying by an external standard method. According to the method, the average recovery rate is 86.3%-93.2%; the relative average standard deviation (RSD) is 4.2%-7.6%; the detection limit is lower than 7.85 microg/kg; and the method has the advantages of simplicity, convenience and fastness in operation, high sensitivity, good repeatability and accurate qualify and quantify, and can meet the technical requirements of uniform standard of 0.01mg/kg of residue limit; and a powerful technical support is provided for guarantee of the food safety for people in China and health development of foreign export trade.
Description
Technical field
The present invention relates to a kind of GC-EI-MS and measure the method that in fruits and vegetables, four chlorantraniliproles are residual, be more particularly the method adopting gas chromatography-electron impact ion source-mass spectrum (GC-EI-MS) qualitative, quantitative to measure four chlorantraniliprole content residual in vegetables and fruit, belong to the determination techniques field of persticide residue.
Background technology
Bisamide insecticides is the pesticide product that the whole world is popular in recent years, the injurious insect control of the crops such as paddy rice, vegetables, cotton can be widely used in, there is the advantages such as low toxicity, Environmental security, high activity, comprise the kinds such as Rynaxypyr, cyanogen insect amide, fipronil bisamide, four chlorantraniliproles (SYP-9080) are the new products managed by the research and development of China National Chemicals Import(Sinochem) subordinate Shenyang Chemical Engineering Inst, Zhong Hua agrochemical company limited, the first bisamide insecticides with independent intellectual property right of China, has obtained the interim registration in National agricultural portion.
Four chlorantraniliproles (SYP-9080) belong to ryanodine receptor activator insecticides, it is combined by ryanodine receptor in pest body, open calcium channel, make to be stored in intracellular calcium ion sustained release in sarcoplasm, calcium ion and sarcoplasm mesostroma protein combination, cause muscle contracts last.Insect bodies Symptoms is tic, food refusal, finally dead.Four chlorantraniliproles are low toxicity, broad spectrum pesticide, all have good activity to lepidoptera pest.Controlling object comprises rice leaf roller, striped rice borer, diamondback moth, beet armyworm, corn borer, sugarcane borer, steinernema, heart-eating worm etc.
Along with the registration of four chlorantraniliproles, popularization and use, about four chlorantraniliprole Residue Degradations dynamically and the research of the environmental behaviour such as final residue certainly will increase, simultaneously, if use agricultural chemicals not register in this country as European Union in China's main exit market, Japan and other countries regulation field, when not formulating corresponding residue limits standard, the food agricultural product being exported to its country comprise " uniform limit " that residue limits in the animal derived foods such as livestock meat all carries out 0.01mg/L.
Up to now, have no the report had about four chlorantraniliprole residues detection methods in food agricultural product both at home and abroad, the gaschromatographic mass spectrometry (GC-EI-MS) in outfit electron impact ionization source is analyzed food Residual Pesticides in Farm Produce tool and is had great advantage, because electron impact ionization source mass spectrum is versatility detecting device, the multi-residue analysis of hundreds of kind agricultural chemicals can be realized, can simultaneously quantitative and qualitative analysis, moderate, therefore existing various testing agency and enterprise are all equipped with gas chromatography-electron impact ion source-mass spectrometer (GC-EI-MS) and detect the residues of pesticides in food agricultural product, therefore, the detection method setting up four chlorantraniliprole residual quantities in gas chromatography-electron impact ion source-mass spectrum (GC-EI-MS) qualitative and quantitative analysis vegetables and fruit is significant.
Summary of the invention
The object of this invention is to provide a kind of GC-EI-MS and measure the method that in fruits and vegetables, four chlorantraniliproles are residual.
For realizing above object, the technical solution adopted in the present invention is: a kind of GC-EI-MS measures the method that in fruits and vegetables, four chlorantraniliproles are residual, comprises the steps:
(1) extract
Take sample in tool plug centrifuge tube, add acetonitrile or extract 1min containing the acetonitrile solution homogeneous of 1% acetic acid, add the one in sodium chloride or sodium acetate 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 after a certain amount of scavenging solution nitrogen dries up, dissolve constant volume with acetone/normal hexane mixed solvent that volume ratio is 1/1, after crossing film, treat that gas chromatography-electron impact ion source-mass spectrum (GC-EI-MS) detects.
