CN104678024A - ECD determination method for residual quantity of N-(3-chloro-5-(trichloromethyl)pyridyl-2-methyl)-2,3,5,6-tetrafluoro-4-methoxybenzamide in vegetables and fruits - Google Patents
ECD determination method for residual quantity of N-(3-chloro-5-(trichloromethyl)pyridyl-2-methyl)-2,3,5,6-tetrafluoro-4-methoxybenzamide in vegetables and fruits Download PDFInfo
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- CN104678024A CN104678024A CN201510109393.4A CN201510109393A CN104678024A CN 104678024 A CN104678024 A CN 104678024A CN 201510109393 A CN201510109393 A CN 201510109393A CN 104678024 A CN104678024 A CN 104678024A
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Abstract
The invention discloses an ECD determination method for residual quantity of N-(3-chloro-5-(trichloromethyl)pyridyl-2-methyl)-2,3,5,6-tetrafluoro-4-methoxybenzamide in vegetables and fruits. The ECD determination method comprises the following steps: homogenizing by using acetonitrile or an acetonitrile solution containing 1% acetic acid to extract residual desflurane bacteria amide in a sample; after dispersing and purifying an extract by using ethidene diamine-N-propylsilane (PSA) and octadecylsilane bonded phase (C18) matrix, determining by using a gas chromatography-electron capture detector (GC-ECD); quantifying by an external standard method. By the ECD determination method, the average recycling rate is 93.3-98.3%, the average relative standard deviation (RSD) is 4.1-6.5%, and the determination limit is lower than 3.16 [mu]g/kg; the ECD determination method has the advantages of simple, convenient and rapid operation, high sensitivity, good repeatability and accurate quantification; by the ECD determination method, a technical requirement on a uniform residue limit of 0.01mg/kg can be met; a powerful technical support is provided for guaranteeing food safety of people in China and healthy development of export trade.
Description
Technical field
The present invention relates to the ECD assay method of fluorine ether bacterium acid amides residual quantity in a kind of vegetables and fruit, be more particularly the method adopting gas chromatography-electron capture detector (GC-ECD) to measure fluorine ether bacterium amide content residual in vegetables and fruit, belong to the determination techniques field of persticide residue.
Background technology
Fluorine ether bacterium acid amides (LH-2010A) is that Shandong United Pesticide Industry Co., Ltd. is in a kind of novel fluorine benzamide series bactericidal agent of innovation synthesis in 2010, chemical name is: N-(the chloro-5-of 3-(trifluoromethyl) pyridine-2-methyl)-2,3,5, the fluoro-4-methoxy benzamide of 6-tetra-, structural formula is:
Containing 7 fluorine atoms in fluorine ether bacterium amide structure formula.The C-F key bond energy that fluorine atom is formed, much larger than c h bond, significantly increases stability and the physiologically active of organofluorine compound.Fluorinated organic compound has higher fat-soluble and hydrophobicity, can promote that it absorbs and transmission in vivo, strengthens the binding ability with biosome, the physiological action of biosome is changed.Fluoro-containing pesticide has such effect equally, and fluoro-containing pesticide also improves greatly to the suppression of pathogen or insect or toxic action.Find according to the study, the virulence of fluorine ether bacterium acid amides to cotton rhizoctonia solani, botrytis cinerea, apple anthrax bacteria, Fulvia fulva, Botryosphaeria berengeriana f. sp, phytophthora infestans, Leaf Spot Caused by Corynespora cassiicola on Cucumber bacterium, phytophthora blight of pepper, Strawberry Fusarium Wilt and Pyricularia oryzae 10 Plants pathogen is all higher, visible, fluorine ether bacterium acid amides sterilization comparatively wide spectrum, can use as a kind of New-type wide-spectrum type germifuge, development prospect is wide.
Along with the registration of fluorine ether bacterium acid amides, popularization and use, about fluorine ether bacterium acid amides Residue Degradation dynamically and the research of the environmental behaviour such as final residue certainly will increase, simultaneously, if use agricultural chemicals not register in this country as European Union in China's main exit market, Japan and other countries regulation field, when not formulating corresponding residue limits standard, the food agricultural product being exported to its country comprise " uniform limit " that residue limits in the animal derived foods such as livestock meat all carries out 0.01mg/L.
Up to now, have no the report had about fluorine ether bacterium acid amides residues detection method in food agricultural product both at home and abroad, containing 7 fluorine, 1 chlorine atom in fluorine ether bacterium amide molecule, belong to electronegativity compound, gas chromatography electron capture detector can be used to analyze its residual quantity, there is good antijamming capability, selectivity is good, highly sensitive, therefore, setting up gas chromatography-electron capture detector (GC-ECD), to analyze the detection method of fluorine ether bacterium acid amides residual quantity in vegetables and fruit significant.
