CN104407090A - Method for determining residue of spirotetramat in fruits and vegetables by GC-NCI-MS (gas chromatography-negative chemical ionization-mass spectrometry) - Google Patents
Method for determining residue of spirotetramat in fruits and vegetables by GC-NCI-MS (gas chromatography-negative chemical ionization-mass spectrometry) Download PDFInfo
- Publication number
- CN104407090A CN104407090A CN201410843021.XA CN201410843021A CN104407090A CN 104407090 A CN104407090 A CN 104407090A CN 201410843021 A CN201410843021 A CN 201410843021A CN 104407090 A CN104407090 A CN 104407090A
- Authority
- CN
- China
- Prior art keywords
- sample
- nci
- ethyl ester
- spiral shell
- shell worm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for determining residue of spirotetramat in fruits and vegetables by GC-NCI-MS (gas chromatography-negative chemical ionization-mass spectrometry). The method is characterized by comprising the steps of homogenizing and extracting residual spirotetramat in a sample by utilizing acetonitrile or an acetonitrile solution containing 1% acetonitrile to obtain an extraction solution, dispersing and purifying the extraction solution by utilizing PSA and an octadecylsilan bonded phase (C18) matrix and detecting by GC-NCI-MS, establishing a standard curve for calibration by adopting a blank matrix solution without a to-be-detected farm chemical, and quantifying by an external standard method. According to the method, an average recovery rate is 89.4 to 94.5 percent, an average relative standard deviation (RSD) is 3.8 to 7.7 percent, and the detection limit is less than 1.46 micrograms per kilogram. The method has advantages of simplicity and rapidness in operation, high sensitivity, good repeatability and accuracy in nature determination and quantification. Technical requirements on the security detection on relevant products in countries such as USA, EU and Japan can be met, and a powerful technical support can be provided for guaranteeing the food security and healthy development of export trade in China.
Description
Technical field
The present invention relates to a kind of GC-NCI-MS and measure the method that in fruits and vegetables, spiral shell worm ethyl ester is residual, be more particularly the method adopting Gas Chromatography-Negative chemical ionization source-mass spectrum (GC-NCI-MS) qualitative, quantitative to measure spiral shell worm ethyl ester content residual in vegetables and fruit, belong to the determination techniques field of persticide residue.
Background technology
Spiral shell worm ethyl ester (Spirotetramat) is the new tetronic acid derivatives insecticides of Bayer A.G's Development and Production, and insecticidal spectrum is wide, and the lasting period is long.Fatty biosynthesizing mainly through interference insect causes dead larvae, reduces the fertility of adult.Due to the mechanism of action of its uniqueness, effectively can prevent and treat the insect existing pesticide being produced to resistance, can be used as the important kind of nicotinic insecticide resistance management simultaneously.Spiral shell worm ethyl ester is the only modern pesticides had at xylem and the two-way Uptake and translocation performance of bast so far.This compound upwards can move down in whole plant, arrives at blade face and bark, thus prevents the insect on hiding on romaine lettuce and Chinese cabbage internal lobe and fruits and vegetables skin.The interior absorption of this uniqueness can protect newly sprout, leaf and root, prevent ovum and the larval growth of insect.Two-way Uptake and translocation means that insect does not have the place that can hide of safety, and preventive and therapeutic effect is more thorough.Therefore, this agricultural chemicals has good application prospect.Chemical name is cis-4-(ethoxy carbonyl oxygen base)-8-methoxyl-3-(2,5-xylyl)-1-azaspiro [4.5]-3-in last of the ten Heavenly stems alkene-2-ketone.English language Chemical name is called cis-4-(ethoxycarbonyloxy)-8-methoxy-3-(2,5-xylyl)-1-azaspiro [4.5] dec-3-en-2-one.CAS accession number is 382608-10-8, and molecular weight is 373.5, and structural formula is:
Spiral shell worm ethyl ester submits registration to 69 countries and regions.Within 2008, spiral shell worm ethyl ester is successful in the U.S., Canada, Austria, New Zealand, Morocco, Turkey and Tunisia registration.Now obtain registration in more countries and regions successively.Spiral shell worm ethyl ester can be used for various crop, comprises the various suckings pest of control such as cotton, soybean, oranges and tangerines, tropical fruit tree, nut, grape, hops, potato and vegetables, as aphid, thrips, wood louse, aleyrodid, mealybug and scale insect etc.Its to important beneficial insect as ladybug, wasp fly and parasitic wasp have good selectivity.