(3) preparation of standard working solution
When same kind matrix blank sample not containing four chlorantraniliproles is processed by above-mentioned steps (1), (2), obtain sample extraction purification residue, add appropriate solvent and mixed standard solution, vortex mixes, and is mixed with four chlorantraniliprole series hybrid standard working fluids of at least 3 concentration.
(4) gas chromatography-electron impact ion source-mass spectroscopy (GC-EI-MS) measures
The standard working solution of each concentration gradient in step (3) is carried out GC-EI-MS mensuration, with the chromatographic peak area of standard working solution, regretional analysis is carried out to its respective concentration, obtain standard working curve; Under the same conditions the sample liquid after purification in step (2) is injected GC-EI-MS to measure, record the chromatographic peak area of four chlorantraniliproles in sample liquid, substitute into typical curve, obtain four chlorantraniliprole content in sample liquid, then the Mass Calculation of sample representated by liquid obtains four chlorantraniliprole residual quantities in sample per sample.
Step (1) if in sample dehydrated vegetables and fruit, need sample weighting amount be reduced, and add suitable quantity of water and fully infiltrate.
Add sodium chloride when adopting acetonitrile to extract in step (1) to saltout, add sodium acetate when adopting the acetonitrile solution containing 1% acetic acid to extract and saltout; A certain amount of water need be added when the sample of moisture content less is saltoutd.
The agent of step (2) mesostroma dispersive solid-phase extraction is by anhydrous magnesium sulfate, C
18with PSA composition, anhydrous magnesium sulfate, C in every volume extract
18150mg, 50mg and 25mg is respectively with PSA addition.
In step (4), GC conditions is: chromatographic column: HP-5MS capillary chromatographic column, column length 30m, internal diameter 0.25mm, thickness 0.25 μm; Injector temperature 250 DEG C; Carrier gas: He, not shunt mode sample introduction, sample size: 1 μ L; Constant current mode, flow velocity 1.0mL/min; Heating schedule: initial temperature 60 DEG C keeps 2min, rises to 200 DEG C, then rises 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 with the speed of 20 DEG C per minute, keeps 10min; Transmission line temperature: 280 DEG C.
In step (4), Mass Spectrometry Conditions is: ion source temperature 230 DEG C; Quadrupole rod temperature 150 DEG C; Ionization pattern: electron impact ionization, i.e. EI pattern, energy 70eV; Scan mode: Salbutamol Selected Ion Monitoring (SIM) pattern, the ion of monitoring is: 297,332,334,336.
When measuring sample liquid and extraction standard working solution in step (4), if sample liquid Pesticides chromatographic peak retention time agricultural chemicals retention time corresponding to standard solution is consistent, and in the sample mass spectrogram after background correction, selected ion all occurs, and abundance of ions than with the abundance of ions of standard solution than consistent, then can judge to exist in sample liquid this agricultural chemicals; If above-mentioned two conditions can not meet simultaneously, then judge not containing this kind of agricultural chemicals.
Beneficial effect of the present invention is:
The present invention utilizes dispersive solid-phase extraction technology, establish sample-pretreating method that is easy, that also can effectively avoid sample mesostroma to disturb fast, this pre-treating method is applied to the qualitative confirmation of four chlorantraniliproles and quantitatively detection in vegetables and fruit in conjunction with GC-EI-MS, average recovery rate is 86.3% ~ 93.2%, average relative standard's deviation (RSD) is 4.2% ~ 7.6%, detection limit, lower than 7.85 μ g/kg, has easy and simple to handle, quick, accurate, highly sensitive and reproducible advantage." uniform limit " technical requirement of 0.01mg/kg residue limits can be met, for guarantee our people food security, export abroad trade sound development provide strong technical support.
Accompanying drawing explanation
Fig. 1 is the Selective ion mode chromatogram of the 100ng/mL tetra-chlorantraniliprole mark liquid be added in blank apple matrix.
Fig. 2 is not containing the Selective ion mode chromatogram of the apple blank sample of four chlorantraniliproles.
The four chlorantraniliprole standard working curves that Fig. 3 is is substrate preparation with the apple blank sample not containing four chlorantraniliproles.
Embodiment
Now with following embodiment, the present invention is described, but is not limit the scope of the invention.
The instrument used in embodiment and reagent
T18Basic homogenizer (IKA, Germany); 5810R hydro-extractor (Eppendorf, Germany); MS3 basic model vortex mixer (IKA, Germany); 7890N gas chromatography-5977C mass spectrometer (Agilent, USA); Primary secondary amine (PSA) adsorbent (40 ~ 60 μm), octadecylsilane Bonded Phase (C
18) cleanser (40 ~ 60 μm) is all 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 pure for analyzing, all purchased from Chemical Reagent Co., Ltd., Sinopharm Group.
