CN104502483B - A kind of GC-EI-MS measures the method for nitrile pyrrole mite ester residual quantity in fruits and vegetables - Google Patents
A kind of GC-EI-MS measures the method for nitrile pyrrole mite ester residual quantity in fruits and vegetables Download PDFInfo
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Abstract
The invention discloses a kind of method that GC-EI-MS measures nitrile pyrrole mite ester residual quantity in fruits and vegetables, extract nitrile pyrrole mite ester residual in sample with acetonitrile or containing the acetonitrile solution homogeneous of 1% acetic acid, extract is through primary secondary amine (PSA) and octadecylsilane Bonded Phase (C
18) after matrix dispersion purification, gas chromatography-electron impact ion source-mass spectrum (GC-EI-MS) detects, and adopts and does not set up the typical curve corrected, quantified by external standard method containing the vehicle solution of agricultural chemicals to be measured.This method average recovery rate is 87.2% ~ 92.6%, and average relative standard's deviation (RSD) is 4.0% ~ 6.5%, is detection limit lower than 1.33? μ g/kg, has easy and simple to handle, quick, highly sensitive, reproducible, qualitative, quantitative advantage accurately.The technical requirement of the countries such as Korea S, Japan, European Union to corresponding product safety detection being met, providing strong technical support for ensureing that our people's food security and export abroad trade develop in a healthy way.
Description
Technical field
The present invention relates to a kind of method that GC-EI-MS measures nitrile pyrrole mite ester residual quantity in fruits and vegetables, be more particularly the method adopting gas chromatography-electron impact ion source-mass spectrum (GC-EI-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) vinyl2, 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-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, but have no the report of the GC-EI-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-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 method that GC-EI-MS measures nitrile pyrrole mite ester residual quantity in fruits and vegetables.
For realizing above object, the technical solution adopted in the present invention is: a kind of GC-EI-MS measures the method for nitrile pyrrole mite ester residual quantity in fruits and vegetables, 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 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-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 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 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: 309.2,294.2,393.3,310.2.
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-EI-MS, average recovery rate is 87.2% ~ 92.6%, average relative standard's deviation (RSD) is 4.0% ~ 6.5%, detection limit, lower than 1.33 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-EI-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-EI-MS Selective ion mode chromatogram of the orange blank sample of nitrile pyrrole mite ester.
Fig. 3 is the GC-EI-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-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: 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, 300mgC are housed
18with in the centrifuge tube of 150mgPSA, 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
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-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 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-EI-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: 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: 309.2,294.2,393.3,310.2, and quota ion is 309.2.
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 | 24.21 | Y＝808.28X+1731 | 0.9999 |
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 91.3% ~ 92.6%, and average relative standard's deviation (RSD) is 4.0% ~ 5.6%, 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-EI-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 0.51 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, 300mgC are housed
18with in the centrifuge tube of 150mgPSA, 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 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-electron impact ion source-mass spectroscopy (GC-EI-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=723.87X-4479.8, and related coefficient is 0.9998.
Recovery of standard addition and repeatability:
The nitrile pyrrole mite ester standard solution of 50, a 100 and 200 μ g/kg3 concentration level 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 87.2% ~ 91.6%, and average relative standard's deviation (RSD) is 5.1% ~ 6.5%, 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-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 nitrile pyrrole mite ester is limited to 1.33 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 (1)
1. GC-EI-MS measures a method for nitrile pyrrole mite ester residual quantity in fruits and vegetables, 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, described Dispersive solid phase extraction agent is by anhydrous magnesium sulfate, C
18with PSA composition, anhydrous magnesium sulfate, C in every milliliter of extract
18150mg, 50mg and 25mg is respectively with PSA addition; 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 GC-EI-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 standard solution, vortex mixes, and is mixed with the nitrile pyrrole mite ester series standard working fluid of at least 3 concentration;
(4) mensuration and result calculate
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: 309.2,294.2,393.3,310.2;
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 nitrile pyrrole mite ester in sample liquid, substitute into extraction standard working 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.
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