Along with the registration of spiral shell worm ethyl ester, popularization and use, as U.S. in China's veterinary antibiotics main exit market and European Union, residue limits standard is formulated to it.Environmental Protection Agency issues circular, and announcing draws up has determined in following food/the residual license limitation [calculating by spirotetramat] of table pesticide-spirotetramat: stem tuber and plant bulbs subgroup 1c:1.0mg/kg; Potato grain/sheet: 2.5mg/kg; Dried onion bulb subgroup: 0.3mg/kg; Leaf type plant 4 groups: 5.0mg/kg except rape class; Rape, head and rhizome subgroup 5a:3.0mg/kg; Rape, leaf class green plants subgroup 5b:16.0mg/kg; Fruit plant 8 groups: 1.0mg/kg; Tomato, dry fruit slag: 2.5mg/kg; Cucurbit class plant 9 groups: 0.2mg/kg; Citrus fruit 10 groups: 0.5mg/kg; Tangerine oil: 4.0mg/kg; The operatic circle 11 groups: 0.5mg/kg; Drupe 12 groups: 2.0mg/kg; Nut 14 groups: 0.5mg/kg; Apricot shell: 9.0mg/kg; Grape: 1.0mg/kg; Raisins: 2.5mg/kg; Hop: 10.0mg/kg; Strawberry: 0.5mg/kg; Regulation has all been made to the maximum maximum permission quantity of spiral shell worm ethyl ester (MRL) in fresh fruit and freezing nut, fresh and beverage, the flavoring such as refrigerated vegetables, dry beans, oil crops, cereal, tea by European Union, and residue limits is from 0.01mg/kg to 7mg/kg; Regulation has also been made to spiral shell worm ethyl ester MRL in food by the countries such as Canada.
Present stage, less to the research of spiral shell worm ethyl ester determination of residual amount method in vegetables and fruit, the detection method of report all adopts liquid chromatography (LC), Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS) measures the detection method of spiral shell worm ethyl 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, spiral shell worm ethyl ester belongs to electronegativity compound, but have no the report of the GC-NCI-MS detection method of spiral shell worm ethyl ester residual quantity in vegetables and fruit up to now, therefore, the detection method setting up spiral shell worm ethyl 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, spiral shell worm ethyl 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, spiral shell worm ethyl 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 spiral shell worm ethyl 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 spiral shell worm ethyl 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 spiral shell worm ethyl ester in sample liquid, substitute into typical curve, obtain spiral shell worm ethyl ester content in sample liquid, then the Mass Calculation of sample representated by liquid obtains spiral shell worm ethyl ester residual quantity in sample per sample.If spiral shell worm ethyl ester residual quantity exceedes the range of linearity upper limit in upper machine solution, with constant volume solvent, upper machine solution concentration need be diluted within the range of linearity.
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: 283,89,284.
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 spiral shell worm ethyl ester and quantitatively detection in vegetables and fruit in conjunction with GC-NCI-MS, average recovery rate is 89.4% ~ 94.5%, average relative standard's deviation (RSD) is 3.8% ~ 7.7%, detection limit, lower than 1.46 μ g/kg, has easy and simple to handle, quick, accurate, highly sensitive and reproducible advantage.The technical requirement of the countries such as the U.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 spiral shell worm ethyl ester mark liquid of 100ng/mL.
Fig. 2 is not containing the GC-NCI-MS Selective ion mode chromatogram of the strawberry blank sample of spiral shell worm ethyl ester.
Fig. 3 is the GC-NCI-MS Selective ion mode chromatogram of the spiral shell worm ethyl ester be added in blank strawberry matrix.
The spiral shell worm ethyl ester standard working curve that Fig. 4 is is substrate preparation with the strawberry blank sample not containing spiral shell worm ethyl 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: purity >=98.0%, purchased from German Dr.Ehrenstorfer company.
Embodiment 1: the detection of spiral shell worm ethyl ester residual quantity in strawberry
(1) sample pre-treatments
Taking strawberry 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
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.Strawberry 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-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 spiral shell worm ethyl 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 spiral shell worm ethyl ester in sample liquid, substitute into typical curve, obtain spiral shell worm ethyl ester content in sample liquid, then the Mass Calculation of sample representated by liquid obtains spiral shell worm ethyl 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: 283,89,284, and quota ion is 283.
