CN104502510A - GC-NCI-MS (Gas Chromatography-Negative Chemical Ionization-Mass Spectrum) detecting method for residual quantity of cyenopyrafen in fruits and vegetables - Google Patents
GC-NCI-MS (Gas Chromatography-Negative Chemical Ionization-Mass Spectrum) detecting method for residual quantity of cyenopyrafen in fruits and vegetables Download PDFInfo
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Abstract
The invention discloses a GC-NCI-MS (Gas Chromatography-Negative Chemical Ionization-Mass Spectrum) detecting method for the residual quantity of cyenopyrafen in fruits and vegetables. The GC-NCI-MS detecting method comprises the steps of homogenizing by using acetonitrile or an acetonitrile liquid containing 1% acetic acid to extract residual cyenopyrafen in a sample; dispersing by using a primary secondary amine (PSA) and octadecylsilane bonded-phase (C18) matrix to purify an extracting liquid; then, carrying out GC-NCI-MS detection; establishing a corrected standard curve by using a blank matrix liquid without a pesticide to be detected; and quantifying by using an external standard method. By using the GC-NCI-MS detecting method, the average recovery rate is 86.3-94.3%, the average relative standard deviation (RSD) is 4.6-8.6%, and the detection limit is lower than 1.12mu g/kg; and the GC-NCI-MS detecting method is simple and convenient to operate, rapid, high in sensitivity, good in repeatability and accurate in qualitation and quantitation. According to the GC-NCI-MS detecting method, the technical requirements of Korea, Japan, European union and other countries on security detection of corresponding products can be met, and the powerful technical support can be provided for ensuring Chinese food safety and the health development of foreign export trade.
Description
Technical field
The present invention relates to a kind of GC-NCI-MS and measure the method that in fruits and vegetables, nitrile pyrrole mite ester is residual, be more particularly the method adopting Gas Chromatography-Negative chemical ionization source-mass spectrum (GC-NCI-MS) qualitative, quantitative to measure nitrile pyrrole mite ester content residual in vegetables and fruit, belong to the determination techniques field of persticide residue.
Background technology
Nitrile pyrrole mite ester (Cyenopyrafen) is the novel pyrazoles acaricide developed by Nissan Chemical company for 2009, be mainly used in preventing and treating fruit tree, the evil such as the red spider of vegetables and green capsicum mite, chemical name is (E)-2-(4-tert-butyl phenyl)-2-cyano group-1-(1, 3, 4-trimethylpyrazol-5-base) thiazolinyl 2, 2-dimethyl propylene acid esters, English language Chemical name is called (E)-2-(4-tert-butylphenyl)-2-cyano-1-(1, 3, 4-trimethylPyrazol-5-yl) vinyl 2, 2-imethylpropionate, CAS accession number is 560121-52-0, molecular weight is 393.52, structural formula is:
Nitrile pyrrole mite ester obtained registration in 2009 in Japan and Korea S, sold, 2010 annual sales amounts about 1,000 ten thousand dollars with trade name Starmite and Valuestar (with the mixture of pyridaben).Be mainly used in preventing and treating the various harmful mite on fruit, vegetables, the green capsicum such as eggplant, green capsicum, cucumber, pears, strawberry, citrus, there is good quick-acting and lasting effect.This medicament is contact killing type acaricide, the mechanism of action is: medicament activates generation activity by being metabolized to OH-form, this OH-form reaches the mitochondrial usefulness of suppression by upsetting Complex II (succinate dehydrogenase) on respiratory electron transport chain, thus obstruction electron transmission, destroy oxidative phosphorylation process.With existing pesticide without cross resistance.
Along with the registration of nitrile pyrrole mite ester, popularization and use, as the Korea S in China's veterinary antibiotics main exit market and Japan, residue limits standard is formulated to it.Korea S's regulation nitrile pyrrole mite ester maximum maximum permission quantity in eggplant is 2.0mg/kg; Japan's regulation nitrile pyrrole mite ester maximum permission residue limits (MRL) is respectively green capsicum (1.0mg/L), eggplant (0.7mg/L), cucumber (1.0mg/L), orange (0.02mg/L), watermelon (0.05mg/L), peach (0.1mg/L), plum (0.2mg/L), orange and lemon (2.0mg/L), citrus (2.0mg/L), pears (2.0mg/L), strawberry (3.0mg/L), grape (5.0mg/L), apricot (5.0mg/L), all carries out " uniform limit " of 0.01mg/L in all the other vegetables and fruit; European Union also carries out " uniform limit " of 0.01mg/L to nitrile pyrrole mite ester.