Standard substance: purity 95.5%, purchased from Zhong Hua agrochemical company limited.
Embodiment 1: the detection of four chlorantraniliprole residual quantities in apple
(1) sample pre-treatments
Taking apple 10.0g through fully mixing in 50mL centrifuge tube, accurately adding 20mL acetonitrile, homogeneous extracts 1min, adds 3g anhydrous magnesium sulfate and 2g sodium chloride, after vortex 1min, and the centrifugal 5min of 7000r/min.After centrifugal, get 6mL acetonitrile extract and be transferred to 900mg anhydrous magnesium sulfate, 300mg C are housed
18with in the centrifuge tube of 150mg PSA, the centrifugal 5min of vortex 1min, 5000r/min.Get 4mL supernatant in nitrogen blowpipe, dry up in 40 DEG C of nitrogen, add acetone/normal hexane mixed solvent dissolved residue that 1mL volume ratio is 1/1, after vortex mixed film, move in sample injection bottle and treat that GC-EI-MS measures.
(2) preparation of standard working solution
Accurately take 25 ± 0.1mg standard items in 25mL volumetric flask, dissolve with acetonitrile, constant volume obtains 1000.0 μ g/mL standard reserving solutions; Pipette 1.0mL standard reserving solution and be placed in 100mL volumetric flask, obtain 10.0 μ g/mL standard intermediate liquids with the acetone/normal hexane mixed solvent constant volume by volume ratio being 1/1; 10 μ g/mL standard solution dilutions are made into 5,2,1,0.5,0.2,0.1 μ g/mL standard solution.Apple blank sample not containing spiral shell worm ethyl ester is pressed above-mentioned pre-treatment step process, obtain sample extraction purification residue, acetone/normal hexane mixed solvent and the above-mentioned mixed standard solution of 100 μ L that 900 μ L volume ratios are 1/1 is added in this residue, vortex mixes, and is made into 10,20,50,100,200,500 μ g/L extraction standard working solutions.
(3) gas chromatography-electron impact ion source-mass spectroscopy (GC-EI-MS) measures
The standard working solution of variable concentrations gradient is injected GC-EI-MS respectively, carries out the quantitative test of four chlorantraniliprole content with external standard method, namely with the chromatographic peak area of standard working solution, regretional analysis is carried out to its respective concentration, obtain typical curve; Under the same conditions sample extracting solution is injected GC-EI-MS to measure, record the chromatographic peak area of four chlorantraniliproles in sample liquid, substitute into typical curve, obtain four chlorantraniliprole content in sample liquid, then the Mass Calculation of sample representated by liquid obtains four chlorantraniliprole residual quantities in sample per sample.
Wherein chromatographic condition is:
Chromatographic column: HP-5MS capillary chromatographic column, column length 30m, internal diameter 0.25mm, thickness 0.25 μm.
Injector temperature: 250.0 DEG C, sample introduction pattern: Splitless injecting samples, sample size: 1 μ L.
Carrier gas: He, constant current mode, flow velocity 1.0mL/min.
Stove case heating schedule: initial temperature 60 DEG C keeps 2min, rises to 200 DEG C, then rises 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 with the speed of 20 DEG C per minute, keeps 10min;
Transmission line temperature: 280 DEG C.
Wherein, mass spectrometry parameters is:
Ionization pattern: electron impact ionization, i.e. EI pattern, energy 70eV.
Ion source temperature: 230 DEG C.
Quadrupole rod temperature 150 DEG C.
Scan mode: Salbutamol Selected Ion Monitoring (SIM) pattern.
The ion of SIM monitoring is: 297,332,334,336, and quota ion is 334.
Qualitative Identification: at identical conditions, if sample liquid Pesticides chromatographic peak retention time agricultural chemicals retention time corresponding to standard solution is consistent, and in the sample mass spectrogram after background correction, selected ion all occurs, and abundance of ions than with the abundance of ions of standard solution than consistent, then can judge to exist in sample liquid this agricultural chemicals; If above-mentioned two conditions can not meet simultaneously, then judge not containing this kind of agricultural chemicals.
With the chromatographic peak area of standard working solution, regretional analysis is carried out to its respective concentration, obtain standard working curve as table 1.