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 spiral shell worm ethyl ester in table 1 strawberry bare substrate
| Title | Retention time (min) | Regression equation | Related coefficient |
| Spiral shell worm ethyl ester Spirotetramat | 28.38 | 106.12 | 0.9992 |
Recovery of standard addition and repeatability:
The spiral shell worm ethyl ester standard solution of 10,20, a 500 and 1000 μ g/kg4 concentration level is added in the strawberry not containing spiral shell worm ethyl ester, add after 30min until agricultural chemicals and carry out the determination of residual amount by above-mentioned treatment step, the sample liquid volume ratio to be measured that 500 μ g/kg and 1000 μ g/kg add concentration be 1/1 acetone/normal hexane mixed solvent measure with GC-MS again after diluting 5 times.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 4 mark-on levels, the average recovery rate of spiral shell worm ethyl ester is 90.4% ~ 94.5%, and average relative standard's deviation (RSD) is 4.7% ~ 6.4%, illustrates that the recovery of the inventive method is higher, reproducible.
The recovery of table 2 spiral shell worm ethyl ester and repeatability (n=6)
Detection limit:
The spiral shell worm ethyl ester matrix standard working solution of variable concentrations is injected GC-NCI-MS, calculate detection limit with the cycles of concentration (cycles of concentration of strawberry 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 spiral shell worm ethyl ester is limited to 1.46 μ g/kg.
Embodiment 2: the detection of spiral shell worm ethyl ester residual quantity in Chinese cabbage
(1) sample pre-treatments
Take Chinese cabbage 10.0g through fully mixing in 50mL centrifuge tube, accurately add the acetonitrile solution of 20mL containing 1% acetic acid, homogeneous extracts 1min, adds 3g anhydrous magnesium sulfate and 2g sodium acetate, 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 after mixing, move in sample injection bottle and treat that GC-NCI-MS measures.
(2) preparation of standard working solution
10 μ g/mL standard solution dilutions are made into 5,2,1,0.5,0.2,0.1 μ g/mL standard solution.Chinese cabbage 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-Negative chemical ionization source-mass spectroscopy (GC-NCI-MS) measures
Operation steps, chromatogram are consistent with the mensuration of spiral shell worm ethyl ester in above-mentioned strawberry sample with Mass Spectrometry Conditions.
Qualitative Identification:
Consistent with the mensuration of spiral shell worm ethyl ester in above-mentioned strawberry 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=9.3543X-79.469, and related coefficient is 0.9991.
Recovery of standard addition and repeatability:
The spiral shell worm ethyl ester standard solution of 0.01,0.02,5 and 10mg/kg4 concentration level is added in the Chinese cabbage not containing spiral shell worm ethyl ester, add after 30min until agricultural chemicals and carry out the determination of residual amount by above-mentioned treatment step, the sample liquid volume ratio to be measured that 5mg/kg and 10mg/kg adds concentration be 1/1 acetone/normal hexane mixed solvent measure with GC-MS again after diluting 50 times.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 4 mark-on levels, the average recovery rate of spiral shell worm ethyl ester is 89.4% ~ 94.0%, and average relative standard's deviation (RSD) is 3.8% ~ 7.7%, illustrates that the recovery of the inventive method is high, reproducible.
The recovery of table 3 spiral shell worm ethyl ester and repeatability (n=6)
Detection limit:
The spiral shell worm ethyl ester matrix standard working solution of variable concentrations is injected GC-NCI-MS, calculate detection limit with the cycles of concentration (cycles of concentration of Chinese cabbage 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 spiral shell worm ethyl ester is limited to 0.79 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, spiral shell worm ethyl 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 spiral shell worm ethyl 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 spiral shell worm ethyl 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 spiral shell worm ethyl ester in sample liquid, substitute into extraction standard curve, obtain spiral shell worm ethyl ester content in sample liquid, then the Mass Calculation of sample representated by liquid obtains spiral shell worm ethyl ester residual quantity in sample per sample.If spiral shell worm ethyl ester residual quantity exceedes the range of linearity upper limit in upper machine solution, with constant volume solvent, upper machine solution concentration need be diluted within the range of linearity.