Up to now, only retrieve a patent " a kind of assay method of nitrile pyrrole mite ester residual quantity ", this patent establishes the detection method adopting Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) to measure nitrile pyrrole mite ester residual quantity in vegetables and fruit, using LC-MS/MS to measure food Residual Pesticides in Farm Produce has fast, easy, sensitivity advantages of higher, but due to its price costly, a lot of testing agency, enterprise or scientific research institutions do not configure this instrument or configuration number of units is less, during due to different compounds employing LC-MS/MS detection, different mobile phases or chromatographic column need be used, such needs constantly change chromatographic column, mobile phase also expends the long time and balances system, this constrains the application of LC-MS/MS to a certain extent.The gaschromatographic mass spectrometry (GC-NCI-MS) in outfit negative chemical ionization source is analyzed food Residual Pesticides in Farm Produce tool and is had great advantage, Negative chemical ionization (NCI source) is called as mass spectrum " soft ionization source ", to the analysis thing containing electronegativity group, there is high selectivity and high sensitivity, because its characteristic is strong, when utilizing it to carry out retention analysis, matrix interference is little, can carry out qualitative and quantitative analysis very accurately to object.Existing various testing agency and enterprise have all purchased gas chromatograph-mass spectrometer (GCMS) (GC-MS), generally also be provided with Negative chemical ionization (NCI), now a lot of class agricultural chemicals is all containing electronegativity group, and organochlorine and pyrethroid pesticide molecule are mostly containing strong electronegative group such as-F ,-Cl ,-Br or-COO-, organophosphorus pesticide molecule is mostly containing the=electronegativity group such as S ,-OR ,-P ,-O-,-Cl or-P=O, and mostly containing-F group in the novel agrochemical developed in recent years, therefore, use GC-NCI-MS conveniently can realize the multi-residue analysis of Multiple Pesticides, compared with GC-NCI-MS, better antijamming capability can be obtained, lower sensitivity and better selectivity, nitrile pyrrole mite ester belongs to electronegativity compound, but have no the report of the GC-NCI-MS detection method of nitrile pyrrole mite ester residual quantity in vegetables and fruit up to now, therefore, the detection method setting up nitrile pyrrole mite ester residual quantity in Gas Chromatography-Negative chemical ionization source-mass spectrum (GC-NCI-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-NCI-MS and measure the method that in fruits and vegetables, nitrile pyrrole mite ester is residual.
For realizing above object, the technical solution adopted in the present invention is: a kind of GC-NCI-MS measures the method that in fruits and vegetables, nitrile pyrrole mite ester is 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-Negative chemical ionization source-mass spectrum (GC-NCI-MS) detects.
(3) preparation of standard working solution
When same kind matrix blank sample not containing nitrile pyrrole mite ester 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 the nitrile pyrrole mite ester series hybrid standard working fluid of at least 3 concentration.
(4) Gas Chromatography-Negative chemical ionization source-mass spectroscopy (GC-NCI-MS) measures
The standard working solution of each concentration gradient in step (3) is carried out GC-NCI-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-NCI-MS to measure, record the chromatographic peak area of nitrile pyrrole mite ester in sample liquid, substitute into typical curve, obtain nitrile pyrrole mite ester content in sample liquid, then the Mass Calculation of sample representated by liquid obtains nitrile pyrrole mite ester residual quantity 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 150 DEG C; Quadrupole rod temperature 150 DEG C; Ionization pattern: negative chemical ionization, i.e. NCI pattern, energy 70eV; Scan mode: Salbutamol Selected Ion Monitoring (SIM) pattern, the ion of monitoring is: 308,309,394.
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 nitrile pyrrole mite ester and quantitatively detection in vegetables and fruit in conjunction with GC-NCI-MS, average recovery rate is 86.3% ~ 94.3%, average relative standard's deviation (RSD) is 4.6% ~ 8.6%, detection limit, lower than 1.12 μ g/kg, has easy and simple to handle, quick, accurate, highly sensitive and reproducible advantage.The technical requirement of the countries such as Korea S, Japan, European Union to corresponding product safety detection being met, providing strong technical support by for ensureing that our people's food security and export abroad trade develop in a healthy way.
Accompanying drawing explanation
The GC-NCI-MS Selective ion mode chromatogram of Fig. 1 to be concentration be nitrile pyrrole mite ester mark liquid of 100ng/mL.
Fig. 2 is not containing the GC-NCI-MS Selective ion mode chromatogram of the orange blank sample of nitrile pyrrole mite ester.
Fig. 3 is the GC-NCI-MS Selective ion mode chromatogram of the nitrile pyrrole mite ester be added in blank orange matrix.
The nitrile pyrrole mite ester standard working curve that Fig. 4 is is substrate preparation with the orange blank sample not containing nitrile pyrrole mite ester.
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-5975C 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: 100mg/L, acetontrile, purchased from German Dr.Ehrenstorfer company.