The typical curve of four chlorantraniliproles in table 1 apple bare substrate
| Title | Retention time (min) | Regression equation | Related coefficient |
| Four chlorantraniliprole SYP-9080 | 25.64 | Y＝116.29X+899.11 | 0.9993 |
Recovery of standard addition and repeatability:
In the apple not containing four chlorantraniliproles, add four chlorantraniliprole standard solution of 10, a 20 and 200 μ g/kg3 concentration level, add after 30min until agricultural chemicals and carry out the determination of residual amount by above-mentioned treatment step.Mensuration concentration and agricultural chemicals theory are added concentration compare, obtain agricultural chemicals TIANZHU XINGNAO Capsul, each Pitch-based sphere replicate determination 6 times, obtain its relative standard deviation, measurement result is in table 2.As can be seen from Table 2, in 3 mark-on levels, the average recovery rate of four chlorantraniliproles is 88.4% ~ 92.1%, and average relative standard's deviation (RSD) is 4.2% ~ 7.2%, illustrates that the recovery of the inventive method is higher, reproducible.
The recovery of table 2 four chlorantraniliprole and repeatability (n=6)
Detection limit:
Four chlorantraniliprole extraction standard working solutions of variable concentrations are injected GC-EI-MS, calculate detection limit with the cycles of concentration (cycles of concentration of apple is 2.0 times) of 3 times of signal to noise ratio (S/N ratio)s of least concentration extraction standard solution chromatographic peak and sample handling processes, detecting of four chlorantraniliproles is limited to 2.35 μ g/kg.
Embodiment 2: the detection of four chlorantraniliprole residual quantities in dehydration green pepper
(1) sample pre-treatments
Taking dehydration green pepper 2.0g through fully mixing in 50mL centrifuge tube, after adding 5mL water recovery 30min, accurately adding the acetonitrile solution of 20mL containing 1% acetic acid, homogeneous extracts 1min, add 3g anhydrous magnesium sulfate, 2g sodium acetate and 2mL water, after vortex 1min, the centrifugal 5min of 7000r/min.After centrifugal, get 6mL acetonitrile extract and be transferred to 900mg anhydrous magnesium sulfate, 300mg C are housed
18with in the centrifuge tube of 150mg PSA, the centrifugal 5min of vortex 1min, 5000r/min.Get 4mL supernatant in nitrogen blowpipe, 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 in sample injection bottle and treat that GC-EI-MS measures.
(2) preparation of standard working solution
By 100ng/mL standard solution volume ratio be 1/1 acetone/normal hexane mixed solvent be diluted to 10ng/mL standard intermediate liquid, by 10 μ g/mL standard solution dilution be made into 5,2,1,0.5,0.2,0.1 μ g/mL standard solution.Dehydration green pepper blank sample not containing four chlorantraniliproles is pressed above-mentioned pre-treatment step process, obtain sample extraction purification residue, acetone/normal hexane mixed solvent and the above-mentioned mixed standard solution of 100 μ L that 900 μ L volume ratios are 1/1 is added in this residue, vortex mixes, and is made into 10,20,50,100,200,500 μ g/L extraction standard working solutions.
(3) gas chromatography-electron impact ion source-mass spectroscopy (GC-EI-MS) measures
Operation steps, chromatogram are consistent with the mensuration of four chlorantraniliproles in above-mentioned apple sample with Mass Spectrometry Conditions.
Qualitative Identification:
Consistent with the mensuration of four chlorantraniliproles in above-mentioned apple sample.
Linear relationship:
Carry out regretional analysis with the chromatographic peak area of standard working solution to its respective concentration, obtaining standard working curve is
Y=175.97X-1494.2, related coefficient is 0.9993.
Recovery of standard addition and repeatability:
Four chlorantraniliprole standard solution of 50,100 and 200 μ g/kg, 3 concentration levels are added in the dehydration green pepper not containing four chlorantraniliproles, add after 30min until agricultural chemicals and carry out the determination of residual amount by above-mentioned treatment step, mensuration concentration and agricultural chemicals theory are added concentration compare, obtain agricultural chemicals TIANZHU XINGNAO Capsul, each Pitch-based sphere replicate determination 6 times, obtain its relative standard deviation, measurement result is in table 3.As can be seen from Table 3, in 3 mark-on levels, the average recovery rate of four chlorantraniliproles is 86.3% ~ 93.2%, and average relative standard's deviation (RSD) is 4.2% ~ 7.6%, illustrates that the recovery of the inventive method is high, reproducible.