Summary of the invention
The object of this invention is to provide the ECD assay method of fluorine ether bacterium acid amides residual quantity in a kind of vegetables and fruit.
For realizing above object, the technical solution adopted in the present invention is: the ECD assay method of fluorine ether bacterium acid amides residual quantity in a kind of vegetables and fruit, 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 capture detector (GC-ECD) detects.
(3) preparation of standard working solution
The certain density standard reserving solution of accurate preparation and standard intermediate liquid, be then mixed with the fluorine ether bacterium acid amides series hybrid standard working fluid of at least 3 concentration;
(4) gas chromatography-electron capture detector (GC-ECD) measures
The standard working solution of each concentration gradient in step (3) is carried out GC-ECD 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-ECD to measure, record the chromatographic peak area of fluorine ether bacterium acid amides in sample liquid, substitute into typical curve, obtain fluorine ether bacterium amide content in sample liquid, then the Mass Calculation of sample representated by liquid obtains fluorine ether bacterium acid amides 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: DB-5 capillary chromatographic column, column length 30m, internal diameter 0.32mm, thickness 0.25 μm; Injector temperature 250 DEG C; Carrier gas: high pure nitrogen, post flow is 1.5mL/min; 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.
In step (4), electron capture detector condition is: detector temperature is 300 DEG C, and make-up gas flow is 30mL/min.
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 fluorine ether bacterium acid amides residue detection in vegetables and fruit in conjunction with GC-ECD, average recovery rate is 93.3% ~ 98.3%, average relative standard's deviation (RSD) is 4.1% ~ 6.5%, detection limit, lower than 3.16 μ g/kg, has easy and simple to handle, quick, accurate, highly sensitive and reproducible advantage." uniform limit " technical requirement of 0.01mg/kg residue limits can be met, for guarantee our people food security, export abroad trade sound development provide strong technical support.
Accompanying drawing explanation
Fig. 1 is the chromatogram of 50ng/mL fluorine ether bacterium acid amides mark liquid.
Fig. 2 is the chromatogram of the apple blank sample of not fluorine-containing ether bacterium acid amides.
Fig. 3 is fluorine ether bacterium acid amides standard working curve.
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 chromatograph (being equipped with electron capture detector, 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 97.8%, purchased from Shandong United Pesticide Industry Co., Ltd..
Embodiment 1: the detection of fluorine ether bacterium acid amides residual quantity in apple
(1) sample pre-treatments
Taking apple 10.0g through fully mixing in 50mL centrifuge tube, accurately adding 20mL acetonitrile, homogeneous extracts 1min, adds 3g anhydrous magnesium sulfate and 2g sodium chloride, after vortex 1min, and the centrifugal 5min of 7000r/min.After centrifugal, get 6mL acetonitrile extract and be transferred to 900mg anhydrous magnesium sulfate, 300mg C are housed
18with in the centrifuge tube of 150mg PSA, the centrifugal 5min of vortex 1min, 5000r/min.Get 4mL supernatant in nitrogen blowpipe, dry up in 40 DEG C of nitrogen, add acetone/normal hexane mixed solvent dissolved residue that volume ratio is 1/1, after vortex mixed film, move in sample injection bottle and treat that GC-ECD 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 are progressively diluted and is made into 10,20,50,100,200,500 μ g/L standard solution.
(3) gas chromatography-electron capture detector (GC-ECD) measures
The standard working solution of variable concentrations gradient is injected GC-ECD respectively, carries out the quantitative test of fluorine ether bacterium amide 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-ECD to measure, record the chromatographic peak area of fluorine ether bacterium acid amides in sample liquid, substitute into typical curve, obtain fluorine ether bacterium amide content in sample liquid, then the Mass Calculation of sample representated by liquid obtains fluorine ether bacterium acid amides residual quantity in sample per sample.
Wherein chromatographic condition is:
Chromatographic column: DB-5 capillary chromatographic column, column length 30m, internal diameter 0.32mm, thickness 0.25 μm.
Injector temperature: 250.0 DEG C, sample introduction pattern: Splitless injecting samples, sample size: 1 μ L.
Carrier gas: high pure nitrogen, constant current mode, flow velocity 1.5mL/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;
ECD detecting device: temperature 300 DEG C, make-up gas flow is 30mL/min.