Embodiment 1: the detection of nitrile pyrrole mite ester residual quantity in orange
(1) sample pre-treatments
Taking orange 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 volume ratio is 1/1, after vortex mixed film, move in sample injection bottle and treat that GC-NCI-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.Orange blank sample not containing nitrile pyrrole mite 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-Negative chemical ionization source-mass spectroscopy (GC-NCI-MS) measures
The standard working solution of variable concentrations gradient is injected GC-NCI-MS respectively, carries out the quantitative test of nitrile pyrrole mite ester 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-NCI-MS to measure, record the chromatographic peak area of nitrile pyrrole mite ester in sample liquid, substitute into typical curve, obtain nitrile pyrrole mite ester content in sample liquid, then the Mass Calculation of sample representated by liquid obtains nitrile pyrrole mite ester residual quantity 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: negative chemical ionization, i.e. NCI pattern, energy 70eV.
Ion source temperature: 150 DEG C.
Quadrupole rod temperature 150 DEG C.
Scan mode: Salbutamol Selected Ion Monitoring (SIM) pattern.
The ion of SIM monitoring is: 308,309,394, and quota ion is 308.
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 nitrile pyrrole mite ester in table 1 orange bare substrate
| Title | Retention time (min) | Regression equation | Related coefficient |
| Nitrile pyrrole mite ester Cyenopyrafen | 24.19 | Y＝96.881X-540.55 | 0.9991 |
Recovery of standard addition and repeatability:
In the orange not containing nitrile pyrrole mite ester, add the nitrile pyrrole mite ester 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 nitrile pyrrole mite ester is 89.3% ~ 92.1%, and average relative standard's deviation (RSD) is 4.6% ~ 8.3%, illustrates that the recovery of the inventive method is higher, reproducible.
The recovery of table 2 nitrile pyrrole mite ester and repeatability (n=6)
Detection limit:
The nitrile pyrrole mite ester group matter standard working solution of variable concentrations is injected GC-NCI-MS, calculate detection limit with the cycles of concentration (cycles of concentration of orange 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 nitrile pyrrole mite ester is limited to 0.35 μ g/kg.
Embodiment 2: the detection of nitrile pyrrole mite ester residual quantity 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-NCI-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 nitrile pyrrole mite 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-Negative chemical ionization source-mass spectroscopy (GC-NCI-MS) measures
Operation steps, chromatogram are consistent with the mensuration of nitrile pyrrole mite ester in above-mentioned orange sample with Mass Spectrometry Conditions.
Qualitative Identification:
Consistent with the mensuration of nitrile pyrrole mite ester in above-mentioned orange 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=85.287X-372.35, and related coefficient is 0.9994.
Recovery of standard addition and repeatability:
The nitrile pyrrole mite ester standard solution of 50,100 and 200 μ g/kg, 3 concentration levels is added in the dehydration green pepper not containing nitrile pyrrole mite ester, 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 nitrile pyrrole mite ester is 86.3% ~ 94.3%, and average relative standard's deviation (RSD) is 5.7% ~ 8.6%, illustrates that the recovery of the inventive method is high, reproducible.
The recovery of table 3 nitrile pyrrole mite ester and repeatability (n=6)
Detection limit:
The nitrile pyrrole mite ester group matter standard working solution of variable concentrations is injected GC-NCI-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 nitrile pyrrole mite ester is limited to 1.12 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-NCI-MS measures the method that in fruits and vegetables, nitrile pyrrole mite ester is 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-Negative chemical ionization source-mass spectrum (GC-NCI-MS) detects;
(3) preparation of standard working solution
Same kind matrix blank sample not containing nitrile pyrrole mite ester 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 the nitrile pyrrole mite ester series hybrid standard working fluid 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-NCI-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-NCI-MS to measure, record the chromatographic peak area of nitrile pyrrole mite ester in sample liquid, substitute into extraction standard curve, obtain nitrile pyrrole mite ester content in sample liquid, then the Mass Calculation of sample representated by liquid obtains nitrile pyrrole mite ester residual quantity in sample per sample.
2. a kind of GC-NCI-MS according to claim 1 measures the method that in fruits and vegetables, nitrile pyrrole mite ester is 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-NCI-MS according to claim 1 measures the method that in fruits and vegetables, nitrile pyrrole mite ester is 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-NCI-MS according to claim 1 measures the method that in fruits and vegetables, nitrile pyrrole mite ester is 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-NCI-MS according to claim 1 measures the method that in fruits and vegetables, nitrile pyrrole mite ester is residual, it is characterized in that, in step (4), GC-NCI-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: negative chemical ionization, i.e. NCI pattern, energy 70eV; Ion source temperature 150 DEG C; Scan mode: Salbutamol Selected Ion Monitoring (SIM) pattern, the ion of monitoring is: 308,309,394.
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