The recovery of table 3 four chlorantraniliprole and repeatability (n=6)
Detection limit:
Four chlorantraniliprole extraction standard working solutions of variable concentrations are injected GC-EI-MS, calculate detection limit with the cycles of concentration (cycles of concentration of dehydration green pepper is 0.4 times) of 3 times of signal to noise ratio (S/N ratio)s of least concentration extraction standard solution chromatographic peak and sample handling processes, detecting of four chlorantraniliproles is limited to 7.85 μ g/kg.
Above embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various modification that the common engineering in this area is made technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.
Claims (5)
1. GC-EI-MS measures the method that in fruits and vegetables, four chlorantraniliproles are residual, it is characterized in that, said method comprising the steps of:
(1) extract
Take vegetables and fruit sample in tool plug centrifuge tube, add acetonitrile or extract 1min containing the acetonitrile solution homogeneous of 1% acetic acid, centrifugal after adding 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, get after a certain amount of scavenging solution nitrogen dries up, dissolve constant volume with acetone/normal hexane mixed solvent that volume ratio is 1/1, after crossing film, treat that gas chromatography-electron impact ion source-mass spectrum (GC-EI-MS) detects;
(3) preparation of standard working solution
Same kind matrix blank sample not containing four chlorantraniliproles is processed by above-mentioned steps (1), (2), obtain sample extraction purification residue, add appropriate solvent and mixed standard solution, vortex mixes, and is mixed with four chlorantraniliprole series hybrid standard working fluids of at least 3 concentration;
(4) mensuration and result calculate
The standard working solution of each concentration gradient in step (3) is carried out GC-EI-MS mensuration, with the chromatographic peak area of standard working solution, regretional analysis is carried out to its respective concentration, obtain extraction standard working curve; Under the same conditions the sample liquid after purification in step (2) is injected GC-EI-MS to measure, record the chromatographic peak area of four chlorantraniliproles in sample liquid, substitute into extraction standard curve, obtain four chlorantraniliprole content in sample liquid, then the Mass Calculation of sample representated by liquid obtains four chlorantraniliprole residual quantities in sample per sample.
2. a kind of GC-EI-MS according to claim 1 measures the method that in fruits and vegetables, four chlorantraniliproles are residual, it is characterized in that, step (1) if in vegetables and fruit sample dehydrated sample, need sample weighting amount be reduced, and add suitable quantity of water and fully infiltrate.
3. a kind of GC-EI-MS according to claim 1 measures the method that in fruits and vegetables, four chlorantraniliproles are residual, it is characterized in that, sodium chloride need be added when adopting acetonitrile to extract in step (1) to saltout, sodium acetate need be added when adopting the acetonitrile solution containing 1% acetic acid to extract and saltout.
4. a kind of GC-EI-MS according to claim 1 measures the method that in fruits and vegetables, four chlorantraniliproles are residual, and it is characterized in that, the agent of step (2) mesostroma dispersive solid-phase extraction is by anhydrous magnesium sulfate, C
18with PSA composition, anhydrous magnesium sulfate, C in every volume extract
18150mg, 50mg and 25mg is respectively with PSA addition.
5. a kind of GC-EI-MS according to claim 1 measures the method that in fruits and vegetables, four chlorantraniliproles are residual, it is characterized in that, in step (4), GC-EI-MS analysis condition is: chromatographic column: HP-5MS capillary chromatographic column, column length 30m, internal diameter 0.25mm, thickness 0.25 μm; Injector temperature 250.0 DEG C; Carrier gas: He, not shunt mode sample introduction, sample size: 1 μ L; Constant current mode, flow velocity 1.0mL/min; Heating schedule: initial temperature 60 DEG C keeps 2min, rises to 200 DEG C, then rises 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 with the speed of 20 DEG C per minute, keeps 10min; Transmission line temperature: 280 DEG C; Ionization pattern: electron impact ionization, i.e. EI pattern, energy 70eV; Ion source temperature 230 DEG C; Scan mode: Salbutamol Selected Ion Monitoring (SIM) pattern, the ion of monitoring is: 297,332,334,336.
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108802215A (en) * | 2018-05-08 | 2018-11-13 | 辽宁通正检测有限公司 | The assay method of Rynaxypyr residual quantity in a kind of vegetables |
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