2. a kind of GC-NCI-MS according to claim 1 measures the method that in fruits and vegetables, spiral shell worm ethyl 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, spiral shell worm ethyl 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, spiral shell worm ethyl 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, spiral shell worm ethyl 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: 283,89,284.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410843021.XA CN104407090B (en) | 2014-12-30 | 2014-12-30 | A kind of GC-NCI-MS measures the method that in fruits and vegetables, spiral shell worm ethyl ester is residual |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410843021.XA CN104407090B (en) | 2014-12-30 | 2014-12-30 | A kind of GC-NCI-MS measures the method that in fruits and vegetables, spiral shell worm ethyl ester is residual |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104407090A true CN104407090A (en) | 2015-03-11 |
| CN104407090B CN104407090B (en) | 2015-12-09 |
Family
ID=52644737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410843021.XA Active CN104407090B (en) | 2014-12-30 | 2014-12-30 | A kind of GC-NCI-MS measures the method that in fruits and vegetables, spiral shell worm ethyl ester is residual |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104407090B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111458439A (en) * | 2020-04-23 | 2020-07-28 | 宁波市农业科学研究院 | Method for detecting spirotetramat and enol metabolite thereof in plant-derived agricultural products by combining common group method with UP L C-MSMS |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102692468A (en) * | 2012-05-22 | 2012-09-26 | 天津出入境检验检疫局动植物与食品检测中心 | Reagent kit for detecting pretreatment of common bactericide in perilla leaf, and method thereof |
| CN103412077A (en) * | 2013-07-14 | 2013-11-27 | 崔淑华 | Method for measuring indazole flusulfamide residue amount |
| 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 |
| CN103675175A (en) * | 2013-12-04 | 2014-03-26 | 广东出入境检验检疫局检验检疫技术中心 | Method for determination of pesticide residues in vegetable oils |
| CN103728401A (en) * | 2014-01-07 | 2014-04-16 | 崔淑华 | Determination method of bistrifluron residual quantity |
| CN103822999A (en) * | 2014-02-28 | 2014-05-28 | 中国农业科学院农产品加工研究所 | Full-automatic QuEChERS preprocessing all-in-one machine and preprocessing method |
| CN103913528A (en) * | 2014-04-24 | 2014-07-09 | 江苏太湖地区农业科学研究所 | Quantitative detection method for pyrethriods pesticides in fresh tea |
| CN103913529A (en) * | 2014-04-24 | 2014-07-09 | 江苏太湖地区农业科学研究所 | Analyzing method for simultaneously determining residues of organophosphorus pesticides and pyrethriods pesticides in soil |
| CN103926362A (en) * | 2014-04-24 | 2014-07-16 | 江苏太湖地区农业科学研究所 | Quantitative detection method for pyrethriods pesticide in soil |
| CN103926348A (en) * | 2014-04-24 | 2014-07-16 | 江苏太湖地区农业科学研究所 | Analytical method of simultaneously measuring residues of organophosphorus pesticide and pyrethriods pesticide in fresh leaves |
-
2014
- 2014-12-30 CN CN201410843021.XA patent/CN104407090B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102692468A (en) * | 2012-05-22 | 2012-09-26 | 天津出入境检验检疫局动植物与食品检测中心 | Reagent kit for detecting pretreatment of common bactericide in perilla leaf, and method thereof |
| CN103412077A (en) * | 2013-07-14 | 2013-11-27 | 崔淑华 | Method for measuring indazole flusulfamide residue amount |
| 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 |
| CN103675175A (en) * | 2013-12-04 | 2014-03-26 | 广东出入境检验检疫局检验检疫技术中心 | Method for determination of pesticide residues in vegetable oils |
| CN103728401A (en) * | 2014-01-07 | 2014-04-16 | 崔淑华 | Determination method of bistrifluron residual quantity |
| CN103822999A (en) * | 2014-02-28 | 2014-05-28 | 中国农业科学院农产品加工研究所 | Full-automatic QuEChERS preprocessing all-in-one machine and preprocessing method |
| CN103913528A (en) * | 2014-04-24 | 2014-07-09 | 江苏太湖地区农业科学研究所 | Quantitative detection method for pyrethriods pesticides in fresh tea |
| CN103913529A (en) * | 2014-04-24 | 2014-07-09 | 江苏太湖地区农业科学研究所 | Analyzing method for simultaneously determining residues of organophosphorus pesticides and pyrethriods pesticides in soil |
| CN103926362A (en) * | 2014-04-24 | 2014-07-16 | 江苏太湖地区农业科学研究所 | Quantitative detection method for pyrethriods pesticide in soil |