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 table 1 fluorine ether bacterium acid amides
| Title | Retention time (min) | Regression equation | Related coefficient |
| Fluorine ether bacterium acid amides LH-2010A | 17.39 | Y＝131.64X-945.19 | 0.9992 |
Recovery of standard addition and repeatability:
In the apple of not fluorine-containing ether bacterium acid amides, add the fluorine ether bacterium acid amides 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 fluorine ether bacterium acid amides is 94.8% ~ 98.3%, and average relative standard's deviation (RSD) is 4.1% ~ 6.5%, illustrates that the recovery of the inventive method is higher, reproducible.
The recovery of table 2 fluorine ether bacterium acid amides and repeatability (n=6)
Detection limit:
The fluorine ether bacterium acid amides standard working solution of variable concentrations is injected GC-ECD, calculate detection limit with the cycles of concentration (cycles of concentration of apple is 2.0 times) of 3 times of signal to noise ratio (S/N ratio)s of least concentration standard solution chromatographic peak and sample handling processes, detecting of fluorine ether bacterium acid amides is limited to 0.82 μ g/kg.
Embodiment 2: the detection of fluorine ether bacterium acid amides 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-ECD measures.
(2) preparation of standard working solution
Acetone/normal hexane the mixed solvent being 1/1 by 10ng/mL standard intermediate liquid solution volume ratio is diluted to 1ng/mL standard intermediate liquid, and 1 μ g/mL standard solution dilution is made into 10,20,50,100,200,500 μ g/L standard working solution.
(3) gas chromatography-electron capture detector (GC-ECD) measures
Operation steps, chromatogram are consistent with the mensuration of fluorine ether bacterium acid amides in above-mentioned apple sample with Mass Spectrometry Conditions.
Recovery of standard addition and repeatability:
The fluorine ether bacterium acid amides standard solution of 50,100 and 200 μ g/kg, 3 concentration levels is added in the dehydration green pepper of not fluorine-containing ether bacterium acid amides, 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 fluorine ether bacterium acid amides is 93.3% ~ 97.0%, and average relative standard's deviation (RSD) is 4.2% ~ 5.1%, illustrates that the recovery of the inventive method is high, reproducible.
The recovery of table 3 fluorine ether bacterium acid amides and repeatability (n=6)
Detection limit:
The fluorine ether bacterium acid amides standard working solution of variable concentrations is injected GC-ECD, 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 standard solution chromatographic peak and sample handling processes, detecting of fluorine ether bacterium acid amides is limited to 3.16 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. the ECD assay method of fluorine ether bacterium acid amides residual quantity in vegetables and fruit, is characterized in that, said method comprising the steps of:
(1) extract
Take vegetables and fruit sample in tool plug centrifuge tube, add acetonitrile or extract 1min containing the acetonitrile solution homogeneous of 1% acetic acid, centrifugal after adding one in sodium chloride or sodium acetate and anhydrous magnesium sulfate vibration;
(2) purify
Pipette sample extracting solution supernatant in centrifuge tube, add Dispersive solid phase extraction agent, vortex oscillation, centrifugal, get after a certain amount of scavenging solution nitrogen dries up, dissolve constant volume with acetone/normal hexane mixed solvent that volume ratio is 1/1, after crossing film, treat that gas chromatography-electron capture detector (GC-ECD) detects;
(3) preparation of standard working solution
The certain density standard reserving solution of accurate preparation and standard intermediate liquid, be then mixed with the fluorine ether bacterium acid amides 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-ECD 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-ECD to measure, record the chromatographic peak area of fluorine ether bacterium acid amides in sample liquid, substitute into typical curve, obtain fluorine ether bacterium amide content in sample liquid, then the Mass Calculation of sample representated by liquid obtains fluorine ether bacterium acid amides residual quantity in sample per sample.
2. the ECD assay method of fluorine ether bacterium acid amides residual quantity in a kind of vegetables according to claim 1 and fruit, 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. the ECD assay method of fluorine ether bacterium acid amides residual quantity in a kind of vegetables according to claim 1 and fruit, 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. the ECD assay method of fluorine ether bacterium acid amides residual quantity in a kind of vegetables according to claim 1 and fruit, 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. the ECD assay method of fluorine ether bacterium acid amides residual quantity in a kind of vegetables according to claim 1 and fruit, it is characterized in that, in step (4), GC-ECD analysis condition is: chromatographic column: DB-5 capillary chromatographic column, column length 30m, internal diameter 0.32mm, thickness 0.25 μm; Injector temperature 250 DEG C; Carrier gas: high pure nitrogen, post flow is 1.5mL/min; 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 rise to 220 DEG C with the speed of 2 DEG C per minute with the speed of 20 DEG C per minute, 280 DEG C are risen to again with the speed of 20 DEG C per minute, keep 10min, detector temperature is 300 DEG C, and make-up gas flow is 30mL/min.
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