| CN103926348A (en) * | 2014-04-24 | 2014-07-16 | 江苏太湖地区农业科学研究所 | Analytical method of simultaneously measuring residues of organophosphorus pesticide and pyrethriods pesticide in fresh leaves |
Non-Patent Citations (7)
| Title |
|---|
| 严会会 等: "高效液相色谱串联质谱法分析烟草中15种农药残留", 《烟草科技》 * |
| 张孟迪 等: "螺虫乙酯分析方法述评", 《农药》 * |
| 施雅 等: "UPLC-MS/MS法测定四种果蔬中螺虫乙酯残留量", 《食品与机械》 * |
| 沈伟健 等: "分散固相萃取-气相色谱-串联质谱法测定蔬菜中107种农药的残留量", 《色谱》 * |
| 王雪娟 等: "利用农药成分监测技术，监控非法添加行为", 《农药科学与管理》 * |
| 赤松成基 等: "残留農藥の多成分—斉分析法にぉけゐ6種農產物への適用", 《兵庫県立健康生活科学研究所健康科学研究センタ一研究报告 第5号》 * |
| 马智玲 等: "气相色谱-三重四极杆串联质谱法快速测定蔬菜水果中129种农药的残留量", 《色谱》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111458439A (en) * | 2020-04-23 | 2020-07-28 | 宁波市农业科学研究院 | Method for detecting spirotetramat and enol metabolite thereof in plant-derived agricultural products by combining common group method with UP L C-MSMS |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104407090B (en) | 2015-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104502504B (en) | The assay method of Rynaxypyr residual quantity in a kind of vegetables and fruit | |
| CN104502507B (en) | A kind of GC-NCI-MS assay method of Rynaxypyr residual quantity | |
| CN104458968B (en) | The GC-EI-MS assay method of spiral shell worm ethyl ester residual quantity in a kind of fruits and vegetables | |
| CN104502484B (en) | A kind of GC-NCI-MS measures the method that in fruits and vegetables, cyanogen insect amide is residual | |
| CN104597189B (en) | A kind of assay method of Pyrifluquinazon residual quantity | |
| CN104502482B (en) | The assay method of fipronil bisamide residual quantity in a kind of vegetables and fruit | |
| CN104535692B (en) | The LC-MS/MS assay method that in a kind of fruits and vegetables, four chlorantraniliproles are residual | |
| CN104655783B (en) | The GC-NCI-MS assay method of metrafenone residual quantity in a kind of fruits and vegetables | |
| CN104407090B (en) | A kind of GC-NCI-MS measures the method that in fruits and vegetables, spiral shell worm ethyl ester is residual | |
| CN104502505B (en) | A kind of GC-EI-MS assay method of spiral shell worm ethyl ester residual quantity | |
| CN104502508B (en) | A kind of GC-NCI-MS assay method of cyanogen insect amide residual quantity | |
| CN104459001B (en) | The assay method of Rynaxypyr residual quantity in a kind of fruits and vegetables | |
| CN104655781B (en) | A kind of assay method of metrafenone residual quantity | |
| CN104502510B (en) | A kind of GC-NCI-MS measures the method that in fruits and vegetables, nitrile pyrrole mite ester is residual | |
| CN104535686B (en) | A kind of GC-NCI-MS assay method of nitrile pyrrole mite ester residual quantity | |
| CN104569210B (en) | A kind of GC-EI-MS measures the method that in fruits and vegetables, four chlorantraniliproles are residual | |
| CN105510506A (en) | Method for GC-MS/MS (gas chromatography tandem mass spectrometry) determination of penflufen remains in fruits and vegetables | |
| CN104502506B (en) | A kind of GC-NCI-MS assay method of spiral shell worm ethyl ester residual quantity | |
| CN104459000A (en) | GC-EI-MS (gas chromatography-electron ionization-mass spectrum) measuring method for chlorantraniliprole residual quantity | |
| CN104407091B (en) | A kind of GC-NCI-MS assay method of fipronil bisamide residual quantity | |
| CN104535691B (en) | The assay method of four chlorantraniliprole residual quantities in a kind of vegetables and fruit | |
| CN105548444A (en) | GC-MS/MS (gas chromatography-tandem mass spectrometry) determining method of aniline pyrazolone residual quantity | |
| CN104614478B (en) | A kind of assay method of Pyrifluquinazon residual quantity | |
| CN105699518A (en) | Measurement method for fluxapyroxad residue in vegetables and fruits | |
| CN105572288A (en) | Method for determining aminobenzene pyrazolone residues in fruits and vegetables through GC-EI-MS |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| CB03 | Change of inventor or designer information |
Inventor after: Liu Hong Inventor before: Yin Peijun Inventor before: Xu Hong Inventor before: Guo Qinglong Inventor before: Wang Zhengguo |
|
| COR | Change of bibliographic data | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160914 Address after: 710077 No. 81, Kam Yip Road, Gaoxin District, Shaanxi, Xi'an Patentee after: Shaanxi Huabang Testing Services Ltd. Address before: 266555 Changjiang Road, Huangdao District, Shandong, China, No. 469, No. Patentee before: Guo Qinglong |